DOI:
10.1039/D5MH00504C
(Review Article)
Mater. Horiz., 2025,
12, 6440-6484
Silicon negative electrodes for lithium-ion batteries: challenges, advances, and future prospects
Received
20th March 2025
, Accepted 16th June 2025
First published on 1st July 2025
Abstract
Due to its remarkably high theoretical capacity, silicon has attracted considerable interest as a negative electrode material for next-generation lithium-ion batteries (LIBs). Nonetheless, its actual application is hindered by numerous problems, including considerable volumetric expansion, unstable solid electrolyte interface (SEI), irreversible capacity loss, and mechanical deterioration. This mini-review offers a systematic examination of the essential concepts of LIBs, succeeded by an in-depth analysis of the primary constraints related to silicon-based negative electrodes. Recent advancements in material design, encompassing nanostructured silicon, silicon–carbon composites, and silicon alloys, are analysed in conjunction with progress in electrolyte engineering intended to address SEI instability. Advancements in binder technology and prelithiation techniques are examined as essential enablers of enhanced cycle stability and coulombic efficiency. We discuss advanced characterisation techniques that provide fundamental insights into the electrochemical and mechanical properties of silicon electrodes. To connect basic research to commercial feasibility, we delineate potential research avenues, including scalable production, complex electrolyte and binder systems, innovative material designs, and sustainability factors. This mini-review evaluates current advancements and guides future approaches for silicon-based negative electrodes in high-performance LIBs.
Wider impact
Silicon-based negative electrodes have emerged as a promising candidate for next-generation lithium-ion batteries (LIBs) due to their exceptionally high theoretical capacity. However, their practical application is hindered by challenges such as drastic volumetric expansion, and mechanical degradation. This review systematically examines recent advancements in material design, including nanostructured silicon, silicon–carbon composites, and silicon alloys, alongside innovations in electrolyte engineering and binder technologies. These developments are of substantial interest to the broader scientific and industrial community, as addressing these challenges is crucial for enabling high-energy-density LIBs with extended cycle life, particularly for electric vehicles and renewable energy storage. The future of this field will likely see a convergence of scalable manufacturing techniques, novel hybrid material architectures, and enhanced characterisation methodologies, facilitating the commercial viability of silicon negative electrodes. By providing a comprehensive analysis of existing limitations and emerging solutions, this review serves as a strategic roadmap for researchers and engineers, guiding the development of next-generation energy storage systems. The insights presented herein will contribute to shaping the future of materials science, fostering advancements in electrochemical energy storage that are critical for achieving sustainable and high-performance battery technologies.
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1. Fundamentals of lithium-ion batteries
Lithium-ion batteries (LIBs) are a kind of secondary (rechargeable) battery in which Li+ ions travel inside the host material.1 The development of LIBs is inextricably linked to intercalation chemistry.2,3 Sony introduced LIBs to the market in 1991.4 By several essential characteristics of the (1) lowest density: 0.53 g cm−3, and (2) least positive electrochemical potential: −3.045 V (versus standard hydrogen electrode), LIBs have the highest energy density in the market.5
1.1 Scheme and components
Fig. 1 illustrates a LIB schematically. There are several critical components: a positive electrode, a separator, a negative electrode, and the current collector. Since the electrochemical potential of the negative electrode is often less positive, the anode is sometimes referred to as the negative electrode.6 During discharge, Li+ ions go from negative electrode to positive electrode, and electrons in the outer circuit maintain the consistent direction. The charging procedure is the reverse of the discharging, in which electricity is imposed. For the subfield of anionic redox, please find the following discussions.7–10
 |
| Fig. 1 Illustration of a LIB. | |
1.2 Electrode reactions
Example electrode reactions are:11 | LiCoO2 positive electrode: LiCoO2 ↔ xLi+ + xe− + Li1−xCoO2 | (1.1) |
| Graphite negative electrode: xe− + 6C + xLi+ ↔ LixC6 | (1.2) |
| Sum: 6C + LiCoO2 ↔ LixC6 + Li1−xCoO2 | (1.3) |
It should be highlighted that the “net reaction” is critical since no electricity can be produced merely by transferring the chemical species through the separator.12
The (theoretical) specific capacity of an electrode (Qtheory) is calculated as follows:13
|  | (1.4) |
where
n: electrons moving in mol (per unit formula),
F: Faraday constant (96
![[thin space (1/6-em)]](https://www.rsc.org/images/entities/char_2009.gif)
485 C mol
−1),
M: the molar mass (g mol
−1) of the reactant.
Example Qtheory calculation with LiCoO2 (assuming all Li+ ions participate):
| Qtheory(LiCoO2) = 96 485 × 1 ÷ (98 × 3.6) = 273.5 mAh g−1 | (1.5) |
An example of graphite with the intercalation compound of LiC
6:
| Qtheory(graphite) = 96 485 × 1 ÷ (72 × 3.6) = 372 mAh g−1 | (1.6) |
1.3 Evaluation metrics
Fig. 2 summarises the critical parameters of LIBs electrodes.14 Alternatively, a spider web chart can be applied to visualise metrics.15 Typically, some metrics are evaluated in the lab, but those metrics are not enough for practical applications.16,17 For example, 80% capacity retention is required in electric vehicles (EVs) after 500 cycles. In other words, it requires a coulombic efficiency (CE) of at least 99.96% of each cycle in a full cell14 (under the assumption that each cycle has the same CE18). An attempt is made to semi-quantitatively predict full-cell capacity retention from half-cell efficiency.19 Critical laboratory parameters are addressed,20–28 and there have been several attempts to standardise the comparison parameters,29–34 such as mixing time of binder solution, calendaring, electrode alignment, etc. However, there seems to be no consensus on the standardisation. Calculations are also applied to study and summarise electrode capacity data.35,36
 |
| Fig. 2 The critical factors affecting LIBs electrodes from the laboratory to the industrial application14 (Creative Commons Attribution 4.0 International License). | |
1.4 Working mechanisms
1.4.1 Intercalation.
The word “intercalation” refers to “the reversible insertion of guest species into a lamellar host structure whilst retaining the host's structural characteristics”.3 It is dissimilar to ‘‘insertion’’ (‘‘in tunnel-like frameworks’’).11 Upon identification, the intercalation chemicals were once called “ternary phases”.37 Goodenough et al. demonstrated the possibility of reversible lithium intercalation in LiCoO2,38 which pioneered a novel category of positive electrode materials, the layered oxides, and has now been extensively commercialised. Li+ ions de-intercalate from the negative electrode and intercalate into the CoO2 planes during discharge.
As battery technology advances, new classes of materials (e.g., spinel structure: LiMn2O439 and olivine structure: LiFePO4,40–46etc.) expand the intercalation context. Channels of Li+ ions diffusion are incorporated: one-dimensional (1D) as LiFePO4, two-dimensional (2D) as LiCoO2, or three-dimensional (3D) as LiMn2O4. Recently, lithium–nickel–manganese–cobalt oxides are rapidly becoming the preferred positive electrode material in vehicle batteries.47 Their success is mainly due to their higher energy density compared with LiFePO4, LiCoO2 or LiMn2O4. It is expected to develop at the fastest rate and will eventually dominate industries such as electric cars and smart grids.
The intercalation mechanism applies to a wide variety of materials. Intercalation negative electrodes are comprised of a variety of carbons,48 TiO2,49 Li4Ti5O12,50,51etc.
The most common intercalation is cation intercalation. However, another type, anion intercalation, sometimes appears in the literature52 and will not be covered here. It is worth noting that the electrolyte, rather than the negative electrode or positive electrode, supplies the ions in anion intercalation. As a result, the solvent, salt type, and salt concentration of the electrolyte all contribute significantly to the performance. The electrolyte must be counted as the active mass.
1.4.2 Alloying (single-phase conversion).
Lithium alloys are often used as negative electrodes because they have a greater capacity than graphite negative electrodes.53 Relevant reviews were conducted.54,55 The general formula of reaction is: | xe− + xLi+ + M → LixM | (1.7) |
in which M could be Si, Ge, Sn, P.
Si, Sn, and P have de-lithiation potentials of 0.45 V, 0.6 V, and 0.9 V, respectively.56
The disadvantages of the alloying mechanism are:57
(1) Huge volume expansion occurs during lithiation: (×4) Si, (×3.7) Ge, (×2.6) Sn, and (×3) P,
(2) Unstable solid electrolyte interface (SEI),
(3) The difficulties in cell design caused by the substantial volume expansion.
It is worth noting that alloying reactions are sometimes classified as conversion reactions due to the exact mechanism in the subsequent step of conversion reactions.58 The word “conversion” is commonly used in the scientific literature for multiphase reaction materials, whilst single-phase conversion materials are called alloying materials.59
1.4.3 Conversion.
The first research paper in this field can be traced back to the millennium.60 The conversion reaction is denoted by the following formula, where transition metal (TM) is in the Li2O matrix:61 | TMaOb + 2bLi+ + 2be− ⇌ bLi2O + aTM | (1.8) |
This sort of reaction has a large capacity.62 The reaction has the benefit of multiple electrons transfer, which is relatively frequent in 3d metals. The downside of conversion reactions is that they produce a large potential hysteresis and a large volume expansion in the material, resulting in inefficient energy conversion.63 This kind of reaction incorporates a large number of compounds, including metal fluoride and sulfide.64 However, there has been no practical application yet, “even with guilt”, if high-impact publications were not considered.65
1.4.4 Displacement.
In 2003, researchers discovered a novel mechanism66 for the reversible reaction of the positive electrode material Cu2.33V4O11 from which copper had been extracted. Several variables (metal ion delocalisation, framework flexibility and copper diffusion) influence the efficiency of this type of reaction. Under this mechanism, materials may develop long or multiple tiny dendrites.67
2. Introduction to silicon negative electrodes and their challenges
2.1 Selection criteria of optimal negative electrodes for LIBs
The following selection criteria might be considered for optimal LIBs negative electrodes:11,68
(1) Intercalation potential is very negative and steady,
(2) Stability of chemical components (solvent/negative electrode/lithium salt) is required,
(3) Specific capacity is relatively high (incorporate Li+ to the maximum),
(4) Structural integrity for a long cycle life,
(5) Good electronic and ionic conductivity for small charge transfer resistance (Rct), good rate capability and slight potential polarisation,
(6) Stable SEI for a high CE (e.g., initial CE requirement for marketed graphite negative electrodes: ≥90%),69
(7) Material manufacturing that is simple and inexpensive for easy industrialisation,
(8) Abundant raw materials and a commitment to environmental protection.
These key points are summarised in Fig. 3.
 |
| Fig. 3 Selection criteria for the optimal negative electrodes for LIBs. | |
It should be observed that graphite is rather extraordinary in that it meets the majority of the requirements.54 Alloying negative electrode researchers have to face the spectacular success of graphite whilst developing novel alloying negative electrodes. Meanwhile, as machine learning advances at a “breakneck” speed,70–75 material selection and application in this approach may have a bright future.
2.2 Overview of silicon negative electrodes in LIBs
Due to their high energy density and long cycle life, LIBs are widely used in various applications, including consumer electronics, electric vehicles, and large-scale energy storage systems.76 The negative electrode material in these batteries plays a critical role in determining overall performance, and traditionally, graphite77 has been the preferred choice because of its excellent electrical conductivity, mechanical stability, and ability to reversibly intercalate Li+ with minimal volume change.78 However, the theoretical capacity of graphite is relatively low at 372 mAh g−1, limiting the energy density of LIBs.79
Researchers have been exploring alternative negative electrode materials with higher capacity and efficiency to meet the growing demand for batteries with higher energy density, longer lifespan, and faster charging capabilities. Silicon has become a prominent contender for next-generation LIBs owing to its remarkably high theoretical capacity, >10 times that of graphite,80 which is due to the ability of silicon to alloy with lithium via lithiation.81 Silicon negative electrode technology is considered as a near-term possibility82–84 rather than a long-term one (e.g., Li–O285). Furthermore, silicon is abundant, environmentally friendly, and inexpensive for scalable and sustainable battery production.86
Due to a high theoretical capacity, the increase in energy density leads to lighter and more compact battery packs, which is particularly advantageous for applications such as electric vehicles and portable electronics, where minimising weight and size is essential.87
2.3 Key challenges
Despite its advantages, the commercialisation of silicon negative electrodes in LIBs faces several significant challenges that must be addressed to achieve reliable, high-performance batteries.
2.3.1 Volume expansion and contraction.
A major issue with silicon as a negative electrode material is its significant volume change during the lithiation and delithiation cycles.88 When fully lithiated, silicon can expand by as much as 300%, creating substantial mechanical stress that causes the silicon particles to break apart.89 This pulverisation disrupts the electrical contact between the active material and the conductive matrix, leading to rapid capacity loss and poor cycle stability.90 Furthermore, the constant expansion and contraction during charge–discharge cycles cause cracks in the silicon particles, exposing fresh surfaces to the electrolyte. This consumes more lithium and accelerates the formation of a thick and unstable SEI.
2.3.2 Solid electrolyte interface formation and instability.
A stable SEI is crucial for the performance and longevity of LIBs.91 The SEI forms on the surface of the negative electrodes during the initial cycles, protecting it and preventing further breakdown of the electrolyte. However, for silicon negative electrodes, the large volume changes during cycling cause the SEI to continuously break and reform, exposing fresh silicon surfaces to the electrolyte.92 This ongoing process leads to further electrolyte decomposition and SEI growth, which depletes the electrolyte and Li+ irreversibly and increases cell impedance. As a result, CE decreases, and capacity fades more rapidly over time.93 This instability of the SEI is a major obstacle in achieving long-term cycling stability for silicon negative electrodes.
