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a) Cycling performance of NCM‐811 half‐cell with addition of 0, 3, 5 wt% Co‐Li2CO3@LCO at 20 mA g⁻¹ (2.8–4.7 V) during initial cycle and 50 mA g⁻¹ (2.8–4.3 V) in subsequent cycle. The bar chart corresponding to the charge and discharge capacity of the initial cycle is inserted. b) Full cell performance in two different scenarios. Voltage profiles during initial cycle of the SiO/C || Li half‐cell (at 40 mA g⁻¹), and the NCM‐811 || SiO/C full‐cell without/with 9 wt% (at 20 mA g⁻¹). c) Galvanostatic charge/discharge curves of NCM‐811 || SiO/C without/with 9 wt% coin‐type full‐cell at 20 mA g⁻¹ (2.0–4.65 V for 1st) and 50 mA g⁻¹ (2.0–4.2 V for 2nd–50th). Cycling performance of d) NCM‐811 || SiO/C and e) NCM‐811 || Gr coin‐type full cells without/with 9/5 wt%. f) Discharge capacity and coulombic efficiency during cycles of the NCM‐811 || Gr pouch‐type full‐cell with 5 wt%. Inset: a photograph of the pouch cell is shown for clarity. g) Galvanostatic charge curves of TM‐Li2CO3@TM source (LiFePO4, NCM‐333, LiCoO2, spent LiCoO2) with 4.7 V cutoff voltage at 50 mA g⁻¹. The spent LiCoO2 collected from waste cells is in the inset.
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Developing sacrificial cathode pre‐lithiation technology to compensate for active lithium loss is vital for improving the energy density of lithium‐ion battery full‐cells. Li 2 CO 3 owns high theoretical specific capacity, superior air stability, but poor conductivity as an insulator, acting as a promising but challenging pre‐lithiation agent candi...
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Electrolytic copper foil is ideal for use in the anode current collectors of lithium-ion batteries (LIBs) because of its abundant reserves, good electrical conductivity, and soft texture. However, electrolytic copper foil is prone to corrosion in electrolytes and weak bonding to the anode substance. Surface modification of copper foil is considered...
Citations
... With the widespread adoption of new energy vehicles and large-scale energy storage devices, traditional Li + batteries are approaching their limits in the energy storage capacity. [1][2][3][4] Lithium-sulfur (Li-S) batteries, with their high theoretical energy density (2600 W h kg À 1 ) and low cost, are emerging as promising candidates for the next generation of energy storage system. [5] However, the real-world application of LiÀ S batteries has encountered significant obstacles, primarily due to limited practical energy density, low coulombic efficiency, and poor cycling stability. ...
Modifying the separator is considered as an effective strategy for achieving high performance lithium‐sulfur (Li‐S) batteries. However, most modification layers are excessively thick, with catalytic active sites primarily located within the material′s interior. This configuration severely impacts Li⁺ transport and the efficient catalytic conversion of polysulfides. Therefore, there is an urgent need to develop a multifunctional separator that integrates ultrathin design, catalytic activity, and ion sieving capabilities. Herein, we successfully linked TCPP(Ni) as a secondary ligand with Zr‐BTB nanosheets to create an ultra‐thin separator modification layer (Zr‐TCPP(Ni)) with efficient ion sieving and catalytic properties. The resultant multifunctional separators provide robust ion sieving capabilities that promote rapid Li⁺ transport and intercept polysulfides shuttling. Therefore, The Zr‐TCPP(Ni)@PP cell maintains 70.0 % of its initial capacity after 600 cycles at a high rate of 3 C, while achieving an impressive areal capacity of 4.55 mA h cm⁻² even with high sulfur content of 80 wt% at 0.5 C. This work provides valuable insights for rational design of MOF interface engineering in high energy density Li‐S batteries.
... In contrast, sacrificial additives in the cathode are more attractive for their high chemical stability. A number of compounds have been reported for sacrificial cathode additives including Li 3 N [ 7 ], Li 3 P [ 8 ], Li 2 CO 3 [ 9 ], Li 4 SiO 4 [ 10 ], Li 2 C 2 O 4 [ 11 ], Li 2 C 4 O 4 [ 12 ], Li 5 FeO 4 [ 13 ], and Li 6 CoO 4 [ 14 ] and composites of LiF [ 15 ], Li 2 O [ 16 ], and Li 2 S [ 17 ] with metals such as Co and Fe. However, their commercial applications are hindered by severe problems including high electrochemical decomposition potential and mass residues. ...
... However, their commercial applications are hindered by severe problems including high electrochemical decomposition potential and mass residues. For instance, Li 2 CO 3 is insulating and difficult to be decomposed below 4.0 V (versus Li + /Li) even with cobalt (Co) modification [ 9 ]. These severely limit the viable additives. ...
