Glycolide additives enrich organic components in the solid electrolyte interphase enabling stable ultrathin lithium metal anodes

Xin-Meng Wang a, Xue-Qiang Zhang b, Peng Shi b, Li-Peng Hou b, Ming-Yue Zhou b, Aibing Chen *a and Qiang Zhang *b
aCollege of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China. E-mail: chen_ab@163.com
bBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China. E-mail: zhang-qiang@mails.tsinghua.edu.cn

Received 5th January 2021 , Accepted 26th January 2021

First published on 28th January 2021


Abstract

Stable lithium (Li) metal anodes are a foundation stone for practical Li metal batteries. An ultrathin Li metal anode (<50 μm) is the premise to realize high-energy-density Li metal batteries. However, the uneven Li plating/stripping induced by the unstable solid electrolyte interphase (SEI) leads to the rapid depletion of active Li and electrolyte, resulting in a poor cycle life of ultrathin Li metal anodes. Herein, an electrolyte additive, glycolide (GL), is proposed to prolong the cycle life of ultrathin Li metal anodes. GL additives decompose on the Li metal anode to enrich the organic components in the SEI. The uniformity of Li deposition is improved with the introduction of GL additives. Under practical conditions with an ultrathin Li metal anode (50 μm) and a high loading LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode (3.0 mA h cm−2), 175 cycles were achieved in Li|NCM523 cells with GL additives compared with 86 cycles without GL additives. This work further promotes the design of electrolyte additives for stabilizing ultrathin Li metal anodes.


Introduction

The pursuit of a non-fossil based and wireless society strongly depends on efficient electrochemical energy storage devices. The development of high-specific-energy, long-cycling, and low-cost secondary batteries has become a strong research focus of the world.1,2 Owing to its extremely low reduction potential (−3.04 V vs. standard hydrogen electrode) and ultrahigh theoretical specific capacity (3860 mA h g−1), lithium (Li) metal is considered as an ideal anode material.3–6 A Li metal anode can be paired with various cathodes, such as LiNi0.5Co0.2Mn0.3O2 (NCM523) and sulfur, to construct high-energy-density batteries.7–13 Despite various alternative battery systems, practical conditions including an ultrathin Li metal anode (<50 μm), a low negative/positive electrode areal capacity ratio (<3.0), and lean electrolytes (<3.0 g A h−1) are generally required to realize high-energy-density Li metal batteries.7,14,15 However, under practical conditions, Li metal batteries usually deliver a poor cycle life mainly because of the rapid decay of ultrathin Li metal anodes, which significantly hinders the practical applications of Li metal batteries. A stable ultrathin Li metal anode is a foundation stone for practical Li metal batteries.

The rapid decay of ultrathin Li metal anodes is directly induced by uneven Li deposition, that is Li dendrites or filaments.16–18 Furthermore, the morphology of Li deposition is mainly dictated by the solid electrolyte interphase (SEI) on the surface of the Li anode.19–22 Due to the strong reducibility, Li metal irreversibly reacts with electrolyte and the solid reaction products precipitate on the Li metal anode to form SEI. The naturally formed SEI is heterogeneous, which leads to uneven Li ion transport and Li deposition. The uneven Li deposition causes the low utilization efficiency of deposited Li and the constant consumption of electrolyte. On the one hand, during the stripping process, partial Li cannot be stripped due to the uneven Li deposition and becomes dead Li, inducing the rapid loss of active Li. As reported, the filament-deposited Li is more prone to lose structural connection, which brings about a low utilization efficiency and a short cycle life.23 The accumulation of dead Li also increases the internal resistance of Li ion transport, deteriorating the stability of batteries.23–25 On the other hand, the unevenly deposited Li exposes a large surface area to react with electrolyte, giving rise to the substantial and rapid consumption of electrolyte. The rapid depletion of limited active Li and electrolyte naturally leads to the short lifespan of working batteries.26 Therefore, regulating the uniformity of Li deposition is critical to improving the stability of ultrathin Li metal anodes.

Tremendous breakthroughs have been achieved over the past decades in terms of the physicochemical characteristics of Li deposition and the SEI.27–35 Various strategies have been proposed to regulate the uniformity of Li deposition and the SEI, such as optimizing electrolyte formulations,35–45 designing artificial coatings,46–53 and constructing three-dimensional hosts.54–57 Among these strategies, regulating the electrolyte formulations to form a uniform and dense SEI is much more effective and exhibits a significant impact. Recently, localized high concentration electrolytes (LHCEs) displays an outstanding performance in improving the uniformity of Li deposition owing to the anion-derived SEI.36,58,59 However, the long cycling performance of ultrathin Li metal anodes under practical conditions using LHCEs remains insufficient for practical applications. The development of LHCEs is necessary to further promote the uniformity of Li deposition and acts as one of the most promising electrolyte formulations for ultrathin Li metal anodes.