2.3.3 Initial irreversible capacity loss.
Silicon negative electrodes suffer from a high initial irreversible capacity loss due to the formation of the SEI during the first lithiation cycle.94 This initial capacity loss can be as high as 10–40%, drastically reducing the overall efficiency and capacity of the battery. In practical full-cell configurations, this necessitates an excess amount of lithium in the cathode to compensate for the loss,95 which adds to the cost and complexity of the battery system.
2.3.4 Mechanical degradation and electrical contact loss.
Mechanical degradation of silicon negative electrodes is closely linked to the volume changes during cycling.96 As silicon expands and contracts, the resulting stress can cause fracture and pulverisation of the silicon particles.97 This mechanical degradation disrupts the electrical pathways within the electrode, leading to a loss of electrical contact between the silicon particles and the conductive additives or current collector.98 The loss of electrical contact significantly reduces the active surface area available for Li+ intercalation, contributing to rapid capacity loss.99 Performance deterioration may result from imperfect contact that develops during manufacture and gets worse with cycling.
2.4 Importance of overcoming these challenges for next-generation energy storage
Confronting these problems is essential for the advancement of next-generation energy storage technologies. Silicon negative electrodes can augment the energy density of LIBs, which is crucial for prolonging the range of electric cars, enhancing the battery longevity of portable gadgets, and optimising the effectiveness of renewable energy storage systems. To actualise this promise, continuous research endeavours concentrate on creating novel material designs, electrolyte compositions, and electrode structures that can manage volume fluctuations, stabilise the SEI, minimise initial capacity degradation, and preserve electrical connectivity throughout cycling.
Furthermore, surmounting these obstacles would allow the extensive commercialisation of silicon negative electrodes, potentially revolutionising the battery business by offering superior energy density, extended cycle life, and reduced prices compared to existing technologies.100 Ongoing materials science and engineering breakthroughs position silicon negative electrodes as a crucial element in next-generation LIBs, enhancing performance and sustainability across many applications.
Key advantages and limitations of silicon negative electrodes
(1) Key advantages:
a. Exceptionally high theoretical specific capacity (∼3579 mAh g−1)
b. Abundant, low-cost, and environmentally benign raw material
c. Potential to increase the energy density of LIBs
(2) Key limitations:
a. Severe volume expansion (∼300%) during lithiation/delithiation
b. Mechanical degradation and electrode pulverisation
c. Unstable and continuously reforming SEI layer
d. High initial irreversible capacity loss
e. Challenges in achieving scalable and cost-effective integration
3. Recent advances in the material design of silicon negative electrodes
Researchers have investigated many advanced material designs to tackle the aforementioned challenges, encompassing nanostructuring methods, composite materials, and innovative structures. These methods seek to augment cycle stability, promote capacity retention, and improve the overall performance of silicon negative electrodes. Several examples are shown in Fig. 4.
 |
| Fig. 4 (a) Schematic representation of the synthesis and the charging/discharging mechanisms of a Si@void@CNF nanostructured electrode designed as a negative electrode in LIBs. Reproduced with permission.101 Copyright 2018 Elsevier. (b) Illustrative Li+ and electron transport pathways representations for pristine and carbon-encapsulated silicon spheres. Reproduced with permission.102 Copyright 2022 Elsevier. (c) Diagram of the Si/CNTs@(S)-C configuration. Reproduced with permission.103 Copyright 2019 Elsevier. (d) Schematics illustrating the hierarchical structural design for Si/po-C@C composite. Reproduced with permission.104 Copyright 2014 Elsevier. (e) Diffusion fluxes of Li+ within the silicon phase of the Gr/μ-Si electrode. Reproduced with permission.105 Copyright 2021 Wiley-VCH GmbH. (f) A novel yolk–shell Si/C architecture. Reproduced with permission.106 Copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA. (g) Development and production of the MP-Si/C composite. Reproduced with permission.107 Copyright 2017 Royal Society of Chemistry. (h) Left: low-magnification SEM image of PH-SiNWs, and right: high-magnification SEM image of PH-SiNWs. Reproduced with permission.108 Copyright 2021 American Chemical Society. (i) Left: SEM side view of the hollow silicon nanospheres, and right: SEM image showcasing hollow silicon nanospheres, meticulously scraped with a sharp razor blade, highlighting the interior voids within the spheres. Reproduced with permission.109 Copyright 2011 American Chemical Society. (j) Schematic illustration of the synthesis process for the proposed Si−C hybrid composite material. Reproduced with permission.110 Copyright 2019 American Chemical Society. | |
3.1 Nanostructured silicon
Nanostructuring silicon into several forms, including nanoparticles, nanowires, and nanosheets, is a highly successful approach for mitigating the mechanical deterioration and volumetric expansion challenges associated with silicon negative electrodes.111 One benefit of nanomaterials is to avoid mechanical failure from substantial volume changes by shrinking the particle size to the nanoscale.112–115 Amorphous spheres with a diameter of up to 870 nm do not fracture during lithiation.116 Nano-silicon with a particle size of roughly 5 nm to 10 nm may present the best charge capacity,117 the critical particle size of ∼150 nm beyond which surface cracking and particle fracture occur during lithiation.118 For nanopillars, the critical diameter is 300 nm. For the thin films, the critical thickness is 100 nm.119 A second benefit is the improved electron transport which results from shorter transport lengths.120 Another advantage is that specially engineered porous silicon negative electrodes could reserve space for massive volume expansion.
3.1.1 Silicon nanoparticles.
Silicon nanoparticles (SiNPs) have been extensively researched because their small size reduces the absolute volume expansion during lithiation, thereby minimising mechanical stress and the risk of fracture.111 Reduced dimensions enhance adhesion, even on uneven surfaces, and nanostructured materials can achieve optimal adhesion strength by size reduction or shape optimisation.121 The increased surface area of SiNPs enhances exposure to the electrolyte, resulting in substantial SEI development and irreversible capacity degradation. Recent studies have concentrated on altering the surface of SiNPs to tackle issues related to their application as negative electrode materials in LIBs. The improvements intend to diminish electrolyte breakdown and enhance SEI stability. Jiang et al. synthesised a covalently linked organic monolayer of ethylene carbonates on silicon nanoparticles, yielding a more stable SEI.122 Li et al. examined the impact of various functional groups attached to silicon nanoparticles, revealing that surface changes substantially affect SEI production and electrochemical performance.123 Qian et al. presented a novel ‘electrolyte-phobic surface’ methodology that restricted electrolyte absorption and enhanced initial CE from ∼60% to 88%.124 This approach also enhanced long-term cycle stability. Yao et al. developed interconnected silicon hollow nanospheres as a durable negative electrode,109 achieving 2725 mAh g−1 initial capacity with only 8% capacity degradation per 100 cycles over 700 cycles. The hollow structure (Fig. 4i) reduces lithium diffusion distances and mitigates volumetric stress, whilst interconnectivity eliminates binders/additives. These investigations underscore the significance of surface chemistry in tackling the issues posed by high surface area SiNPs and present interesting ways for improving their efficacy in LIBs.
3.1.2 Silicon nanowires.
Silicon nanowires (SiNWs) have several benefits owing to their 1D structure, which enables rapid electron transport and offers a resilient framework capable of enduring substantial volume alterations without breaking.125 SiNWs may stretch and contract more easily during cycling, hence minimising mechanical damage and preserving electrical connection.126 SiNWs grown directly on current collectors have shown promise as binder-free and conductive additive-free negative electrodes for LIBs.127 This approach enhances performance by eliminating components that can degrade over time. SiNWs grown on carbon cloth demonstrated high areal capacities and stable long-term cycling,128 whilst those transferred to copper electrodes exhibited high specific capacity and excellent rate performance. Template growth through anodised aluminium oxide nanopores can prevent the formation of parasitic silicon islands, greatly improving cycling stability.129 Chang et al. developed a high-performance negative electrode by integrating phosphorus-hyperdoped silicon nanowires (PH-SiNWs) (Fig. 4h) into a bilayer fabric with carbon nanotubes (CNTs). Through a scalable supercritical fluid–liquid–solid method, PH-SiNWs with P doping achieved ultralow resistivity (4.3 × 10−3 Ω m), enabling stable cyclability of 820 mAh g−1 after 1000 cycles at 2 A g−1, which mitigates volume expansion and enhances Li+ diffusion.108
3.1.3 Silicon nanosheets.
Silicon nanosheets are another type of nanostructured silicon that offers distinct benefits. High surface area and thin structure allow for faster lithium diffusion and minimise stress buildup during lithiation and delithiation.130 Silicon nanosheets can be low-cost precursors used in the production of silicon–graphite nanosheet composites.131,132 Meanwhile, nanosheets can deform elastically to accommodate volumetric changes without cracking, which improves cycle stability133–135 and is enhanced by surface modifications such as protective coatings or the addition of functional groups.136 First-principles calculations reveal that lithium atoms preferentially bind to the silicon nanosheet surface, with binding energies dependent on nanosheet thickness.137 Notably, silicon nanosheets exhibit significantly higher lithium diffusivity compared to bulk silicon. Chemically synthesised porous silicon nanosheets have shown impressive cycling performance, maintaining high capacities over numerous cycles at high rates.138 The porous structure of silicon nanosheets contributes to their structural stability and enhances the amount of active lithium atoms during cycling.130,138
Numerous nano-silicon negative electrodes have been manufactured,139–145 yet concerns continue to exist.146 Whilst nanoscale materials are beneficial, they are not a panacea for batteries since their increased surface area may lower their efficiency and cyclability as well as incur a high production cost.147 Meanwhile, it calls for attention that nano-strategy does not always relate to superior electrode performances.65 Besides, certain nanomaterials (e.g., carbon nanotubes) are being substituted within the European Union due to carcinogenicity and reproductive toxicity.148 In summary, whilst nanostructuring provides an effective strategy to mitigate the volume change and mechanical degradation of silicon negative electrodes, each type of nanostructure would demonstrate distinct long-term stability characteristics under practical cycling conditions. Silicon nanoparticles offer high initial capacity but suffer from high surface area-induced SEI growth and low initial CE unless protected by coatings or embedded in a composite matrix.149–151 Silicon nanowires, due to their direct attachment to current collectors and flexible 1D morphology, exhibit exceptional cycling stability and mechanical resilience.152,153 However, their low tap density and integration challenges limit commercial translation.154 Silicon nanosheets, though promising for their short Li+ diffusion paths and elastic compliance, face hurdles in aggregation and scalability.155 Future efforts may focus on hybrid designs156 which combine the merits of each nanostructure whilst addressing their intrinsic weaknesses in terms of mechanical integrity, interfacial stability, and industrial feasibility.
3.2 Silicon–carbon composites
A carbon matrix could be considered to prevent silicon from contacting the electrolyte whilst cushioning volume increases. In addition, carbon matrix has low electrolyte reactivity, good electrical conductivity and high CE. Therefore, research on silicon/carbon materials was conducted.157–163 Dahn and co-workers first showed pioneering work in 1995.164,165 Such materials could be engineered so that silicon grains are contained inside spaces of the carbon matrix, thus creating particles with zero volume expansion. Studies have shown that tailoring the silicon–carbon interface with atomic oxygen can improve cycle life and capacity retention.166 Embedding silicon nanoparticles in micro-carbon spheres allows for self-rearrangement of silicon pieces, resulting in excellent cyclability and high rate capability.167In situ growth of graphitic carbon to encapsulate silicon nanoparticles has demonstrated improved electronic conductivity and suppression of volume expansion.102 Besides, creating hierarchical carbon/mesoporous silicon composite sponges with interconnected carbon–silicon–CNT skeletons has shown promise in facilitating Li+ diffusion and electron transport whilst buffering volume expansion.168