The continuous lithium consumption during cycling severely reduces the energy density of the lithium battery, and thus, lithium compensation is essential. Herein, LixC6O6 (x = 2, 4) was proposed as an air-stable high-efficiency sacrificial additive in the cathode to compensate for the lost lithium ions in solid-state lithium batteries. Below a delithiation (oxidation) potential as low as 3.8 V, Li2C6O6 can release most of its Li⁺ ions (294.8 mAh g⁻¹ in theory). Similarly, Li4C6O6 is also characteristic of low oxidation potential and high delithiation capacity (547.8 mAh g⁻¹ in theory). The feasibility of using LixC6O6 as the self-sacrificial additive in the cathode was verified with the marked increase of the initial charge capacity of the Li||LiFePO4 (half) cells and the initial discharge capacity of Cu||LiFePO4 (full) cells, and the improved electrolyte/cathode interface stability and interface contact, in the solid-state poly(ethylene oxide)-lithium bis(trifluoromethane)sulfonimide (PEO-LiTFSI) electrolyte. In addition, the structure and delithiation of LixC6O6 and the impacts of its decomposition product on the PEO-LiTFSI solid electrolyte were also evaluated on the basis of the comprehensive physical characterizations and the density functional theory (DFT) calculations. These findings open a new avenue for elevating the energy density and/or elongate the lifespan of the solid-state secondary batteries.
... However, its poor stability, poor electrical conductivity, and low initial Coulomb efficiency limit its practical applications. A common strategy to overcome these problems is compounding with conductive materials such as carbon and prelithiation [14,15] . ...
Van der Waals heterostructures made up of different two-dimensional (2D) materials have garnered considerable attention as anodes for lithium-ion batteries (LIBs), and doping can significantly influence their electronic structures and lithium diffusion barriers. In this work, the effects of heteroatom (X = N, O, P, and S) doping in the graphene of the graphene/silicene (G/Si) heterostructure are comprehensively examined by using first-principles calculations. The stacking stability and mechanical stiffness of G/Si and doped G/Si (XG/Si) exhibit that N-doping can improve the structural stability of G/Si, thereby ensuring good cycling performance. The densities of states reveal that the dopants (N, O, and S) can greatly increase the electronic conductivity of G/Si. Importantly, the adsorption and diffusion behaviors of Li are primarily affected by the dopant and the doping site, resulting in ultrafast Li diffusivity. Therefore, N-doped G/Si at doping site 1 (S1) shows a good and balanced property, which exhibits high potential to enhance the electrical performance of G/Si materials and offers a reference for selecting dopants in other 2D anode materials for LIBs.
Li‐ and Mn‐rich layered oxides exhibit high specific capacity due to the cationic and anionic reaction process during high‐voltage cycling (≥4.6 V). However, they face challenges such as low initial coulombic efficiency (~70 %) and poor cycling stability. Here, we propose a combination of H3BO3 treatment and low temperature calcination to construct a shell with cationic vacancy on the surface of Li1.2Ni0.2Mn0.6O2 (LLNMO). The H3BO3 treatment produces cationic vacancy and lattice distortion, forming an oxidized Oⁿ⁻ (0<n<2) on the surface, accompanied by electrons redistribution. Low temperature calcination eliminates lattice distortion, activates metastable Oⁿ⁻ and promotes coherent lattice formation. In addition, the cationic vacancy shell reduces the diffusion energy barrier of Li⁺, allowing more Li⁺ and oxygen to participate in deeper reactions and increasing the oxidation depth of oxygen. The modified material (LLNMO‐H10‐200) exhibits an initial coulombic efficiency of up to 88 % and a capacity of 256 mAh g⁻¹. Moreover, similar enhancements were observed with Co‐containing lithium‐rich materials, with a 280 mAh g⁻¹ discharge capacity and 89 % coulombic efficiency. These findings reveal the correlation between cationic vacancy, metastable oxygen activation and bulk phase activity, offering a novel approach to enhancing the initial coulombic efficiency and cycle stability of Li‐rich materials.