Herein, glycolide (GL) was demonstrated as an electrolyte additive for the pristine LHCEs to further improve the uniformity of Li deposition and the cycle life of ultrathin Li metal anodes. The pristine LHCE consists of lithium bis(fluorosulfonyl)imide (LiFSI), dimethyl carbonate (DMC), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (HFE) with a mole ratio of 1.0[thin space (1/6-em)]:[thin space (1/6-em)]1.8[thin space (1/6-em)]:[thin space (1/6-em)]2.0. GL additives decompose on the Li metal anode before LiFSI and enrich the organic components in the SEI. The effectiveness of GL additives was verified in Li|LiNi0.5Co0.2Mn0.3O2 (NCM523) cells under practical conditions with an ultrathin Li anode (50 μm) and a high loading NCM523 cathode (3.0 mA h cm−2). The cells with GL additives delivered a stable cycling performance of 175 cycles in comparison to 86 cycles without GL additives at 0.4 C.

Experimental

Materials

Lithium (Li) metal foils (50 μm) from China Energy Lithium Co., Ltd. were rolled on copper foil and punched into disks with a diameter of 15 mm. Glycolide (GL, 97.0%) was purchased from Alfa Aesar Chemical Co., Ltd. Lithium bis(fluorosulfonyl)imide (LiFSI, 99.9%), dimethyl carbonate (DMC, 99.9%), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (HFE, 99.9%) were purchased from Suzhou Duoduo Chemical Technology Co., Ltd. All solvents and Li salts were used as received. The mole ratio of LiFSI, DMC, HFE, and GL in the electrolyte with GL additives is 1.0[thin space (1/6-em)]:[thin space (1/6-em)]1.8[thin space (1/6-em)]:[thin space (1/6-em)]2.0[thin space (1/6-em)]:[thin space (1/6-em)]0.3. The LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode with an areal capacity of 3.0 mA h cm−2 (measured value) was acquired from Guangdong Canrd New Energy Technology Co., Ltd., and was punched into disks with a diameter of 13 mm. A polyethylene (PE) separator with a diameter of 19 mm was purchased from Asahi Kasei Technosystem Co., Ltd. All materials were kept and used in an Ar-filled glove box with oxygen and water contents below 0.1 ppm.

Electrochemical tests

All coin cells (2032-type) were assembled in an Ar-filled glove box and tested on a LAND multichannel battery cycler (Wuhan LAND Electronics Co., Ltd.). Symmetric Li|Li cells were assembled with ultrathin Li anodes of 50 μm, and tested at a current density of 1.0 mA cm−2 and a capacity of 2.5 mA h cm−2 after two pre-cycles at 0.1 mA cm−2. Li|Cu cells were tested at a current density of 1.0 mA cm−2 and a capacity of 2.5 mA h cm−2. The galvanostatic cycling test of Li|NCM523 cells was charged/discharged within the voltage range of 2.8–4.3 V at 25 °C. The amount of electrolyte in each coin cell is 12 μL mA h−1. Electrochemical impedance spectroscopy (EIS) was performed on a Solartron 1470E electrochemical workstation (Solartron Analytical) with a frequency from 105 to 10−1 Hz at an amplitude of 10 mV at the end of the charge. The cyclic voltammetry (CV) test was conducted on a Solartron 1470E electrochemical workstation (Solartron Analytical) at a scanning rate of 0.5 mV s−1 from 0.01 V to 2.0 V.

Characterization

Li-deposited anodes were disassembled from the cycled Li|NCM523 cells. The cycled anodes were cleaned with DMC solvent and dried until the solvent volatilized thoroughly in the glove box. The Li deposition morphologies were characterized using a scanning electron microscope (SEM) operated at 5.0 kV (JSM 7401F, JEOL Ltd., Tokyo, Japan). X-ray photoelectron spectroscopy (XPS) experiments were conducted on a scanning X-ray microprobe (Quantera SXM, ULVAC-PHI. INC) operated at 250 kV, and 55 eV with monochromated Al Kα radiation.