3.2.1 Carbon-coated silicon.
Carbon coating on silicon nanoparticles, with multiple benefits including improved conductivity, protection against excessive SEI formation,169 and mechanical support to accommodate volume changes of silicon during cycling,170–172 is a widely adopted strategy to enhance the performance of silicon negative electrodes in LIBs. Meanwhile, the carbon coating facilitates more uniform electrode processing, leading to better electronic connections within the electrode.173 Various methods have been employed to create carbon coatings, such as the graphitisation of π–π stacking precursors, pyrolysis of polymer precursors, and chemical vapour deposition (CVD).171,173 Zhao et al. developed a self-catalytic method to encapsulate silicon nanoparticles with highly graphitic carbon, enhancing electronic conductivity and suppressing volume expansion (Fig. 4b).102 The optimised sample exhibited a high specific capacity of 2126 mAh g−1 at 0.1 A g−1, excellent rate capability (750 mAh g−1 at 5 A g−1), and stable cycling over 450 cycles. Zhang et al. designed a 3D porous Si/CNTs composite with voids and a carbon shell to enhance performance, demonstrating that the double-layered carbon coating stabilised the SEI and improved cycling stability (Fig. 4c).103 The optimised Si/CNTs@(S)-C exhibited a high reversible capacity of 943 mAh g−1 after 1000 cycles at C/5. Zhang et al. developed a hierarchical core–shell structured Si/C composite microsphere via spray drying and carbonisation, integrating a porous carbon framework (Si/po-C core) and a compact PAN-derived carbon shell,104 which mitigated Si volume expansion through porous carbon buffering whilst suppressing electrolyte penetration with the dense shell (Fig. 4d), achieving stable cyclability (>900 mAh g−1 after 30 cycles). Kim et al. developed a graphite–silicon diffusion-dependent electrode for all-solid-state batteries,105 leveraging nanometre-scale silicon to minimise Li+ diffusion pathways and enhance interparticle contact with superior rate capability (93.8% capacity retention at 0.5C) and long-term cyclability (72.7% after 200 cycles at a current density of 1.77 mA cm−2) through optimised ion transport and structural integrity (Fig. 4e). Shen et al. developed a pomegranate-structured Si/C composite via a facile one-step hydrothermal method,107 embedding Si nanoparticles (50–100 nm) into a mesoporous carbon matrix with 3–4 nm pores (Fig. 4g), which synergised structural confinement, enhanced conductivity via interconnected carbon frameworks, and facilitated Li+ diffusion, delivering exceptional cyclability (581 mAh g−1 at 0.2 A g−1 after 100 cycles) and high-rate capability (421 mAh g−1 at 1 A g−1). Kwon et al. developed a scalable, low-cost Si–C hybrid composite negative electrode110 using corn starch-derived carbon spheres encapsulating Si nanoparticles (∼28 nm) with dual carbon layers (inner amorphous carbon and outer graphitic shell) (Fig. 4j). This hierarchical structure achieved 1800 mAh g−1 initial capacity (2.7 mAh cm−2 areal capacity) with 80% retention over 500 cycles, and robust cyclability in full cells with NCM622/NCA80 cathodes. The dual carbon matrix mitigates silicon volume expansion and enhances electrical conductivity (∼0.857 S cm−1). Silicon carbide and resorcinol-formaldehyde carbon coatings enhance capacity retention and cycle longevity by preserving structural integrity and shielding silicon from electrolyte interactions.174 Graphite-like amorphous carbon coatings with low incident energy deposition can create porous structures with Li+ conducting channels and restore their structure after deformation.175 The compactness and ordering of carbon coatings influence the lithiation/delithiation process, with ordered compact coatings promoting two-phase transformations and disordered porous coatings favouring solid solution reactions.176 Different silicon–carbon composite structures, such as core–shell, hollow, porous, and embedded, can effectively accommodate volume expansion and enhance performance.163 Overall, the quality and thickness of the carbon coating play a pivotal role in determining the electrochemical performance of silicon–carbon composites.170,172 Thin, uniform, and conformal carbon layers—typically in the range of 5–10 nm—have been found optimal for simultaneously enhancing electrical conductivity, suppressing continuous SEI formation, and accommodating moderate volume changes without diluting the capacity contribution of silicon. Highly graphitic carbon coatings improve electron transport but may sacrifice interfacial elasticity, whereas amorphous carbon provides better mechanical adaptability at the cost of lower conductivity.177–179 Dual-layer strategies that combine an inner elastic layer with an outer graphitised shell have shown particular promise.180 From a manufacturing standpoint, practical control over coating morphology can be achieved through scalable techniques such as pyrolysis of polymer precursors, CVD, and spray-drying with carbon-rich binders.181,182 Continued progress in tuning carbon coating parameters—alongside in situ characterisation of interfacial evolution—will be key to developing silicon–carbon composites suitable for commercial implementation.183
3.2.2 Silicon–graphene composites.
Graphene was first discovered in a laboratory.184 Graphene is a sp2 carbon sheet structured in a honeycomb pattern.185 Note that the critical feature is the thickness. If the number of carbon layers is increased, several definitions will be created according to the ISO standard.186 Graphene has been widely investigated as a negative electrode material in LIBs187–197 and potassium-ion batteries.198 Aside from being directly applied as negative electrodes, graphene has been recently adopted as a matrix for different negative electrodes.194,199 For example, graphene is an ideal candidate for creating silicon–graphene composites.200 These composites form a conductive matrix around silicon particles, supporting their structure and buffering volume changes during cycling.201,202 The flexible nature of graphene allows it to accommodate the expansion of silicon without losing electrical contact, enhancing the cycling stability and rate capability of the negative electrode.203,204
Recent research has explored diverse manufacturing techniques to enhance silicon–graphene composites for negative electrodes in LIBs.205 Green synthesis methods, such as ball milling and spray drying, have been developed to create stable core–shell structures of silicon wrapped in graphene, improving cycle stability.206,207 Self-assembly, spray-drying, and freeze-drying processes have been established as scalable techniques for producing high-performance Si/G composites.162,208 A pomegranate-like Si/rGO composite, synthesised through electrostatic self-assembly and spray-drying, demonstrated enhanced capacity and cycle stability.209
3.3 Yolk–shell and core–shell structures
Yolk–shell and core–shell structures have emerged as promising solutions to address the challenges of volume expansion and mechanical degradation in silicon negative electrodes for LIBs. These designs feature a protective outer layer that accommodates size changes of silicon, maintaining structural integrity and electrical connectivity.210–212
3.3.1 Yolk–shell structures.
Yolk–shell structures feature a silicon core surrounded by a shell, with an internal void which allows the silicon to expand during lithiation without damaging the integrity of the shell.213 The design reduces the mechanical stress on the silicon core and keeps it shielded from direct contact with the electrolyte, which in turn stabilises the SEI and enhances cycle stability.211,214,215 A range of materials, such as silicon106,211,213 and iron oxide,216 have been explored for the core, whilst the shell can be made from carbon106,211 or silica,213 with capacity retention rates of 74% and 95%, respectively. Fine-tuning the void space is key to optimising volume expansion and energy density.216 Incorporating conductive materials like carbon nanotubes can further boost the overall conductivity and performance.106 Choi et al. developed 3D yolk–shell Si@void@CNF nanostructured anodes for LIBs, demonstrating that an optimised void portion effectively alleviates volumetric expansion, achieving a high reversible discharge capacity of 304.9 mAh g−1 at 200 mA g−1 after 500 cycles with superior rate performance (Fig. 4a).101 Zhang et al. proposed a yolk–shell structured silicon negative electrode (YS-Si/C) featuring a rigid C/SiO2 double-shell for volume confinement and a conductive ‘highway’ of Fe2O3-embedded CNTs networks, which achieved superior conductivity, and exceptional cyclability, delivering 95% capacity retention after 450 cycles at 0.5 A g−1 and stable performance in full cells with LiFePO4 or Li2V2O5 cathodes106 with high tap density (Fig. 4f).
3.3.2 Core–shell structures.
Core–shell structures featuring a silicon core surrounded by a protective outer layer have emerged as a promising design for negative electrodes in LIBs. These structures offer mechanical support and improved electrical conductivity, enhancing the overall performance of negative electrodes.210,217 The shell is a physical barrier, limiting direct contact between silicon and the electrolyte, lowering SEI development and capacity degradation.218 Core–shell architectures have demonstrated the capacity to preserve the structural integrity of the negative electrode and enhance cycling stability by mitigating mechanical deterioration throughout successive lithiation and delithiation cycles.219 Different shell materials, including carbon, silica, and titanium oxide, have been examined to tackle the issues related to the volumetric expansion of silicon.210,220,221 Double core–shell systems, e.g., Si@C@SiO2, exhibit exceptional cycle stability by integrating the advantages of several shell materials.220 Hollow core–shell architectures have been engineered to accommodate volumetric variations and mitigate silicon fragmentation.221 Amorphous TiO2 shells have enhanced elastic buffering capabilities relative to crystalline TiO2, resulting in higher cycle stability and safety. These core–shell configurations substantially reduce capacity degradation, enhance electronic conductivity, and stabilise the SEI, tackling critical issues in silicon-based negative electrodes for LIBs.210
3.4 Porous silicon
Porous silicon materials are designed to accommodate substantial volume changes by including internal voids and channels that alleviate expansion and contraction during cycling.222 These permeable structures diminish mechanical stress and assist in preserving structural integrity and electrical connectivity. Porous silicon facilitates improved electrolyte penetration and accelerated Li+ diffusion, hence boosting the overall electrochemical performance of the negative electrode.223 Diverse techniques have produced porous silicon structures with regulated pore dimensions and distribution. Dealloying of silicon–metal alloys, combined with chemical etching, has demonstrated the production of three-dimensional networked porous silicon with improved lithium storage capabilities.224,225 Template-assisted and non-template methods have synthesised porous silicon, each presenting distinct structural characteristics.223 The porosity of these materials mitigates volume fluctuations during charging and discharging, enhancing ion transport and hence improving capacity retention and rate performance.225 The design of pores and walls, surface area, and particle shape of porous electrodes substantially affect their electrochemical characteristics, such as utilisation, specific capacities, and structural stability during cycling.226
3.5 Silicon alloys
Silicon alloys, including silicon–tin (Si–Sn), silicon–germanium (Si–Ge), and silicon–aluminium (Si–Al), have been engineered to enhance cycle stability and mitigate the volumetric expansion of silicon negative electrodes.227,228 Alloying silicon with other elements can reduce the total volume change during lithiation and delithiation, hence improving the mechanical characteristics of the negative electrode material.229 These alloys can establish more stable phases during cycling, therefore diminishing mechanical deterioration and enhancing the long-term durability of the negative electrode.230 Research has focused on optimising the composition and microstructure of silicon alloys to achieve a balance between high capacity and cycling stability. Table 1 presents a comparison of material designs and performances of silicon negative electrodes in LIBs.
Table 1 Comparison of material designs and performances of silicon negative electrodes in LIBs
Material design |
Key characteristics |
Advantages |
Challenges |
Example references |
Capacity |
Cycling |
Silicon nanoparticles |
Small, spherical silicon particles with sizes typically in the range of 1–100 nm |
High capacity; good lithium-ion diffusion |
Volume expansion during cycling, leading to mechanical degradation and capacity loss |
231–234
|
∼3500 mAh g−1 |
∼2200 mAh g−1 after 250 cycles at 0.511 A g−1 |
|
Silicon nanowires |
1D structures with high aspect ratios, typically ranging from tens of nanometres to micrometres in length |
High conductivity, flexibility, and high capacity; tolerance to volume changes |
May suffer from low packing density and poor electrode conductivity at higher currents |
80, 235 and 236
|
∼4100 mAh g−1 |
∼3300 mAh g−1 after 100 cycles at 1C |
|
Silicon nanosheets |
Thin, flat layers of silicon, often produced by top-down fabrication methods like exfoliation or chemical vapour deposition |
Large surface area for lithium-ion storage; good structural stability; efficient ion transport |
Limited scalability and challenges with mass production; may have issues maintaining stability at high charge/discharge rates |
237–240
|
∼870 mAh g−1 |
∼720 mAh g−1 after 1800 cycles at 0.1 A g−1 |
|
Carbon-coated silicon |
Silicon core coated with a thin layer of carbon (e.g., graphene, CNTs) to improve electrical conductivity and structural integrity |
Improved mechanical properties and conductivity; reduced expansion and stress during cycling |
The carbon coating must be thin and uniform to avoid compromising the capacity and the balance of coating thickness and performance |
172, 241–246
|
∼2400 mAh g−1 |
∼1120 mAh g−1 after 500 cycles at 2 A g−1 |
|
Silicon-graphene composites |
Combination of silicon and graphene to leverage the high conductivity and mechanical properties of graphene |
Improved conductivity, high structural stability, and enhanced performance; synergistic effect in improving cycling stability |
Balancing the right amount of graphene to silicon ratio is crucial, and the material processing can be complex |
247 and 248
|
∼2850 mAh g−1 |
∼800 mAh g−1 after 120 cycles at 1.8 A g−1 |
|
Yolk–shell structures |
Core–shell nanostructures where silicon forms the core and a soft shell (e.g., carbon) is used to mitigate stress during cycling |
Exceptional strain tolerance, high capacity, and excellent cycling stability due to core–shell structure |
Complex fabrication process and potential scalability issues. |
249–254
|
∼3060 mAh g−1 |
∼1720 mAh g−1 after 200 cycles at 0.42 A g−1 |
|
Porous silicon |
Silicon with a highly porous structure, created by techniques like electrochemical etching |
High surface area, enhanced ion diffusion, and reduced volume expansion |
Reduced material density and mechanical fragility can limit performance |
255–258
|
∼2500 mAh g−1 |
∼1200 mAh g−1 after 370 cycles at 2.6 A g−1 |
|
Silicon alloys |
Alloying silicon with elements to improve its stability and reduce volume expansion |
Good cycling stability, reduced volume change, and improved electrical conductivity |
Alloying elements must be carefully chosen to prevent adverse reactions with lithium and maintain capacity |
259–261
|
∼3350 mAh g−1 |
∼1270 mAh g−1 after 50 cycles at 0.05C |
4. Electrolyte engineering for silicon negative electrodes
Electrolyte engineering is essential for improving the performance of silicon negative electrodes in LIBs by stabilising the SEI and minimising side reactions.262 Silicon negative electrodes present distinct electrolyte issues because of substantial volume fluctuations during cycling, resulting in ongoing SEI disruption and regeneration, excessive electrolyte depletion, and heightened cell impedance.263 Researchers have concentrated on creating enhanced electrolytes and additives that can establish stable SEI layers, inhibit excessive side reactions, and improve overall cell performance.264,265
4.1 Conventional electrolyte systems and their limitations
Standard electrolytes employed in LIBs generally comprise a lithium salt, such as lithium hexafluorophosphate (LiPF6), dissolved in a blend of organic solvents, including ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC).266 These electrolytes provide good ionic conductivity and a stable SEI for graphite negative electrodes, but they are not ideal for silicon negative electrodes.267 The significant volume changes of silicon during lithiation and delithiation cause the SEI to crack and reform repeatedly, consuming electrolytes and forming a thick, unstable SEI layer that increases cell impedance and reduces cycling stability.268
Moreover, conventional electrolytes can undergo decomposition reactions at the high surface area of silicon, especially when exposed to newly formed surfaces during cycling.269 This leads to the continuous formation of fresh SEI and further electrolyte degradation, which results in a loss of active lithium and reduced battery life. Researchers are formulating novel electrolytes and additives to stabilise the SEI and minimise parasitic reactions to overcome these constraints.
