Mesoscopic open-eye core–shell spheroid carved anode/cathode electrodes for fully reversible and dynamic lithium-ion battery models

We report on the key influence of mesoscopic super-open-eye core–shell spheroids of TiO2- and LiFePO4-wrapped nanocarbon carved anode/cathode electrodes with uniform interior accommodation/storage pockets for the creation of fully reversible and dynamic Li-ion power battery (LIB) models. The mesoscopic core–shell anode/cathode electrodes provide potential half- and full-cell LIB-CR2032 configuration designs, and large-scale pouch models. In these variable mesoscopic LIB models, the broad-free-access and large-open-eye like gate-in-transport surfaces featured electrodes are key factors of built-in LIBs with excellent charge/discharge capacity, energy density performances, and outstanding cycling stability. Mesoscopic open-eye spheroid full-LIB-CR2032 configuration models retain 77.8% of the 1st cycle discharge specific capacity of 168.68 mA h g−1 after multiple cycling (i.e., 1st to 2000th cycles), efficient coulombic performance of approximately 99.6% at 0.1C, and high specific energy density battery of approximately 165.66 W h kg−1 at 0.1C. Furthermore, we have built a dynamic, super-open-mesoeye pouch LIB model using dense packing sets that are technically significant to meet the tradeoff requirements and long-term driving range of electric vehicles (EVs). The full-pouch package LIB models retain a powerful gate-in-transport system for heavy loaded electron/Li+ ion storage, diffusion, and truck movement through open-ended out/in and then up/downward eye circular/curvy folds, thereby leading to substantial durability, and remarkable electrochemical performances even after long-life charge/discharge cycling.

As a liquid electrolyte solution, we used a LiPF 6 conductive salt (1 M), which is dissolving in (CH 2 O) 2 CO, ethylene carbonate/ C 5 H 10 O 3 , diethyl carbonate mixture with 1:1 v/v ratio. To engineer the P-and N-working electrodes by using mesoscopic 3D-LFPO@nano-C cathodic materials, and ETO@nano-C anode material, we used a mixture of the active cathode or anode materials: carbon-black: PVDF with equivalent mass fraction ratio of 0.75: 0.15: 0.1, respectively.
The prepared mixture is mixed with stirring for 1 h in a rational amount of NMP. Then the prepared slurry mixtures were cast into 10 µm-aluminum (Al) and 8 µm-cupper (Cu) foils, and dried under vacuum condition (12 h/80 o C). The active materials' loading mass of cathode and anode electrodes are 14.87 and 6.99 mg/cm 2 , respectively.
It is important to note that the dried electrode films were compressed between the double rollers for the following key facts; (i) enhancement of the packing density, (ii) reduction of the voids and space vicinities along film surfaces, and (iii) ensuring the intimate contact of the super-openmesoeye materials onto electrode surfaces and their electric current collector. Circular perforated electrodes (i.e., 16 mm / diameters for Li-chip reference or counter electrodes, and super-openmesoeye anode/cathode working electrodes, respectively), and 20 mm for porous-membrane separators are prepared and combined in half-/full-scale CR2032-type coin cells using crimper machine for cell pressing.
The electrochemical performances of the designed LIB-coin-cells were tested by using galvanostatic charge/discharge merits (using multichannel battery system, LAND CT2001A, Wuhan, China). Cyclic voltammetry analysis (CV) is recorded by using CHI 660c electrochemical workstation). We used Zennium/ZAHNER-Elektrik GmbH & CoKG to measure the electrochemical impedance spectroscopy (EIS). In addition, ZS-102 tap density meter was used measure the tap density of the electrodes. All the electrochemical measurements of half-and fullscale LIB cells are carried out at 25 o C.

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The specific mass value of P-and N-electrode materials presented in the ETO@nano-C-anode and 3D-LFPO@nano-C cathode designed CR2032-coin LIB formulations is key to control the electrochemical performance features including energy density, cell capacity, and safety factors.
One of electrochemical optimization and safety fabrication factor are firmly related with P / N mass proportion ratio. For instance, the mas loading affect the formation of lithium plating/deposition along anode surfaces during the charge or delithiation procedure.
The safety issue and maintaining high specific energy have a great concern tradeoff factor during the configuration of LIB-CR2032-coin-cells. Thus, controlling of the balancing (P/N) Cap ratio is the key design of ETO@nano-C//SSB@nano-C full-scale LIB-CR2032-coin-cells configuration and also the ordering sets of stacked-layers of ETO@nano-C LIB-CR2032-coin anode (Nelectrode), and SSB@nano-C LIB-CR2032-coin cathode (P-electrode) packing into pouch models.
To avoid the negative impacts and shortcomings of lithium plating mechanism during the multiple charge process, which is largely a deteriorating aging of LIB design and effectively affect the large-scale LIB safety manufacture, we fabricate the ETO@nano-C layers along the anode surfaces with (P: N) Cap ratio of 1: >1. A slight increase in the overall mass loading capacity of the ETO@nano-C anode is furthermore required for both furtherance safety and maintaining high specific energy storage [1-10]. We also kept, to high extent, the balancing (P: N) Cap ratio of 1:1 to obtain full-scale LIBs with high specific energy storage.
Per of our experimental sets, the balancing capacity of 3D-LFPO@nano-C cathode and ETO@nano-C anode with (P: N) Cap ratio ≈1: 1.07-1.2, to obtain an optimal tradeoff relationship.