Results and discussion

The stability of ultrathin Li metal anodes in LHCEs with or without GL additives was firstly evaluated in symmetric Li|Li cells at a current density of 1.0 mA cm−2 and a capacity of 2.5 mA h cm−2. As shown in Fig. 1a, the electrolyte with GL additives exhibits stable cycling performance within 700 h. The polarization increases from 45 mV at the initial stage to 100 mV at 700 h, while the electrolyte without GL displays random voltage oscillations after 315 h, which is related to the accumulation of dead Li and dendrite-induced local soft short circuit. The polarization increases from 25 mV at the initial stage to 160 mV at 315 h. In particular, the voltage profiles around 300 h were compared. The Li|Li cell without GL additives has a higher overpotential of 160 mV than that with GL (60 mV) at 300 h (Fig. 1b). Moreover, the polarization voltage of cells with GL additives remains steady at around 105 mV for 690 h (Fig. S1, ESI). The addition of GL additives into LHCEs significantly enhances the cycle stability of ultrathin Li metal anodes and suppresses the increase of polarization.
image file: d0qm01134g-f1.tif
Fig. 1 Electrochemical performance of half cells with and without (w/o) GL. (a) Cycling performance of Li|Li symmetric cells at 1.0 mA cm−2 and a capacity of 2.5 mA h cm−2 after two pre-cycles at 0.1 mA cm−2, and (b) the corresponding partially enlarged voltage–time curves. (c) Cycling performance of Li|Cu cells at 1.0 mA cm−2 and a capacity of 2.5 mA h cm−2, and (d) the corresponding voltage profiles at the 20th cycle.

To evaluate the reversibility and utilization of ultrathin Li metal anodes, tests for the Coulombic efficiency (CE) of the Li|Cu cells were conducted at a current density of 1.0 mA cm−2 with a capacity of 2.5 mA h cm−2. The average CE (97.5%) of the LHCEs with GL additives is higher than that without GL additives (97.0%). The cells with GL additives can maintain stable cycling within 47 cycles, while the cells without GL additives begin to fluctuate after 20 cycles and are overcharged after 30 cycles (Fig. 1c). The low CE during the initial 4 cycles with GL additives is inferred to be induced by the chemical/electrochemical formation process of the SEI, which is familiar in Li-ion batteries based on graphite anodes. Fig. 1d shows the voltage profiles of the Li stripping/plating process at the 20th cycle. The voltage gap between the charge and discharge curves is 189 mV for the cell with GL additives, while it is 270 mV for the cell without GL additives. Moreover, the voltage profile in the cell with GL additives is flat instead of fluctuant. The electrolyte with GL additives improves the utilization efficiency of the deposited Li and decreases the polarization, finally contributing to more than twice the lifespan.

The compatibility of GL as an electrolyte additive for rechargeable Li metal batteries was also investigated for Li|NCM523 batteries. An ultrathin Li metal anode (50 μm, ca. 10 mA h cm−2) and a high loading NCM523 cathode (3.0 mA h cm−2) were employed in the Li|NCM523 cell. The cell with GL additives displays superior cycling performance of 175 cycles with a capacity retention of 95% (Fig. 2a). The reproductivity of the cell with GL additives was also confirmed (Fig. S2a, ESI). In contrast, the rapid decline in capacity is observed in the cell without GL additives which fades to 80% retention after only 86 cycles (Fig. 2a). According to charge–discharge voltage profiles (Fig. S2b, ESI), the polarization voltage of the cell with GL additives increases by 117 mV, lower than that of the cell without GL additives (156 mV) after 100 cycles based on the mid-voltage of the cells. The reduced polarization voltage indicates that the introduction of GL additives retards the electrolyte consumption and the accumulation of dead Li.


image file: d0qm01134g-f2.tif
Fig. 2 (a) Cycling performance of Li|NCM523 cells with and without GL additives at 0.4 C after two pre-cycles at 0.1 C. (b) The evolution of the interfacial resistance of Li|NCM523 cells with different types of electrolyte after 5 and 50 cycles. (c–f) The deposition morphology and cross-sectional views of the remaining Li after cycling without (c and e) and with (d and f) GL additives after 30 cycles.

Electrochemical impedance spectroscopy (EIS) was conducted to detect the evolution of internal resistance in Li|NCM523 cells (Fig. S3, ESI). The semicircle at high frequency can be assigned to the resistance of Li ion transport through the SEI (RSEI), and the semicircle at low frequency represents the resistance of charge transfer (Rct) which reflects the accumulation of dead Li.37,54 Obviously, the increase in RSEI and Rct is much smaller when GL additives were added. From the 5th cycle to the 50th cycle, RSEI increases from 14.7 to 31.7 Ω. However, the RSEI of the cells without GL additives rapidly increases from 15.2 to 50.3 Ω (Fig. 2b). Moreover, the ohmic resistance of the electrolyte with GL additives decreases from 31.2 to 16.7 Ω at the 50th cycle (Fig. S3, ESI). The addition of GL additives significantly decreases the growth of RSEI and the accumulation of dead Li.