4.2 Development of fluorinated electrolytes
Fluorinated electrolyte additives have been explored to enhance the stability of the SEI on silicon negative electrodes. Fluorinated additives, including fluoroethylene carbonate (FEC)270,271 and difluoroethylene carbonate (DFEC),272 are recognised for their decomposition at the negative electrode surface, resulting in the formation of a stable lithium fluoride (LiF)-rich SEI. This layer exhibits reduced susceptibility to cracking and enhances mechanical strength, hence diminishing SEI deterioration and augmenting cycle stability.
FEC is extensively utilised as an electrolyte additive for silicon negative electrodes because it enhances the formation of a more resilient SEI that can accommodate the volumetric variations of silicon whilst maintaining electrical connectivity.273,274 Research indicates that FEC-containing electrolytes markedly enhance the cycling stability of silicon negative electrodes by creating a more homogeneous and stable SEI, which diminishes capacity fading and improves CE.274,275 Meanwhile, FEC seems to increase the capacity retention of half-cells,276 possibly by forming a less porous and more stable SEI,276 though the exact mechanism by which FEC improves capacity retention remains unclear.277 However, using FEC to improve cycling may worsen the battery via gas generation.278 An electrolyte with 10 wt% to 15 wt% FEC seems to provide the optimum of low cost, low impedance, and excellent capacity retention.279–281 In the case of silicon/carbon composite electrodes, the involvement of FEC may lead to a capacity drop.282
DFEC, a derivative of FEC, has been investigated for its capacity to generate stable SEI on silicon negative electrodes. DFEC demonstrates superior SEI stability and enhanced Li+ transport relative to FEC, resulting in increased cycle performance and rate capability.283
Whilst fluorinated electrolytes and additives have shown promising results in half-cell configurations, translating these benefits to full cells introduces several critical challenges.284–287 The absence of an infinite lithium reservoir in full cells makes the initial CE of the negative electrode a decisive factor for overall performance.287–289 Additives such as FEC and DFEC must promote stable SEI formation whilst minimising lithium consumption during the first cycle.290–292 The compatibility of such additives with high-voltage cathodes (e.g., NCM, NCA) is nontrivial—fluoride species generated during additive decomposition may corrode cathode surfaces or induce gas generation under high-voltage cycling.293–295 High additive concentrations can increase electrolyte viscosity and impair ionic conductivity, which becomes more pronounced under commercial circumstances.296–298 Recent full-cell studies have demonstrated that moderate additive loadings (e.g., 5–10 wt%) can achieve improved cycling performance when paired with electrode prelithiation, tailored cathode coatings, or balanced formulation strategies.299 Thus, full-cell validation, including realistic areal capacities and cathode loadings, remains essential for establishing the practical viability of fluorinated additives and tailoring their use across different electrode chemistries.
4.3 SEI-forming additives
SEI-forming compounds facilitate the formation of a stable SEI on silicon negative electrodes300 by preferential breakdown during the initial cycles, forming a protective layer which impedes further electrolyte decomposition and reduces parasitic reactions. Vinylene carbonate (VC) is a commonly employed SEI-forming additive, noted for its ability to generate a thin, flexible SEI which accommodates the volumetric changes of silicon.301 The impedance of the SEI layer generated in the VC-containing electrolyte remained almost constant throughout cycling, owing to the impermeability of the SEI to the electrolyte.302 It was discovered that although VC produced more resilient coatings on silicon alloys than FEC, these films were very resistive, favouring low-rate performance over high-rate performance.303 Note that the bulk of these improvements on electrolyte additives was made in half-cells with the lithium metal as the negative electrode, and may not be transferable to full cells where the capacity fading would be less remarkable304 with parameters (e.g., tap density) optimised.305
Recent studies have explored the use of lithium bis(oxalate)borate (LiBOB) and lithium difluoro(oxalato)borate (LiDFOB) as additives to enhance the performance of silicon negative electrodes in LIBs.306,307 When combined with trans-difluoroethylene carbonate (DFEC), LiDFOB promotes the development of a LiF-rich SEI with a polymer-interlaced outer layer, enhancing ionic conductivity and mechanical stability.283 Direct incorporation of LiDFOB into the silicon electrode has been shown to effectively stabilise the SEI, reduce volume expansion, and improve long-term cycling performance. The SEI formed with these additives contains various components, including lithium ethylene dicarbonate, LiF, oxalate-containing species, and borates, which contribute to the overall stability and performance of the electrode–electrolyte interface.307
4.4 Hybrid and solid-state electrolytes
4.4.1 Hybrid electrolytes.
Hybrid electrolytes combine the strengths of both solid and liquid electrolytes to enhance the performance of silicon negative electrodes.308 Such electrolytes can help form stable SEI and accommodate the volume changes in silicon negative electrodes, leading to improved cycle stability and better rate performance (e.g., combined with ionic liquids309).310,311 Nanoporous hybrid electrolytes, created by infusing liquid electrolytes into ceramic or polymer membranes with pore sizes below 200–450 nm, have demonstrated an exceptional ability to stabilise lithium electrodeposition.312
4.4.2 Solid-state electrolytes.
Solid-state electrolytes (SSEs) offer a promising solution to the challenges faced by silicon negative electrodes by creating a rigid matrix that helps prevent dendrite growth and accommodates the volume changes during cycling.313 Several efforts have combined silicon negative electrodes with solid electrolytes.314–316 A combination of inorganic/organic solid electrolytes can be quite promising.317–331 Garnet-based solid electrolytes, such as Ta-substituted Li7La3Zr2O12, have shown promise in improving the electrode–electrolyte interface, enabling stable cycling of silicon negative electrodes.332 Sulfide solid electrolytes have demonstrated the ability to passivate microsilicon negative electrodes, eliminating continuous interfacial growth and irreversible lithium losses.314,333,334 Various electrolyte design strategies have been investigated to mitigate thermal runaway in silicon-based batteries, including thermally stable SEI, non-flammable electrolytes, and solid-state electrolytes.335 High ionic conductivity and chemical stability contribute to the development of high-energy-density batteries with improved cycle stability and safety.336
Despite their inherent safety and mechanical stability advantages, solid-state and hybrid electrolytes face serious interfacial challenges when paired with silicon-based anodes.337,338 The large volume change of silicon during lithiation and delithiation cycles leads to repeated disruption of the solid–solid interface, resulting in mechanical delamination, contact loss, and rapid impedance growth.339,340 Moreover, chemical incompatibilities between silicon and certain solid electrolytes (e.g., sulfide SSEs) can lead to undesirable interfacial reactions, forming resistive interphases such as lithium silicates or sulfides. These interphases impede Li+ transport and degrade electrochemical performance.341–343 Poor physical contact at the interface also limits ionic conductivity, particularly in composite electrodes where continuous ion-conductive pathways are challenging to establish.344 To address these issues, several strategies have emerged:345–347 incorporating interfacial buffer layers (e.g., Li3PO4, LiNbO3), surface coating of silicon particles using ALD or sol–gel techniques, and engineering composite negative electrodes with flexible, mixed ionic–electronic conductive (MIEC) binders. Pressure-assisted interface stabilisation348,349 and the use of polymer–ceramic hybrid electrolytes350,351 have also shown promise in maintaining interfacial integrity during prolonged cycling. These approaches will be vital to realising high-performance, mechanically robust silicon-based solid-state batteries. An overview of electrolyte additives and their effects on the performance of silicon negative electrodes is summarised in Table 2.
Table 2 Overview of electrolyte additives and their effects on the performance of silicon negative electrodes
Additive |
Effect on performance |
Key benefits and applications |
Ref. |
Fluoroethylene carbonate (FEC) |
Improves cycling stability and capacity retention by enhancing the SEI |
Widely used in enhancing SEI stability, improving high-rate performance, and reducing side reactions |
352–355
|
Difluoroethylene carbonate (DFEC) |
Enhances the formation of a stable SEI and improves battery life |
Improves the cycling stability, helping to manage the expansion and contraction during cycling |
356
|
Vinylene carbonate (VC) |
Forms a stable SEI layer, reducing the capacity fade |
Widely used in batteries for its ability to prevent electrolyte decomposition and improve performance over cycles |
279, 302 and 357
|
Lithium bis(oxalato)borate (LiBOB) |
Stabilises the SEI layer, enhancing cycling performance and thermal stability |
Improves thermal stability and capacity retention, making it effective for high-performance battery applications |
358 and 359
|
Lithium difluoro(oxalato)borate (LiDFOB) |
Enhances the stability of the SEI, improving performance at high rates and low temperatures |
Excellent for fast-charging and low-temperature applications; improves cycling efficiency |
360–362
|
Tris(trimethylsilyl) phosphite (TTSP) |
Reduces the formation of undesired SEI layers, promoting better cycling stability. |
Helps improve the overall cycling performance in high-power applications |
363–366
|
Tris(trimethylsilyl) borate (TTSB) |
Stabilises the SEI, enhancing high-rate performance and long-term cycling stability |
Improves performance by reducing impedance growth during cycling, ensuring better battery efficiency and longevity |
367–369
|
5. Innovations in binder technologies
Binders are crucial elements in LIBs, significantly contributing to the structural integrity and electrochemical efficacy of silicon negative electrodes. Traditional binders used for graphite negative electrodes are not well-suited for silicon negative electrodes due to the huge volume expansion of silicon during cycling. Developing improved binder materials is essential for overcoming the mechanical and chemical problems associated with silicon negative electrodes.
Binders tend to be a secondary consideration in battery books.370–373 The function of the binder is to bind active mass together and to the current collector at all times.374
The selection criteria for the binder are
(1) Stability to heat (during the material drying process),
(2) Stability to solvents (in the batteries), and
(3) Electrochemical stability during the oxidative and reductive processes in electrodes.
The binder is classified as either an aqueous or organic system. Several representatives are:
(1) Fluorine-containing polymers:
a. aqueous system: polytetrafluoroethylene (PTFE), or
b. organic system: polyvinylidene fluoride or polyvinylidene difluoride (PVDF).
PTFE was reported to have less stability than PVDF, and side reactions appear due to surfactants applied with PTFE. PVDF requires the toxic and costly organic solvent N-methyl pyrrolidinone (NMP) to produce the slurry. Solvay speciality developed a water-soluble PVDF binder to alleviate safety and ecological considerations.375
(2) Styrene–butadiene rubber (SBR) and carboxymethylcellulose (CMC): SBR has been widely acknowledged as an ideal choice to buffer volume changes with improved cycling.376 The mechanical property of SBR is positively related to the ratio of styrene monomer in the composition.377 In batteries, SBR was employed in nearly 70% of negative electrodes (with CMC as a thickener).378 In comparison to PVDF, SBR and CMC have better battery characteristics. Moreover, as water-based binders, they are environmentally friendly, whilst NMP has been identified as a reproductive toxicant (Californian Environmental Protection Agency in 2001 and the European Commission in 2003).374 The application examples of SBR and CMC can be obtained from the manual.379
It was later found that CMC-only electrodes outperformed CMC/SBR electrodes in terms of cycle performance.380 The reason could be that the hydrogen bonds within CMC and nano-silicon enable self-healing during volume expansion and contraction.381 Moreover, it was discovered that sodium alginate provided superior coverage than CMC binder since (1) the carboxylic groups are more concentrated and consistently distributed; the groups may form ester-like bonds with the hydroxyl groups that develop on metal surfaces,382 and (2) the SEI is stabilised.383 A sound review of bio-derived polymers could be traced.384
(3) Minimal information was disclosed in polyacrylates, polyamide, polyester, and ethylene–propylene–diene rubber.385 A comparison study between polyacrylic acid and CMC binders on silicon negative electrodes indicated that CMC (with citric acid) was more efficient as a binder at a low weight percentage. In contrast, polyacrylic acid was more efficient at a high weight percentage, which might be rooted in its molecular structure.386
Several representative binders are shown in Fig. 5. Gendensuren et al.387 developed a dual-crosslinked alginate-polyacrylamide binder for Si/graphite anodes, achieving 840 mAh g−1 capacity retention after 100 cycles (Fig. 5a). The dual crosslinking (ionic via Ca2+ and covalent via MBAA) enhances mechanical resilience, and accelerates Li+ diffusion (Li+ diffusion coefficient: 2.33 × 10−7 cm2 s−1), suppressing volumetric expansion to near-theoretical limits (97% vs. 310% for silicon). In situ dilatometry confirms reduced irreversible SEI growth and electrode pulverisation, enabling stable cyclability and high-rate capability (422 mAh g−1 at 10C). The binder design synergises adhesion, ion transport, and stress accommodation for next-generation high-energy anodes. Liu et al. proposed a 3D interpenetrating network as the binder by synergistically combining stiff poly(furfuryl alcohol) and soft polyvinyl alcohol polymers,388 which achieved >10 mAh cm−2 areal capacity in Si anodes with 73.6% capacity retention after 300 cycles at 300 mA g−1 (Fig. 5b). The strategy applies to other high-capacity negative electrodes. Cai et al. developed a dual-crosslinked fluorinated binder network combining ester bonds and dynamic hydrogen bonds,390 enabling 1557 mAh g−1 capacity retention after 200 cycles at 4 A g−1 in silicon negative electrodes. The synergistic dual network of fluorinated copolymer and sodium alginate (Fig. 5d), provides mechanical resilience through covalent crosslinking and stress dissipation via reversible hydrogen bonding. The water-based, cost-effective binder offers a scalable solution for practical Si/SiO–graphite anodes in advanced LIBs. Li et al. proposed a hard/soft-modulated trifunctional network binder (Fig. 5e) composed of partially lithiated polyacrylic acid (P-LiPAA) and Nafion (P-LiNF) via hydrogen bonding.390 This design synergises a rigid P-LiPAA framework and a flexible P-LiNF buffer, whilst enabling Li+ transport through lithiated groups. The binder achieves 93.18% initial CE and stable cycling over 500 cycles at 0.2C in Si negative electrodes, even at an ultrahigh mass loading of 28.88 mg cm−2 with an areal capacity of 49.59 mAh cm−2. Kim et al. developed a mucin-inspired amphiphilic DNA-alginate binder392 with a hydrophobic protein backbone and hydrophilic oligosaccharide branches (Fig. 5f), forming a 3D fractal network, which enhances electrode integrity, enabling Si and Si–graphite anodes to retain 80.1% capacity at 0.5C after 160 cycles and 93.5% retention at 0.6C over 120 cycles.