S3. Large scale, collar packing of CR2032-coin cell sets in pouch LIB-model (i) The mass fraction analysis of designated pouch LIB models
The pouch LIB models, the stacking layers of super-open-mesoeye 3D-LFPO@nano-C (such as SSB@nano-C, MS@nano-C and DCS@nano-C) cathode P-electrodes, and ETO@nano-C anode N-electrode are controlled according the depicted contents used for formation the model. Figure   S2 shows the mass composition ratio of cathodic materials used for working P-electrode fabrication is 75% from the total content. However, the content ratio used for fabrication of Pelectrode is 0.75: 0.15: 0.10, for cathodic materials (SSB@nano-C): C: PVDF linker, respectively.
The SSB@nano-C cathode P-electrodes, and ETO@nano-C N-electrodes connected and arranged in the CR2032 coin cells and then packed into a collar-like shape (Scheme 1). The mass fraction

(ii) Electrochemical parameters of cell battery pouch LIB-models
The ETO@nano-C (N-electrode)//SSB@nano-C (P-electrode) stacked in pouch LIB-model is designed with specific 3D dimensions of 35 mm (width), 55 mm (length) and ~2.5-3mm (thickness), respectively. The stacked-layers of ETO@nano-C anode (N) // SSB@nano-C-cathode (P) electrodes are designed in pouch LIB-models by control the (N/P) Cap balancing ratios with 5-/6-layers with 10 sides for Cu-electrode and Al-electrode, respectively. Well-packed and dense ETO@nano-C anode//SSB@nano-C-cathode coin cells are contiguously connected into a series of the stacking layer configurations of pouch LIB-types. As shown in Figure S2, we consider the mass component and fraction constitutes to control the pouch LIB-design. Accordingly, the actively-loaded mass in the stacking-layer SSB@nano-C (cathode) is 2.23 g, and ETO@nano-C (anode) is 1.0 g in pouch LIB-types.

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To optimize the pouch LIB-design, the electrode area is selected with the following dimensions of (3*5=15 cm 2 ) and (3*4.75 = 14.3 cm 2 ) for SSB@nano-C cathode and ETO@nano-C anode, respectively. Thus, the total area of the SSB@nano-C cathode and ETO@nano-C anode coverage the pouch LIB cells are 150 and 143 cm 2 ; respectively. Therefore, the SSB@nano-C cathode and ETO@nano-C anode mass stacking is 14.87 and 6.99 mg/cm 2 , respectively. Accordingly, the areal discharge capacity the SSB@nano-C cathode and ETO@nano-C anode is 2.51 and 1.18 Ah/cm 2 , respectively.
To evaluate the pouch LIB designs volumetric energy density, we used the following equation: (S3 (f) and S4(g)); respectively. It is evident that, exposed