Li deposition morphology at the 30th and 100th cycles was investigated by scanning electron microscopy (SEM) to gain insights into the role of GL additives in regulating the uniformity of Li deposition. The porous and crumpled morphology was observed in the electrolyte without GL additives at the 30th cycle (Fig. 2c). In contrast, the surface of deposited Li, with a diameter of 3.0 μm, is smooth in the electrolyte with GL additives (Fig. 2d). In addition, 43 μm-thick active Li remains in the electrolyte with GL additives compared with only 30 μm-thick active Li remaining in the electrolyte without GL additives after 30 cycles (Fig. 2e and f), which implies that the utilization of ultrathin Li metal anodes is obviously improved. Remarkable differences in the Li deposition morphology were also observed at the 100th cycle to confirm the above conclusions (Fig. S4, ESI). Evidently, GL additives can improve the uniformity of deposited Li after long cycles and reduce the accumulation of dead Li.

As mentioned, the SEI composed of the decomposition products of the electrolyte plays a vital role in regulating the uniformity of Li deposition. The decomposition features of the electrolyte with GL additives were monitored by cyclic voltammetry (CV) tests (Fig. S5, ESI). GL additives decompose at 1.45 V before the decomposition of LiFSI (1.35 V), implying that GL additives possibly participate in the formation of the SEI. To verify the above speculation, the chemical composition of the SEI was detected by X-ray photoelectron spectroscopy (XPS). In O 1s spectra (Fig. 3a and b), the content of components with the C[double bond, length as m-dash]O functional group in the presence of GL additives is 3–6 times as high as that without GL (the proportions are 69.6% vs. 20.6%, 66.2% vs. 10.4%, and 56.7% vs. 14.6% at sputtering time of 5, 7, and 9 min). This feature is maintained after sputtering for 9 minutes. A similar increase of the components with the C[double bond, length as m-dash]O functional group was also reflected in the C 1s spectra (Fig. 3c and d); the ratios with and without GL additives are 36.7% vs. 6.0%, 38.7% vs. 5.6%, and 31.0% vs. 9.6% at sputtering time of 5, 7, and 9 min. According to the atomic concentration (Fig. S6, ESI), the content of C and O elements with GL additives is about 5% higher than that without GL at different sputtering times, respectively. In addition, the SEI generated by adding GL additives in the LHCEs is rich in LiF (Fig. S7, ESI) which comes from the decomposition of LiFSI. LiF can regulate the Li ion transport in the SEI and promote the uniform deposition of Li.36,50,60–63 Accordingly, GL additives enrich the organic components in the LiF-rich SEI formed by the LHCEs, effectively promoting uniform deposition of Li ions and improving the cycle stability of ultrathin Li metal anodes (Fig. 4).


image file: d0qm01134g-f3.tif
Fig. 3 XPS spectra of the SEI on ultrathin Li metal anodes in Li|NCM523 cells without (a and c) and with (b and d) GL additives after 5 cycles at different sputtering times. (a and b) O 1s and (c and d) C 1s.

image file: d0qm01134g-f4.tif
Fig. 4 The schematic of the role of GL additives in stabilizing ultrathin Li metal anodes.

Conclusions

Glycolide was demonstrated as an effective electrolyte additive in the pristine LHCEs to further improve the uniformity of Li deposition and the cycle life of ultrathin Li metal anodes. GL additives decompose before LiFSI to participate in the formation of the SEI and enrich the components with the C[double bond, length as m-dash]O functional group in the LiF-rich SEI, further promoting the uniformity of Li deposition and decreasing the accumulation of dead Li. As a consequence, superior cycle stability of ultrathin Li metal anodes was achieved in the symmetric Li|Li cells and Li|Cu cells with a stable polarization by adding GL additives. Moreover, 175 stable cycles were achieved in the Li|NCM523 cells with GL additives under practical conditions, including an ultrathin Li anode (50 μm) and a high loading NCM523 cathode (3.0 mA h cm−2), compared with 86 cycles without GL additives. This work promotes the electrolyte additive design for stabilizing practical Li metal anodes.

Author contributions

Q. Z. and A. C. conceived this work; X. M. W. and X. Q. Z. designed all experiments; X. M. W. measured the cell performance; X. M. W. and X. Q. Z. wrote the paper; and all the authors participated in the analysis of the experimental data and discussions of the results as well as in preparing the paper.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (21825501, 21808125, 21808121, and U1801257), the National Key Research and Development Program (2016YFA0202500 and 2016YFA0200102), and the Tsinghua University Initiative Scientific Research Program.

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Footnote

Electronic supplementary information (ESI) available: SEM images, EIS, CV, and so on. See DOI: 10.1039/d0qm01134g

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