 |
| Fig. 5 (a) Synthesis of Alg-g-PAAm and c-Alg-g-PAAm. Reproduced with permission.387 Copyright 2018 Elsevier. (b) Schematic representation of the silicon anode utilising both hard and soft composite binders. Reproduced with permission.388 Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA. (c) Illustration of the chemical structure of the SHP-PEG binder. Reproduced with permission.389 Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA. (d) Schematic representations of silicon-based binder configurations for a linear binder, a highly cross-linked binder, and the dual cross-linked binder during the processes of lithiation and delithiation. Reproduced with permission.390 Copyright 2019 American Chemical Society. (e) Schematic representation of the functional mechanism of the N-P-LiNP binder within the silicon electrode. Reproduced with permission.391 Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA. (f) Illustration depicting the proposed reDNA/ALG hybrid binder at the interfaces of silicon and carbon within electrodes. Reproduced with permission.392 Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA. (g) Schematic representation of the freestanding SiSHP electrode showcasing a uniform distribution of SiMPs and SHP. Reproduced with permission.393 Copyright 2018 Royal Society of Chemistry. | |
5.1 Conductive polymers
Binders are a key component in the electrode formulation, holding the active material particles together and ensuring adhesion to the current collector.394 For silicon negative electrodes, binders must accommodate substantial volume changes, provide mechanical flexibility, and maintain electrical conductivity.395
Conductive polymer binders396–398 of high mechanical flexibility and electrical conductivity, e.g., polyaniline (PANI),399,400 have been developed to improve the performance of silicon negative electrodes, offering mechanical reinforcement and enhanced electrical conductivity. Various PANI structures, including star-like, cross-linked, and linear forms, have been investigated, with star-like PANI demonstrating superior performance due to its 3D-conjugated conductive network.399 PANI doped with phytic acid has shown promise as both a binder and conductive additive, improving the cycling stability and rate capability of silicon nanoparticles.400 Silicon/PANI nanocomposites have exhibited higher capacity than graphite negative electrodes and improved cycling stability compared to nano-silicon without PANI.401 Besides, a PANI–polyacrylic acid (PAA) composite binder has demonstrated stable cycling and high silicon material utilisation by acid–base interaction with PAA.402,403 PPy–Si core–shell nanofibres demonstrated high capacity (>2800 mAh g−1) and excellent cycling stability (91% retention after 100 cycles).404
5.2 Self-healing binders
Self-healing binders which repair themselves after damage, have emerged as a promising solution to address the mechanical degradation of silicon negative electrodes in LIBs. The binders utilise dynamic chemical bonds, such as host–guest interactions405 and hydrogen bonding,406 to accommodate the volume changes of silicon during cycling. Moreover, incorporating ionic conductivity into self-healing binders improves rate performance and Li-ion transport.389,405
Zhang et al.407 developed a self-healing CMC–CPAM composite binder for improved cycling stability, retaining 78% of its capacity after 350 cycles. In another study, Zhang et al.408 introduced a supramolecular binder featuring triple hydrogen bonding to maintain good capacity over 110 cycles. Lopes et al.409 investigated binders of excellent cycling stability with a relaxation interval of 0.1 s, retaining 80% of their capacity after over 175 cycles. Chen et al.410 created a self-healing poly(ether-thioureas) binder with outstanding structural stability and electrochemical performance, holding 85.6% of its capacity after 250 cycles, even at higher current rates. Zhang et al.407 developed a composite binder of carboxymethyl cellulose and cationic polyacrylamides, which exhibits self-healing properties via reversible electrostatic interactions, achieving a capacity of 1906.4 mAh g−1 after 100 cycles. Jang et al.411 developed a cross-linked poly(acrylic acid) binder modified with dynamic carbon radicals, enhancing adhesion and mechanical capabilities, resulting in a capacity of 1774.45 mAh g−1 after 500 cycles. Munaoka et al. developed an ionically conductive self-healing binder by integrating polyethene glycol (PEG) into a hydrogen-bonded supramolecular network (Fig. 5c).389 This dual-functional binder achieves 80% capacity retention after 150 cycles at 0.5C in Si microparticle anodes, with rate performance up to 900 mAh g−1 at 2C. The PEG moieties enhance Li+ transport, whilst dynamic hydrogen bonds enable autonomous crack healing, preserving electrical connectivity during Si volume changes. This approach balances mechanical resilience and ionic kinetics, offering a scalable solution for high-performance, low-cost Si anodes in advanced LIBs. Kim et al. developed a freestanding silicon microparticle and self-healing polymer composite electrode with a hydrogen-bonded matrix (Fig. 5g), enabling free volume expansion and robust electrical contact recovery,393 which achieved 91.8% capacity retention at 0.1C after 100 cycles (1050 mAh g−1) and 95% recovery after cutting/reassembly.
5.3 Ionic conductive binders
Ionic conductive binders integrate ionic conductive groups into their polymer framework, offering mechanical support and improved Li+ transport inside the electrode. Seng et al.412 formulated a polymer binder exhibiting 14-fold more Li+ diffusivity than traditional binders, resulting in substantial capacity retention after 500 cycles. Cai et al.413 presented a slidable, ionic conductive binder which enhanced initial CE and long-term cycling stability. Salem et al.414 revealed that ionically functionalised poly(thiophene) binders surpassed merely ionic and conductive binders, attaining superior capacities for silicon negative electrodes. Park et al.397 developed side-chain conducting polymeric binders that preserved electrode integrity and enhanced rate performance via self-assembled nanostructures.
5.4 Synergistic interactions of binders and electrolytes with silicon negative electrodes
The interplay between binders and electrolytes is essential for enhancing the efficacy of silicon negative electrodes. Efficient binder-electrolyte systems can collaboratively boost SEI stability and augment ionic conductivity. Nam et al.415 formulated a cohesive binder-electrolyte system utilising p-phenylenediamine, thereby improving ionic conductivity and mechanical characteristics. Zhang et al.416 discovered that the interaction between Li2CO3 and LiF inside the SEI enhanced Li+ transport and decreased electron leakage, increasing cycle efficiency. Jin et al.417 developed a zwitterionic binder which modulated the solvation environment on silicon-based negative electrodes, leading to a thin, homogeneous, and durable SEI.
5.5 Novel binder-electrolyte combinations and their effects on SEI stability and negative electrode performance
Research is being conducted on novel binder-electrolyte combinations to enhance the performance of silicon negative electrodes. These combinations produce a synergistic effect that improves SEI stability, mechanical durability, and electrochemical performance. Recent studies have concentrated on creating multifunctional hybrid binders to enhance the efficacy of silicon-based negative electrodes in LIBs. These binders utilise covalent and non-covalent interactions to improve mechanical and electrochemical capabilities. Zhang et al.407 introduced a self-healing network binder of carboxymethyl cellulose and cationic polyacrylamides, exhibiting remarkable cycle stability. Hwang et al.418 created a thiourea polymer network binder, including covalent cross-linking and hydrogen bonding, which improves structural integrity and interfacial stability. Ko et al.419 presented a catechol-functionalised binder which reduced microstructural alterations and enhanced cycling performance. Huet et al.420 introduced coordinatively cross-linked Zn(II)–poly(carboxylate) binders which improved the cohesion, adhesion, and mechanical characteristics of electrode coatings. These new binders jointly solve the difficulties of silicon negative electrodes, such as volume expansion and capacity fading, by offering stronger adhesion, greater structural integrity, and higher ionic conductivity, eventually leading to superior electrochemical performance and cycle life.
The continued innovation in binder (Table 3) and electrolyte technologies is expected to play a critical role in enabling the widespread commercialisation of silicon-based LIBs.
Table 3 Binders for silicon negative electrodes in LIBs
Name |
Loading (mg cm−2) |
Binder ratio (wt%) |
Retention rate (%) |
Expansion rate (%) |
Ref. |
PEO-PEDOT:PSS/PEI |
∼1 |
20 |
83% after 500 cycles at 1 A g−1 |
105 |
412
|
PAHT |
∼6 |
10 |
89% after 100 cycles at 0.1 A g−1 |
106 |
421
|
AD-PA |
∼2 |
10 |
77% after 500 cycles at 0.3 A g−1 |
106 |
422
|
SHPET |
∼1.2 |
20 |
85.6% after 250 cycles at 4.2 A g−1 |
108 |
410
|
ACC/PAA |
∼0.97 |
10 |
75% after 100 cycles at 0.6 A g−1 |
112 |
423
|
MXENE |
∼0.9 |
30 |
69% after 70 cycles at 1.5 A g−1 |
120 |
424
|
TUPN10 |
— |
20 |
73.3% after 200 cycles at 1 A g−1 |
122 |
418
|
6. Prelithiation strategies for silicon negative electrodes
Prelithiation techniques are essential in advancing silicon negative electrodes to mitigate the considerable early irreversible capacity loss occurring during the initial cycles of battery operation.425 Prelithiation of the active material refers to the lithiation of the silicon or silicon-based material itself before electrode fabrication. Prelithiation of the electrode refers to lithiation conducted after electrode assembly where the active layer is already integrated with binder and conductive agents. Multiple prelithiation techniques have been established, including electrochemical prelithiation, which can reduce initial irreversible capacity losses by up to 51%. Prelithiation methods may be classified according to the steps of battery assembly, including active material manufacturing, slurry mixing, electrode pretreatment, and battery manufacture.426 Although these solutions demonstrate potential, obstacles persist for extensive commercial implementation.427 Choosing suitable prelithiation reagents and strategies is essential for improving the electrochemical performance of complete cells.428 Several examples are shown in Fig. 6.