S5. Textural parameters of mesoscopic supper-open-eye core/shell spheroids
We measured the N 2 adsorption−desorption isotherms mesoscopic supper-open-eye core/shell spheroid 3DLFPO@nano-C cathodes to determine the specific surface areas (S BET m 2 /g) of mesoporous spheroid structures, and pore size using non-linear density functional theory (NLDFT), SI- Fig.S5(a, b). Our finding indicated that the N 2 isotherms featured a type IV with H 2 hysteresis loop for all tested cathode samples. This finding indicates the formation of mesocage caves and high surface coverages of the entire spheroid-structures. The spheroid design, active facet-surface type orientation, variable model structures, and nano -particles dressed along the particles surface are affected the textural parameters, dynamic arrangement of space holes, mesocages and pore entrances, and surface coverage area. For instance, the (S BET , m 2 /g) value decreases in this order SSB@nano-C > MS@nano-C > DCS@nano-C spheres, respectively.
Among all prepared spheroid structures, the SSB@nano-C design can be considered as diverse surface texture electrode in terms of large surface-to-pore volume ratios, uniformly-arranged cage cavity and well-ordered entrances for long-timescale stability, excellent specific capacities, highenergy-density, and high LIBs electrochemical performances. The calculated surface areas are 294.5, 81.0 and 13.1 m 2 .g −1 and the corresponding pore size diameters are 12.52,44.69; 13.98,and 16.67,52.74 nm for @nano-C, @nano-C and @nano-C, respectively.  anions has multi-peaks associated with its vibration mode, symmetric stretching mode ν 1 appear at 972 cm -1 , the ν 2 mode around 510 cm -1 ; and the ν 3 , ν 4 modes in the region 1051-1093 cm −1 . The area around 3250 cm −1 is sensitive to Li localization region of Li 3 PO 4 . The weak peak at 3350 cm −1 , 1536 cm −1 , and 1615 and 1718 cm -1 can be attributed to the existence of-OH group, CH 2bending vibration, and C=O stretching, respectively.

S8. Chemical bonding and composition of mesoscopic supper-open-eye core/shell spheroid cathodes
Raman spectroscopy enables investigation of surface composition of mesoscopic supper-open-eye core/shell spheroid anode/cathode. In this regards, Raman spectroscopy of SSB@nano-C composite material is recorded with 10 scans of 5s in the range of 500-2000 cm −1 , as shown in in SSB@nano-C, respectively. The C-D-peak match to a disordered carbon of highly defective graphite and the C-G-peak is related to (graphite, in-plane vibrations with E 2g symmetry).
Therefore, according to Raman and FT-IR analysis, it confirms the present of thin carbon layer on surface of SSB@nano-C which is partially cross-linked via C=C, C=N, C=O bonds after carbonization.

XPS analysis is investigated the materials compositions, oxidation states and valences of 3D-
LFPO@nano-C cathode materials such as SSB@nano-C geometrics (Fig. S9).
The plane indicates the feasible Li + -ion lithiation and delithiation pathways for superb electron-ion kinetics and fast ionic diffusion during discharge-charge cycle process, see Figure S10 (b). The SSB@nano-C crystal structure shows highly-exposed ac-plane orientation, leading to formulate low surface energy topologies for fast electrons/ Li + -ions diffusion dynamics within lithiation/delithiation process. Figure S10c shows diffraction peaks of ETO@nano-C anode with tetragonal structure with I4 1 /amd space symmetry. The XRD pattern indicates the formation of

S11. Stability of anode and cathode structures for fully-reversible cycles
We investigate the stability of anode and cathode structures for fully-reversible cycles through the microscopic analyses using SEM and EDX profiles of anode and cathode material structures after multiple 100 th cycles ( Figure S11).

Figure S11
SEM and EDX patterns of SSB@nano-C cathode material structures after multiple 100 th cycles.
Overall, the electrochemical cycling performance analysis clarified the stability of structurallystable anode/cathode electrodes designed in half-or full-cell cathode LIB-CR2032 designs. The retention of anode/cathode structure geometry and surface topology leads to full dynamic LIB storage and accommodation systems, in which heavily loaded Li + -ion diffusion, and minimized electron transport distance are characterized for cycled electrodes. The electrode uniqueness in its sustainability of electronic conductivity would enhance the rate capability, and kinetic Li + -ion transport efficiency during the lithiation (discharge)/delithiation (charge) processes. For instance, the microscopic patterns show the stability of SSB@nano-C material designed in half-and full-cell LIB-CR2032 designs. This finding leads to stable design configurations due to the retention of functional surface interfaces of spheroids/cuboids and its rich spatial distribution in complexity,

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anisotropy, and heterogeneity. The patterns of cycled cathode materials show the retention of mesoscopic supper-open-eye core/shell spheroids, and interiorly uniform accommodation/storage space pockets (i.e., surface mesogrooves and mesoeye entrances, interior innumerable caves and core hollowness-like nests), and the 6-facet cuboid-capped gradients that indicate the functional ability of the SBB@nano-C module in simultaneous, full-scale LIB models. Furthermore, the stability of well-and large-scale surface dispersion of thin C-shell dressings along SBB@nano-C cathode layers plays an important role in preventing Fe dissolution or atomic dislocation (i.e., wellstructured robustness) against severe treatment conditions, thereby enabling excellent sustainability of the electronic surface mobility and conductivity within cycles.

S12. Functional cell parameters of super-open-mesoeye half-, and full-cell LIB-CR2032
designs