Li‐ and Mn‐rich layered oxides exhibit high specific capacity due to the cationic and anionic reaction process during high‐voltage cycling (≥ 4.6 V). However, they face challenges such as low initial coulombic efficiency (~70%) and poor cycling stability. Here, we propose a combination of H3BO3 treatment and low temperature calcination to construct a shell with cationic vacancy on the surface of Li1.2Ni0.2Mn0.6O2 (LLNMO). The H3BO3 treatment produces cationic vacancy and lattice distortion, forming an oxidized On‐ (0<n<2) on the surface, accompanied by electrons redistribution. Low temperature calcination eliminates lattice distortion, activates metastable On‐ and promotes coherent lattice formation. In addition, the cationic vacancy shell reduces the diffusion energy barrier of Li+, allowing more Li+ and oxygen to participate in deeper reactions and increasing the oxidation depth of oxygen. The modified material (LLNMO‐H10‐200) exhibits an initial coulombic efficiency of up to 88% and a capacity of 256 mAh g‐1. Moreover, similar enhancements were observed with Co‐containing lithium‐rich materials, with a 280 mAh g‐1 discharge capacity and 89% coulombic efficiency. These findings reveal the correlation between cationic vacancy, metastable oxygen activation and bulk phase activity, offering a novel approach to enhancing the initial coulombic efficiency and cycle stability of Li‐rich materials.
Compared to commercial current collectors (CCs), polymer‐based current collectors (PBCCs) significantly enhance the energy and safety of lithium‐ion batteries. However, the inherent transverse non‐conductivity of traditional PBCCs necessitates the use of complex welding processes during cell assembly thus sacrificing the energy density, stemming from the insulating nature of the intermediate polymer layer in PBCCs. Here, newly designed PI‐CNTs‐Al and PI‐CNTs‐Cu PBCCs are developed by integrating highly conductive carbon nanotubes (CNTs) into the polymer interlayer, which is coated with two metal layers to facilitate longitudinal conductivity. The incorporation of CNTs forms a 3D conductive network within the interlayer, substantially improving the transverse conductivity of PI‐CNTs‐Al and PI‐CNTs‐Cu from 2.19×10⁻⁹ and 1.89×10⁻⁹ S m⁻¹ to 1.02 and 1.15 S m⁻¹. Furthermore, the addition of CNTs enhances the bonding strength at the metal‐polymer interface, effectively mitigating separation defects commonly observed in traditional PI‐Al and PI‐Cu CCs. The engineered PBCCs can be utilized directly as CCs for cell assembly without complex conductive components. Importantly, the fully charged 1.5 Ah cell, achieving an energy density of 235.8 Wh kg⁻¹ with a 9.0% improvement, successfully endures rigorous needling tests, which can be attributed to the enhanced tensile strength and reduced fracture strain ratio of the PBCCs.
Modifying the separator is considered as an effective strategy for achieving High performance lithium‐sulfur (Li‐S) batteries. However, most modification layers are excessively thick, with catalytic active sites primarily located within the material's interior. This configuration severely impacts Li+ transport and the efficient catalytic conversion of polysulfides. Therefore, there is an urgent need to develop a multifunctional separator that integrates ultrathin design, catalytic activity, and ion sieving capabilities. Herein, we successfully linked TCPP(Ni) as a secondary ligand with Zr‐BTB nanosheets to create an ultra‐thin separator modification layer (Zr‐TCPP(Ni)) with efficient ion sieving and catalytic properties. The resultant multifunctional separators provide robust ion sieving capabilities that promote rapid Li+ transport and intercept polysulfides shuttling. Therefore, The Zr‐TCPP(Ni)@PP cell maintains 79.45% of its initial capacity after 400 cycles at a high rate of 3 C, while achieving an impressive areal capacity of 4.55 mA h cm‐2 even with high sulfur content of 80 wt% at 0.5 C. This work provides valuable insights for rational design of MOF interface engineering in high energy density Li‐S batteries.
Pre-lithiation, which is capable of supplying additional active lithium sources to lithium-ion batteries, has been widely accepted as one of the most promising approaches for addressing the issue of active lithium loss during the entire process of initial charging and subsequent cycling. In comparison with anode pre-lithiation, cathode pre-lithiation exhibits a facile operating procedure and good compatibility with current lithium-ion battery production processes. However, cathode pre-lithiation additives suffer from high decomposition voltage and low decomposition efficiency. In view of this, a variety of nanocatalysts have been developed in recent years to enhance the decomposition kinetics of cathode pre-lithiation additives. Nevertheless, a comprehensive review of nanocatalysis in cathode pre-lithiation is still lacking. This timely review aims to present the crucial role of nanocatalysis in cathode pre-lithiation and provide an up-to-date overview of this field. After demonstrating the significance of nanocatalysts for cathode pre-lithiation, recent progress in the application of nanocatalysts for high-efficiency cathode pre-lithiation is briefly introduced. Finally, future challenges and directions for the commercialization of the cathode pre-lithiation technique in conjunction with nanocatalysts are reviewed. The current review provides important insights into nanocatalysis as a cutting-edge strategy for favorable cathode pre-lithiation and builds a bridge between academic research and industrial applications of nanocatalytic cathode pre-lithiation for lithium-ion batteries with high capacity and good cyclability.