 |
| Fig. 6 (a) Electrochemical analyses of pre-lithiated Si/Gr electrodes based on the degree of pre-lithiation. Left: the open circuit potential versus Li|Li+ of the working electrode was recorded in Si/Gr‖Li metal cells following pre-lithiation with varying amounts of PLMP (25%, 50%, and 75%) and a 24-hour rest period in a dry state; and right: investigation of the delithiation behaviour of Si/Gr electrodes following a 24-hour rest period in a dry state, along with an additional 48-hour rest with electrolyte, during the initial discharge in cyclic voltammetry measurements. Reproduced with permission.429 Copyright 2021 The Authors, Advanced Energy Materials published by Wiley-VCH GmbH. (b) The lithiation and delithiation process of prelithiated Si/SiOx involves using a Li–arene complex beforehand, which addresses volume expansion and active lithium loss before the assembly of the cell. Reproduced with permission.430 Copyright 2020 Wiley-VCH Verlag GmbH & Co. KGaA. (c) Left: CV curves of the electrolytic cell were obtained using the Cu-wire electrode as the working electrode and the Si electrode as the counter electrode, with a scan rate of 1 mV s−1 and potentials ranging from −0.1 to 0.07 V versus the Ag/AgCl reference (−3.17 to 3.34 V vs. Li/Li+), cycling three times at various lithiation states of the Si electrode. The third cycle was evaluated utilising the fully lithiated silicon counter electrode; and right: galvanostatic profiles for the prelithiation of the Si electrode and the corrosion of the Cu wires utilising the electrolytic cell at a discharge current density of 1 AgSi−1 (or a Cu corrosion current density of ≈53 μA cmCu−2). The initial discharge curve of the silicon electrode, obtained from a lithium/silicon half cell using a 1 M LiPF6 in EC/DEC (3 : 7 v/v) electrolyte at a discharge current density of 1 AgSi−1, is presented for comparison with the prelithiation curve. Reproduced with permission.431 Copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA. (d) L-Gr/SiOx anodes in half-cells before (black) and following (red) prelithiation. Reproduced with permission.432 Copyright 2021 American Chemical Society. (e) Left: electrochemically pre-lithiated electrodes at a current density of 100 mA g−1 for 5 hours, and right: electrochemically prelithiated electrodes at a current density of 2000 mA g−1 for 15 minutes. Reproduced with permission.433 Copyright 2021 The Authors, Batteries & Supercaps published by Wiley-VCH GmbH. (f) Schematic representation of the pre-lithiation process on a SiO electrode. Reproduced with permission.434 Copyright 2021 American Chemical Society. (g) Left: the pristine and prelithiated SiNWs underwent galvanostatic cycling between 0.01 and 1.0 V, commencing with the charging phase (Li insertion), and right: voltage profiles for the first, second, and tenth cycles of 20-minute prelithiated silicon nanowires. Reproduced with permission.435 Copyright 2011 American Chemical Society. (h) Left: SiOx electrode featuring RBL-regulated prelithiation, and on the right: the cross section of the SiOx electrode with RBL-regulated prelithiation. Reproduced with permission.436 Copyright 2019 American Chemical Society. | |
6.1 Overview of prelithiation techniques
Prelithiation involves introducing lithium to the negative electrode before the first charge–discharge cycle, compensating for the lithium consumed during SEI formation and the initial lithiation.437 This process can be achieved using different chemical, electrochemical, or mechanical methods, each with its own set of benefits and challenges.427 Choosing an appropriate prelithiation technique for LIBs involves considering several key factors. These include the required lithium load, compatibility with existing production processes, safety considerations, and cost-effectiveness.438,439
6.2 Chemical prelithiation
Direct chemical prelithiation of silicon negative electrodes offers a promising solution to the issue of active lithium loss in LIBs, with precise control and even distribution of lithium. Methods include the use of molecularly designed complexes for solution-based prelithiation,430 contact prelithiation with passivated lithium metal powder,429 and thermal evaporation of lithium metal.440 The methods can adjust the prelithiation level according to specific battery designs, improving energy density and overall performance. A new lithium–metal-free prelithiation method,431 with a lithium-containing aqueous solution, has also been developed, which constructs full LIBs with lithium-deficient electrodes. Jang et al. developed a molecularly engineered lithium–arene complex (Li–DMBP) with a tailored redox potential (<0.2 V vs. Li+/Li) to achieve homogeneous chemical prelithiation of Si/SiO2 negative electrodes (Fig. 6b).430 They controlled lithium doping by modulating reaction temperature/time and delivered a full-cell energy density of 504 Wh kg−1. The above methods bring advantages such as uniform reactions, simplicity, and scalability, addressing mass production challenges and paving the way for high-performance LIBs with greater energy density and longer cycle life. Choi et al. introduced a reductive Li−aromatic hydrocarbon (arene) complex (LAC) solution to achieve stable chemical prelithiation of graphite–SiOx negative electrodes (Fig. 6d).432 By regulated solvation power, they attained a near-ideal energy density of 506 Wh kg−1 energy density (98.6% of the theoretical limit) and 87.3% capacity retention after 250 cycles.
6.3 Electrochemical prelithiation
Electrochemical prelithiation has emerged as a promising strategy to enhance the performance of silicon-based negative electrodes in LIBs,425 greatly improving initial CE, energy density, and cycle life by reducing irreversible capacity losses, indicating reductions of 51.03% for electrodes containing multi-walled carbon nanotubes and 39.55% for those based on carbon black.
6.3.1 Galvanostatic lithiation.
In galvanostatic lithiation, a constant current is applied between the silicon negative electrode and a lithium metal counter electrode, driving Li+ into the silicon structure. The galvanostatic lithiation of silicon electrodes in LIBs involves complex mechanisms. During initial lithiation, a phase boundary separates crystalline silicon from the amorphous lithiated phase depending on crystal orientation.441 The process prompts a crystalline-to-amorphous phase transition, where lithium diffuses faster in amorphous silicon than crystalline silicon.442 Lithium insertion breaks silicon rings and chains, creating ephemeral structures that transform into Si–Si dumbbells and isolated silicon atoms.443 The formation of distinct amorphous lithiated silicide structures is associated with the electrochemical profiles observed after the first discharge. During subsequent cycles, lithiation of amorphous silicon forms small clusters. Understanding these mechanisms at the atomic level is crucial for improving silicon-based LIBs.444 Zhou et al. developed a Li–metal-free electrolytic cell for prelithiating Si-based negative electrodes using a Cu corrosion mechanism in aqueous electrolytes (Fig. 6c).431 By controlling reaction conditions, they achieved a high initial CE (∼99%) and assembled MnOx/Si and S/Si full cells with specific energies of 349 Wh kg−1 and 732 Wh kg−1, respectively. The method eliminates Li metal handling risks, and enhances safety. Overhoff et al. compared electrochemical and direct-contact Li–metal foil prelithiation of Si/C negative electrodes,433 demonstrating both methods enhance first-cycle CE from ∼69% to >80% via SEI formation and lithium reservoirs. Whilst electrochemical prelithiation (100–2000 mA g−1) offered superior control and scalability (Fig. 6e), both techniques achieved comparable long-term cyclability improvements in NCM111‖Si/C full-cells, highlighting their potential for mitigating active lithium loss in high-energy LIBs.
It should be mentioned that a persuasive method of maintaining cycle performance whilst minimising volume change in a silicon negative electrode is restricting the cut-off potential and avoiding the crystalline silicon.445–451 The method is consistent with the fundamental electrochemistry of silicon,81 where a behaviour change occurs at a potential of 50 mV, above which Li+ can be inserted and removed from a-LixSi in a strictly single-phase region. If the potential falls below 50 mV, however, the Li15Si4 phase forms and a two-phase Li15Si4–LixSi region will appear during subsequent delithiation, which is detrimental to cycling452 due to the instability and reactivity towards the electrolyte.453 As a result, silicon alloy design typically incorporates strategies for mitigating the effects of volume expansion as well as suppressing the formation of Li15Si4. On the other hand, experimental data on the diffusivity of lithium in amorphous silicon are inconsistent throughout a four-order-of-magnitude range, from 10−14 to 10−10 cm2 s−1 (typical value: 10−12 cm2 s−1).454
6.3.2 Potentiostatic lithiation.
Potentiostatic lithiation entails maintaining the silicon negative electrode at a designated potential to a lithium reference electrode, facilitating the intercalation of Li+ into the silicon until equilibrium is achieved. This method has been employed to investigate the kinetics and mechanisms of lithiation in amorphous silicon thin films.455 The process features a distinct boundary between the lithiated and unlithiated phases, where lithium diffusion within the lithiated phase serves as the rate-limiting factor.
6.4 Mechanical prelithiation
Mechanical prelithiation techniques combine silicon with lithium metal or lithium-rich substances to facilitate lithiation via mechanical forces, including ball milling456 or compression.
6.4.1 Ball milling.
Ball milling involves a mechanical procedure where silicon and lithium metal powders are combined and exposed to high-energy milling, resulting in the continuous fracturing and welding of the particles. This process facilitates lithiation by establishing close contact between silicon and lithium, forming lithiated silicon compounds. The method results in nanostructured materials which exhibit enhanced electrochemical properties compared to non-milled powders.457 The procedure entails the combination of silicon and carbon materials, leading to composite negative electrodes which exhibit enhanced capacity and cycling stability.456 The wet ball milling process, utilising organic solvents, effectively prevents particle agglomeration and improves particle distribution, resulting in enhanced electrochemical performance.458 Ball-milled silicon-based negative electrodes exhibit impressive capacity retention, even under elevated current densities, positioning them as strong candidates for high-power applications. Although bottom-up synthesis techniques can tackle the volume expansion challenges associated with silicon, ball milling continues to be preferred in industrial environments because of its straightforwardness and economical nature.459 Nonetheless, the impact of ball milling parameters on product quality necessitates additional exploration to enhance large-scale production efficiency.
6.4.2 Compression lithiation.
Compression lithiation entails the application of pressure and temperature to silicon and lithium metal to facilitate their interaction. This approach facilitates lithiation via direct contact and mechanical force, usually in ultra-thin foils or powder, under regulated pressure and temperature conditions,460,461 resulting in a prelithiated silicon structure. The process facilitates lithiation via mechanical force, resulting in a prelithiated silicon structure that offsets active lithium loss during battery operation. Research indicates that optimising factors like prelithiation duration, pressure, and temperature can greatly enhance the initial CE and cycle longevity of silicon-dominant negative electrodes.462 Mechanistic insights demonstrate that lithiation occurs even in the absence of electrolytes, leading to SEI formation upon introducing an electrolyte.429 This prelithiation method shows promise in improving the performance of silicon-based negative electrodes, achieving cycle life increases of up to 150% compared to non-prelithiated negative electrodes.461
6.5 Lithium powder mixing
Mixing lithium powder is a simple, scalable prelithiation method where lithium metal powder is combined with silicon particles before the construction of negative electrodes.463 This process allows the lithium powder to react with the silicon during the early charge cycles, forming lithiated silicon compounds which compensate for the initial lithium loss. Integrating stabilised lithium metal powder into pre-fabricated negative electrodes minimises early capacity losses and enhances energy density.463,464 Bärmann et al. elucidated the pre-lithiation mechanism of Si/Gr electrodes using passivated lithium metal powder (PLMP), demonstrating dry-state lithiation driven by direct Li–metal contact, forming LiC6 (graphite) and c-Li15Si4 phases.429 Electrolyte addition triggers SEI formation and de-lithiation of graphite, whilst c-LiSi remains stable, which highlights the relation between pre-lithiation extent and SEI-related Li losses, guiding optimised PLMP application for Si-based anodes (Fig. 6a). Huang et al. developed a simple and scalable prelithiation strategy for SiO negative electrodes using stabilised lithium metal powder (SLMP) embedded in a styrene–butadiene rubber (SBR)/toluene suspension (SST) (Fig. 6f).434 By tuning the SST volume (0–50 μL) and activation pressure (10–30 MPa), they achieved adjustable initial CE from 60% to 120%, with optimal performance at 30 μL SST and 20 MPa pressure.
Lithium powder as a prelithiation method is scalable, compatible with existing production processes, and offers precise control over the amount of lithium added, making it adaptable to specific application needs. Compared to other prelithiation techniques, lithium powder stands out for its safety, cost-efficiency, and minimal impact on the overall mass and volume of the cell.315 Other methods, such as ex situ electrochemical prelithiation in stirred-tank reactors, are also being explored.465,466
On the other hand, lithium foil may be easier to operate. Liu et al. pioneered a fast prelithiation method for SiNWs using lithium foil via a self-discharge mechanism.435 By optimising prelithiation time (20 min) and pressure, they achieved ∼50% lithium loading (∼2000 mAh g−1) whilst maintaining SiNW nanostructure integrity. The method enabled stable cyclability (75% capacity retention after 10 cycles) (Fig. 6g) and demonstrated full-cell feasibility with a sulfur cathode, achieving 80% capacity retention after 10 cycles. Meng et al. developed a controllable prelithiation strategy for SiOx negative electrodes using a resistance buffer layer (RBL) to regulate Li+/electron transfer (Fig. 6h).436 The RBL-enabled homogeneous lithiation improved initial CE from 79% to 89% in half-cells and ∼69% to 87% in full cells (NCM622‖SiOx). Notably, the lithiated SiO anode maintained 77% capacity retention after 200 cycles at 0.5C, demonstrating enhanced cyclability and practical feasibility for high-energy LIBs.
6.6 Thermal lithiation
Thermal lithiation is a promising pre-lithiation method for improving the performance of LIBs. This process involves heating silicon negative electrodes in the presence of lithium sources, such as lithium foil or lithium-containing gases, to promote lithiation through solid-state diffusion. The method provides additional benefits, offering precise control over the lithiation process to ensure uniform lithium deposition on silicon surfaces440 for various silicon nanostructures, such as nanotubes and nanowires, which show promise as high-capacity negative electrodes.444 Moreover, exposure to lithium vapour at high temperatures creates amorphous silicon and lithium oxide without forming lithium silicides.467
One approach to thermal lithiation is the thermal evaporation of lithium metal, introduced by Adhitama et al.440 This method allows for precise control over the pre-lithiation level and ensures uniform lithium distribution across the silicon surface, which helps form a stable SEI and reduces mechanical fractures caused by volume changes. Adhitama et al. also revisited the ‘dry-state’ and ‘wet-state’ pre-lithiation methods, examining how the inclusion of an electrolyte affects the lithiation process. Their findings showed that this pre-lithiation method improves capacity retention and reduces lithium loss in silicon negative electrodes.
Further studies by Housel et al.468 employed isothermal microcalorimetry to investigate parasitic processes during silicon lithiation. They discovered that solid-state amorphisation notably impacts the entropic heat flow, providing valuable insights for optimising silicon-based negative electrodes for better performance of LIBs.
7. Advanced characterisation techniques for silicon negative electrodes
Advanced characterisation techniques are crucial for understanding the complex processes in silicon-based negative electrodes for LIBs. These methods provide insights into structural changes, SEI formation, and electrode degradation mechanisms.469 Multi-modal approaches, combining techniques like XPS, AES, EDS, and STEM, offer a comprehensive view of SEI composition and structure in silicon–graphite composite negative electrodes.470 Studies have revealed the dynamic nature of electrode porosity, showing how initial micrometric pores are gradually filled with SEI products, leading to capacity fading.471In situ and operando techniques, including cryogenic electron microscopy, have enabled atomistic visualisation of SEI, whilst theoretical simulations complement experimental findings by elucidating thermodynamic and kinetic properties.472
Characterisation methods for battery negative electrodes can be divided into ex situ and in situ approaches, each offering unique advantages. Ex situ techniques provide detailed information on electrode materials under specific conditions but may not fully reflect real-time reactions.473In situ methods allow for the observation of active materials during charge/discharge processes, capturing short-lived intermediates and structural evolutions.473,474 Combining both approaches enables a comprehensive understanding of the behaviour and performance optimisation of silicon negative electrodes.475
7.1
In situ transmission electron microscopy
In situ transmission electron microscopy (TEM)476 is a powerful technique for directly observing the structural and morphological changes in silicon negative electrodes at the atomic level during lithiation and delithiation. It enables real-time monitoring of silicon materials,477 such as nanoparticles, nanowires, or thin films, as they undergo mechanical stress, phase transitions, and fractures. This capability provides valuable insights into the dynamic behaviour of silicon-based negative electrodes during cycling. Several examples are shown in Fig. 7.
 |
| Fig. 7 (a) Left: TEM images of d-SiO, and right: d-SiO/G/C. Reproduced with permission.478 Copyright 2017 Elsevier. (b) Left: HRTEM images of Si/G/PDA-C, and right: Si/G. Reproduced with permission.479 Copyright 2016 Elsevier. (c) Left: ex situ TEM images of 5 nm sized Si particles (red lines indicate n-Si crystallites), and right: 10 nm sized particles (red lines indicate n-Si particles). Reproduced with permission.117 Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA. (d) TEM images of mpSi@Void@mpC at different magnifications. Reproduced with permission.480 Copyright 2014 Royal Society of Chemistry. (e) Left: hollow Si/SiO2 nanospheres, and right: TEM images of Si/SiOx-DSHSs. Reproduced with permission.481 Copyright 2018 Royal Society of Chemistry. (f) Left: TEM images of porous Si nanowires etched with 0.02 M AgNO3 and right: HRTEM image of a nanowire. Reproduced with permission.482 Copyright 2012 American Chemical Society. | |
7.1.1 Observing volume expansion and fracture mechanics.
Silicon experiences a substantial volume increase of 300–400% during lithiation, which leads to mechanical degradation and capacity loss.483 TEM allows researchers to directly observe this expansion and the formation and progression of fractures. Studies show that the mechanical interactions between silicon nanostructures can help resist fractures by reducing tensile stress.484 The design of silicon negative electrodes at the micron scale, such as hollow or anisometric structures, can also improve fracture resistance and alleviate strain.485 Pan et al. fabricated a micro-sized SiO-based composite anode (d-SiO/G/C) via a disproportionation reaction and pitch pyrolysis,478 during which TEM highlights how heat treatment and carbon encapsulation optimise SiO structure (Fig. 7a). Zhou et al. developed a Si/G/PDA-C composite with superior cyclability, rate capability, and SEI stability compared to bare Si/G,479 in which high-resolution TEM images showed crystalline lattice fringes for both silicon (0.31 nm) and graphite, alongside an amorphous carbon layer likely derived from PDA-C (Fig. 7b). Ru et al. developed a yolk–shell structure,480 mesoporosity and void space, which were validated by TEM (Fig. 7d). Yang et al. fabricated a double-shelled hollow superstructure.481 TEM provided critical insights into the unique double-shelled hollow structure, structural integrity, and compositional uniformity of the composite (Fig. 7e), which are pivotal for its exceptional lithium-storage performance. Ge et al. developed a porous doped silicon nanowires synthesised by direct etching of boron-doped silicon wafers.482 The TEM analysis provided critical insights into the unique porous structure and crystalline properties of the boron-doped silicon nanowires (Fig. 7f), which underpin their exceptional electrochemical performance and structural stability.
7.1.2 Phase transformations and amorphisation.
In situ TEM has been instrumental in shedding light on the phase transitions and amorphisation processes in silicon during battery cycling.486 Studies have shown that as silicon undergoes lithiation, its crystalline and amorphous forms transform into an amorphous LixSi phase, which can eventually crystallise into Li15Si4 through a natural phase transition. Interestingly, when silicon nanoparticles are encapsulated with graphene, an unexpected shift occurs from an isotropic to an anisotropic structure after initial lithiation. The change is linked to the uniform distribution of localised voltage within the material.487 Research on the cyclic indentation of crystalline silicon reveals that, as the material undergoes pressure, it gradually shifts toward the high-pressure Si-III and Si-XII phases, a transformation which triggers a distinct ‘pop-out’ phenomenon.488 Kim et al. identified 10 nm as the optimal size, balancing high initial capacity (4210 mAh g−1) with superior cyclability (Fig. 7c).117 Smaller particles (5 nm) suffered from higher irreversible capacity loss due to increased surface area, whilst larger particles (20 nm) showed lower efficiency and faster degradation.
7.2
In situ and operando X-ray diffraction and X-ray absorption spectroscopy
X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) provide valuable insights into how the crystal structure evolves and phase transitions unfold.
7.2.1
In situ X-ray diffraction.
In situ XRD provides a powerful way to track the crystallographic changes in silicon negative electrodes as they cycle. It can reveal the formation of different LixSi phases and monitor transitions between crystalline and amorphous states.489–491 XRD data has shown that silicon shifts to an amorphous state after the first lithiation, with a phase coexistence range of about 3350 ± 200 mAh g−1.492 Notably, at higher lithiation voltages, the metastable Li15Si4 phase emerges, but this can be minimised by carefully controlling the potential at around 70 mV, which can enhance cycle stability and overall performance.489
7.2.2
Operando X-ray absorption spectroscopy.
Operando X-ray absorption spectroscopy (XAS), including techniques like X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), is useful for understanding the local structure and electrical properties of electrode materials in real time.493 Researchers have used operando XAS to investigate redox reactions, changes in cathode materials, and the formation and evolution of the SEI on silicon negative electrodes.494 Techniques like synchrotron X-ray imaging and neutron reflectometry are often used alongside XAS to examine the microstructural shifts and measure the volume expansion of silicon electrodes during lithiation and delithiation.495,496
7.3 Atomic force microscopy and scanning probe microscopy
Atomic force microscopy (AFM) and scanning probe microscopy (SPM) are powerful tools for the topography and mechanical properties of the electrode surface such as roughness, morphology, and the formation of the SEI, helping us understand how the surface interacts with the electrolyte during cycling.497–499 By mapping surface changes at a very fine scale, AFM and SPM can reveal important details about how the silicon reacts over time and how its structure evolves, shedding light on factors that affect battery performance.
7.3.1 Topographical mapping and SEI analysis.
Atomic force microscopy (AFM) is particularly effective for investigating the nanoscale characteristics of the SEI and understanding how its development influences the electrochemical behaviour of silicon negative electrodes. AFM is also highly effective in monitoring the evolution of silicon electrodes in LIBs over time, offering detailed observations of surface feature changes, SEI formation, and electrode degradation. In situ and operando AFM studies have revealed how particle size, electrode structure, and SEI thickness change during cycling.500 These studies show that the early stages of SEI formation can be stabilised before lithium insertion occurs, with the formation rates varying depending on surface properties and cycling conditions.94
AFM has been used to explore how artificial SEI coatings, such as LiF, can help prevent electrolyte breakdown and extend electrode lifespan.501 When combined with cyclic voltammetry, in situ AFM studies have provided valuable insights into how different electrolyte solutions impact SEI formation and fracture in silicon thin-film electrodes, highlighting the critical role stable SEI plays in improving cycling stability and performance.502
7.3.2 Electrochemical strain microscopy.
Electrochemical strain microscopy (ESM) is a scanning probe technique that quantifies localised electrochemical strains resulting from ionic flows and reactions within solid materials.503 An alternating current voltage is applied to the probe tip, which focuses the electric field in a localised area, leading to interfacial electrochemical processes.504 ESM has been employed to explore Li+ mobility and concentration within battery materials.505,506 This method enables the investigation of Li+ concentration, diffusivity, and energy dissipation linked to electromigration with nanometre-level precision. Interpreting ESM data presents challenges from multiple factors influencing the measured response, such as electrostatic interactions, and charge injection.505 Given these challenges, ESM offers insights into nanoscale electrochemistry and ionic phenomena within solid-state materials.503
7.4 Raman spectroscopy
Raman spectroscopy is a non-invasive method that reveals insights into the vibrational characteristics of silicon and various other materials. This facilitates the examination of the structural and chemical alterations in silicon negative electrodes throughout the cycling process.
7.4.1 Phase identification and amorphisation.
Raman spectroscopy can identify various phases of silicon and can detect amorphisation during the lithiation process. The lithiation process in silicon negative electrodes for LIBs has been investigated using Raman spectroscopy and X-ray diffraction techniques. These techniques can identify various phases of silicon and track amorphisation throughout the lithiation process.507,508In situ Raman spectroscopy has uncovered novel signals, enabling the distinction between morphological changes and interphase development. Observing ‘crystalline core–amorphous shell’ particle formation and the evolution of internal strain throughout lithiation/delithiation cycles has been documented. Raman spectroscopy demonstrated a notable decrease in signal intensity during lithiation, followed by recovery at specific potentials.509 The influence of dopants on silicon lithiation has been studied, showing that boron-doped surfaces enhance lithium insertion at higher voltages yet demonstrate lower insertion levels than phosphorus-doped and undoped surfaces.510
7.4.2 SEI composition and stability.
Raman spectroscopy, particularly surface-enhanced Raman spectroscopy (SERS), is a powerful tool for investigating the composition and stability of the SEI on silicon negative electrodes in LIBs. It allows for detailed identification of SEI components, such as organophosphate derivatives and alkyl carboxylates like lithium propionate.511,512
In situ Raman spectroscopy further enhances this capability by enabling real-time monitoring of structural changes, electrode degradation, and SEI formation throughout charge and discharge cycles.513 This technique has revealed that the SEI composition can vary depending on the silicon surface termination. For instance, breakdown products like diethyl carbonate514 can lead to the formation of silicon–ethoxy intermediates, observable through Raman spectroscopy.
7.5 Fourier-transform infrared spectroscopy
Fourier-transform infrared spectroscopy (FTIR) is an essential tool for studying the SEI on silicon negative electrodes.515 It identifies both organic and inorganic compounds within the SEI, shedding light on the chemical interactions between the silicon negative electrode and the electrolyte.
7.5.1 SEI composition and formation mechanisms.
FTIR spectroscopy is a valuable tool for studying the SEI on silicon negative electrodes in LIBs. In situ FTIR studies have demonstrated that SEI formation occurs during both lithiation and delithiation, with lithium alkyl carbonates produced from the reduction of ethylene carbonate and dimethyl carbonate.516 This technique can also identify various functional groups, such as carboxylates and oxalates, shedding light on the reduction processes of electrolyte components like LiBOB.517
In situ ATR–FTIR has revealed that SEI formation is influenced by the surface coating on silicon negative electrodes, which affects the breakdown products of electrolyte additives like FEC.518 Furthermore, nano-FTIR has been employed to examine the structure and composition of SEI, highlighting the accumulation of PF6− and its decomposition products within the organic phase of the SEI.519
7.5.2 Electrolyte decomposition products.
FTIR spectroscopy is a crucial tool for studying the formation and evolution of the SEI on silicon negative electrodes in LIBs. Research has shown that the SEI composition changes drastically during cycling, with lithium ethylene dicarbonate (LiEDC) and LiPF6 breakdown products appearing during lithiation and disappearing during delithiation.520 This dynamic behaviour, often referred to as the ‘breathing’ effect, contributes to the instability of the silicon negative electrode interface. In situ FTIR studies have revealed that ethylene carbonate is rapidly reduced to LiEDC on lithiated silicon surfaces.521 Whilst SEI formation begins during lithiation, most SEI material forms during delithiation.516 The findings highlight the complex nature of SEI development and emphasise the critical role that electrolyte composition plays in influencing battery performance.
7.6 Nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy is a valuable tool for investigating the local chemical environment and atomic-level interactions in silicon negative electrodes and their materials.443,522 By providing detailed insights into the bonding and arrangement of atoms, NMR helps uncover the complexities of how silicon interacts with other components in the battery, giving us a deeper understanding of its behaviour during cycling.
7.6.1 Solid-state NMR for lithium environments.
Solid-state NMR spectroscopy is a powerful tool for studying lithium environments in silicon negative electrodes in LIBs. It enables tracking structural changes during lithiation and delithiation, providing valuable insights into the evolution of silicon throughout cycling.443,523 NMR is particularly effective for identifying distinct lithiated silicide structures and monitoring the breakdown of silicon clusters during these processes.
In situ and operando NMR techniques allow real-time observation of metastable LixSi phases and SEI formation,522,524 during which lithium concentration in LixSi remains relatively stable over time, despite overall charging changes.523 However, NMR also highlights unintended interactions between lithium silicide and the electrolyte, which can lead to self-discharge and potential capacity loss.
7.6.2 SEI characterisation and decomposition pathways.
NMR spectroscopy is a valuable tool for investigating the SEI and electrolyte degradation in silicon negative electrodes, uncovering ion solvation structures, the byproducts of electrolyte breakdown, and the chemical makeup of the SEI.525 For example, voltage-dependent growth of the SEI on silicon electrodes has been observed through NMR techniques, including hydrogen (1H), lithium (7Li), and fluorine (19F) isotopes. The observations correlate with irreversible capacity loss,526 shedding light on the complex processes that occur during cycling and their impact on battery performance.524,527
7.7 Mechanical and thermal characterisation techniques
Characterisation techniques for mechanical and thermal properties are crucial for comprehending the mechanical attributes and thermal stability of silicon negative electrodes. These play a vital role in guaranteeing safe and dependable battery performance.
7.7.1 Nanoindentation and scratch testing.
Nanoindentation and scratch testing serve as methods to evaluate the mechanical properties of silicon negative electrodes, including hardness, elastic modulus, and adhesion strength. Applying these methods has facilitated the investigation of the SEI developed on silicon electrodes, uncovering values for Young's modulus of 0.5–10 MPa.528
Nanoindentation has been applied to study silicon composite electrodes in various conditions, showing that both Young's modulus and hardness increase with higher lithium concentration but decrease as the electrodes cycle.529,530In situ nanoindentation during the electrochemical lithiation of silicon surfaces has demonstrated a reduction in modulus and hardness, with amorphous LixSi presenting a modulus of 45 GPa and a hardness of 1 GPa.531
7.7.2 Thermogravimetric analysis and differential scanning calorimetry.
Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) are essential techniques for evaluating the thermal stability and decomposition properties of silicon-based negative electrodes in LIBs. These methods provide insights into how factors like particle size, state of charge, and electrolyte composition influence the thermal behaviour of the electrodes.532 For example, smaller silicon particles and higher lithiation levels tend to reduce thermal stability, whilst integrating oxygen into the material matrix and adjusting FEC concentration in the electrolyte can enhance stability.380 DSC profiles of lithiated electrodes typically reveal distinct temperature ranges, each associated with thermal events such as SEI decomposition and LiF formation.533Table 4 summarises advanced characterisation techniques for silicon negative electrodes.
Table 4 Advanced characterisation techniques for silicon negative electrodes
Characterisation |
Functions |
Applications |
Ref. |
In situ TEM |
Real-time visualisation of structural changes, phase transformations, and fracture mechanics during lithiation/delithiation |
Observing nanoscale phenomena, understanding failure mechanisms, and phase transitions |
476 and 534
|
In situ XRD |
Monitoring crystallographic changes and phase transitions in silicon negative electrodes during cycling |
Phase identification, tracking structural evolution |
489, 490 and 535
|
Operando XAS |
Provides information on oxidation states, local chemical environment, and electronic structure changes |
Studying electronic structure, phase changes, and SEI formation |
493, 536 and 537
|
AFM |
High-resolution topographical and mechanical mapping, SEI analysis |
Surface characterisation, mechanical property mapping |
500 and 538
|
Raman spectroscopy |
Identification of vibrational modes to study phase changes and amorphisation |
Structural analysis, SEI composition |
513, 539 and 540
|
Fourier-transform infrared spectroscopy (FTIR) |
Identification of chemical bonds and functional groups, SEI composition analysis |
Studying SEI formation and electrolyte decomposition |
517 and 541–543
|
NMR spectroscopy |
Local chemical environment, lithium environments, SEI |
Studying lithium distribution, local chemistry, and SEI properties |
527, 544 and 545
|
Nanoindentation and scratch testing |
Mechanical properties such as hardness, elastic modulus, and adhesion strength |
Assessing mechanical stability and coating adhesion |
531 and 546–548
|
TGA and DSC |
Thermal stability, decomposition behaviour of silicon negative electrodes and their components |
Thermal analysis, safety assessment |
532 and 549–551
|
8. Conclusion and future outlook
8.1 Summary of current progress and challenges
In the last ten years, notable advancements have been achieved in tackling the inherent difficulties of silicon negative electrodes, including substantial volume fluctuations during cycling, unstable SEI, mechanical deterioration, and considerable initial irreversible capacity loss. Various strategies have been developed to enhance the performances of silicon negative electrodes, including:
1. Nanostructuring silicon. Reducing the size of silicon to the nanoscale, such as through nanoparticles, nanowires, and hollow structures, allows for improved accommodation of volume expansion and contraction during lithiation and delithiation. This approach minimises mechanical stress and lowers the risk of fracture and pulverisation.552
2. Composite material design. Silicon–carbon composites and silicon–graphene hybrids offer improved electrical conductivity, structural integrity, and mechanical buffering, successfully addressing volume change challenges and enhancing overall electrochemical performance.
3. Advanced surface coatings. Carbon layers, inorganic materials, and conductive polymers can reduce pulverisation, enhance conductivity, and preserve the surface stability of silicon particles.136
4. Innovative binder and electrolyte technologies. The advancement of conductive, self-healing, and ionic-conductive binders, in conjunction with innovative electrolytes and additives, has significantly enhanced the mechanical resilience, SEI stability, and overall cycling performance of silicon negative electrodes.
5. Prelithiation techniques. Multiple prelithiation techniques, such as electrochemical and mechanical approaches, have been established to address the initial irreversible capacity loss and enhance the initial CE of silicon negative electrodes.
Even with these advancements, numerous obstacles persist in commercialising silicon negative electrodes, such as scalability, manufacturing expenses, safety considerations, environmental effects, and challenges in recycling. Creating affordable and scalable production techniques that reliably produce high-quality silicon materials is crucial for broad acceptance. Furthermore, it is essential to guarantee safety and adhere to regulatory standards (e.g., SiH4553–560), especially concerning the thermal and mechanical stability of silicon negative electrodes, to attain market acceptance.
8.2 Future research directions and emerging opportunities
Future research should address several key areas to unlock the full potential of silicon negative electrodes in commercial LIBs.
8.2.1 Scalable and sustainable manufacturing.
Given Panasonic's prior withdrawal of silicon technology, it seemed there had been few real-world applications for silicon negative electrodes.146 Indeed, various efforts have been made to commercialise silicon negative electrodes. To boost cell energy, Hitachi Maxell–Kopin added a small quantity of silicon (mainly as SiOx) to the carbon negative electrode.561 Nexeon pioneered the development of two distinct kinds of silicon negative electrode materials:562 NSP-1 with 10 wt% silicon loading and NSP-2 with up to 80 wt% silicon loading. BTR Inc. produced composite negative electrodes based on silicon with a specific capacity of 600 mAh g−1 to 650 mAh g−1 at 0.1C.563 The negative electrodes of Tesla's Model 3 batteries contained 10% silicon.564 Sila, a new company dedicated to silicon negative electrodes, was founded565 and claimed to produce batteries of 10% to 15% more capacity for wearable gadgets in 2019 and electric vehicles in 2023.566 In commercial cells, the amount of silicon in graphite was only ∼5 wt%561 or 10 wt% of fine silicon.567 With the engagement of prominent firms such as Panasonic and Samsung SDI, patent literature may be available for inspection.
One of the primary objectives will be the development of scalable and sustainable manufacturing methods essential for reducing the production costs associated with silicon negative electrodes. Emphasis should be placed on energy-efficient synthesis techniques, such as low-temperature CVD,568,569 or scalable mechanical processes like ball milling, which serve to minimise both energy consumption and waste generation. Moreover, investigating sustainable chemical approaches for synthesising silicon and composite materials, using environmentally benign solvents and reagents, could lessen the ecological footprint of silicon negative electrode production. Advanced manufacturing strategies, including optimised binder configurations and laser patterning, have been investigated to improve the performance and longevity of silicon/graphite composite anodes.570 Whilst silicon-based anodes show great potential for high-energy-density LIBs, further research is needed to optimise their production and performance, particularly in comparison to other promising materials like phosphorus-based anodes.571
8.2.2 Enhanced electrolyte and binder systems.
Advancements in electrolyte and binder systems572 will be pivotal in enhancing the cycle stability and capacity retention of silicon negative electrodes. The development of novel electrolyte additives capable of forming a stable SEI with silicon, whilst mitigating detrimental side reactions, is of critical importance.
8.2.3 Novel architectures and hybrid materials.
An intriguing area of investigation lies in the design of innovative electrode architectures573,574 and hybrid materials that can accommodate the volumetric expansion and contraction of silicon, whilst simultaneously enhancing both mechanical stability and electrical conductivity. Hybrid structures, such as silicon–graphene composites or core–shell designs, could offer a balanced combination of high capacity, structural stability, and cycle longevity. The architectures may be optimised further through modifications to material dimensions, forms, and compositions.
8.2.4 Advanced characterisation and modelling techniques.
Recent advancements in characterisation techniques have significantly enhanced our understanding of silicon-based negative electrodes for LIBs. In situ TEM has enabled real-time observation of morphological changes in silicon negative electrodes from microscale to nanoscale, providing insights into capacity fading mechanisms.575In situ NMR spectroscopy has revealed lithium-silicide phase transformations in nano-structured silicon negative electrodes, offering atomic-level insights into alloying reactions during cycling.576 XRD and neutron depth profiling techniques have allowed the study of lithiation processes, electrode swelling, and phase transformations in silicon negative electrodes.577 These advanced characterisation methods, along with computer simulations, have provided valuable information on the structural, chemical, and electrochemical transformations occurring during battery operation.469 The integration of these techniques is crucial for developing more resilient and efficient silicon-based negative electrodes, addressing challenges such as volume expansion and capacity loss in next-generation LIBs.
Modelling lithium intercalation/deintercalation in silicon particles has revealed the importance of considering metastable amorphous phase transitions and volume changes.578 The high theoretical capacity of silicon is attributed to its ability to accommodate up to 22 lithium atoms per 5 silicon atoms, though this causes considerable volume expansion.579 For instance, if the lithiated state has the highest packing density (cubic or close hexagonal packing),580,581 then the unlithiated state will have a packing density of
(the volume expansion ratio is 3.7 if Vfinal = 3.7Vinitial),582 though the model did not consider conductive additives, binders, and properties of pores.304 First-principles simulations have been crucial in understanding the atomic-level mechanisms of lithiation in silicon electrodes, including bulk Li–Si compounds and Si nanostructures.444
8.2.5 Recycling and end-of-life management.
As silicon negative electrodes become more widely adopted, it will be vital to establish effective recycling systems to mitigate environmental impact and recover valuable materials. The recycling of circular energy materials from waste resources, including batteries, and glass sectors, offers potential economic and environmental benefits.583 However, challenges remain in developing cost-efficient, sustainable processes that yield high-quality recycled materials suitable for new battery applications. Research efforts should prioritise the design of silicon negative electrodes with recyclability in mind, incorporating materials and structures that facilitate disassembly and reuse. In parallel, exploring chemical and electrochemical techniques to recover silicon and other valuable components from spent negative electrodes will be crucial for enhancing the sustainability of silicon-based batteries.
8.2.6 Commercialisation strategies and market adoption.
The commercialisation of silicon-based negative electrodes is advancing rapidly, with several companies (e.g., Sila Nanotechnologies, Amprius Technologies, Group14) operating at the pilot to commercial scale. Early integration in wearable electronics and premium EV segments is expected between 2025 and 2027, with broader market penetration dependent on cost reduction, cycling stability, and manufacturing scalability. The successful commercialisation of silicon negative electrode technology will depend on strategic partnerships between academia, industry, and government. Promoting market acceptance of silicon negative electrodes will require demonstrating their distinct advantages, such as improved energy density, extended cycle life, and cost-effectiveness in real-world applications. Support from government bodies, including research and development incentives and subsidies for early adopters, could play a key role in easing market entry and advancing silicon-based battery technologies.
8.3 Long-term vision for silicon-based negative electrodes
The long-term goal for silicon-based negative electrodes in LIBs is their widespread integration across a variety of applications, including portable electronics, electric vehicles, grid energy storage, and renewable energy systems. By surmounting existing hurdles and enhancing the development of silicon negative electrodes, these materials can transform the battery industry, providing superior energy densities, extended cycle lifetimes, and more sustainable energy storage options.
As research advances, the emphasis will probably transition to optimising the complete battery system, encompassing the cathode, electrolyte, and separator, to enhance the advantages of silicon negative electrodes. Ultimately, the goal is to develop batteries with silicon negative electrodes which are high-performing and cost-effective but also safe, sustainable, and scalable for global energy needs.
Author contributions
Pin-Yi Zhao: conceptualisation, methodology, investigation, software, formal analysis, data curation, visualisation, writing – original draft, and writing – review and editing. Shengbo Zhang: writing – review and editing. Kwang-Leong Choy: project administration, funding acquisition, supervision, and writing – review and editing. Yongyi Song: writing – review and editing of Sections 2–4. Shudong Zhang: writing – review and editing of Sections 5 and 6. Decai Guo: writing – review and editing of Sections 7 and 8. Chengkai Yang: writing – review and editing. All the authors have read and agreed to the published version of the manuscript.
Conflicts of interest
The authors declare that they have no known conflicting financial interests or personal relationships that would seem to have influenced the work presented in this work.
Data availability
Data will be available upon request to the authors.
Acknowledgements
There was no external funding for this study.
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