Li-ion Diffusion Kinetics Research Articles

Mitigating the Kinetic Hysteresis of Co-Free Ni-Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon.

Co-free Ni-rich layered oxides are considered a promising cathode material for next-generation Li-ion batteries due to their cost-effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li-ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si-O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co-free Ni-rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li-ion diffusion kinetics in atomic and electrode particle scales, the as-obtained cathodes (LiNixMn1-xSi0.01O2, 0.6≤x≤0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li-ion transport properties, and the concept will inspire more researchers to conduct an intensive study.

Dual-Seed Strategy for High-Performance Anode-Less All-Solid-State Batteries.

Interest in all-solid-state batteries (ASSBs), particularly the anode-less type, has grown alongside the expansion of the electric vehicle (EV) market, because they offer advantages in terms of their energy density and manufacturing cost. However, in most anode-less ASSBs, the anode is covered by a protective layer to ensure stable lithium (Li) deposition, thus requiring high temperatures to ensure adequate Li ion diffusion kinetics through the protective layer. This study proposes a dual-seed protective layer consisting of silver (Ag) and zinc oxide (ZnO) nanoparticles for sulfide-based anode-less ASSBs. This dual-seed-based protective layer not only facilitates Li diffusion via multiple lithiation pathways over a wide range of potentials, but also enhances the mechanical stability of the anode interface through the in situ formation of a Ag-Zn alloy with high ductility. The capacity retention during full-cell evaluation is 80.8% for 100 cycles when cycled at 1mA cm-2 with 3 mAh cm-2 at room temperature. The dual-seed approach provides useful insights into the design of multi-seed concepts in which, from a mechanochemical perspective, various lithiophilic materials synergistically impact upon the anode-less interface.

One-step surface-to-bulk modification of single-crystalline Ni-rich Co-poor cathodes for high-rate and long-life Li-ion batteries at high-voltage operations

Single-crystalline Ni-rich Co-poor cathodes operating at high-voltage are attractive owing to their higher energy density for meeting the requirements of next-generation Li-ion batteries, yet they usually suffer from sluggish Li-ion diffusion kinetics and serious Li/Ni disordering. Herein, an in-situ co-precipitation strategy is implemented to achieve the novel In-doped and Li3InO3 coated single-crystalline LiNi0.90Co0.05Mn0.05O2 cathodes with a highly ordered layered structure. The In-doping facilitates grain growth by decreasing the surface energy of crystal faces, reducing the synthesis temperature by about 20 °C, which thus drastically suppresses Li/Ni disordering and lattice oxygen loss. Furthermore, the pillar effect of In-ion doping and the in-situ formation of the ultrafast Li-ion conductive Li3InO3 coating synergistically enhance the Li-ion diffusion kinetics. These merits enable the as-obtained Ni-rich Co-poor cathodes with a high reversible capacity of 229.4 mAh g−1 at 0.1C and 124.6 mAh g−1 at 7C. In a pouch-type full cell, 93.9 % of the initial capacity is still maintained after 500 cycles at 1C within 2.7–4.5 V. This finding opens up a new path for improving the rate performance and cycle life of single-crystalline Ni-rich cathodes for high-voltage Li-ion batteries.

Adjusting Ion Diffusion Kinetics of Li Deposition Enabled by an Elastic Porous Melamine Sponge Host for Stable Lithium Metal Anodes.

Lithium (Li) dendritic growth and huge volume expansion seriously hamper Li-metal anode development. Herein, we design a lightweight 3D Li-ion-affinity host enabled by silver (Ag) nanoparticles fully decorating a porous melamine sponge (Ag@PMS) for dendrite-free and high-areal-capacity Li anodes. The compact Ag nanoparticles provide abundant preferred nucleation sites and give the host strong conductivity. Moreover, the high specific surface area and polar groups of the elastic, porous melamine sponge enhance the Li-ion diffusion kinetics, prompting homogeneity of Li deposition and stripping. As expected, the integrated 3D Ag@PMS-Li anode delivered a remarkable electrochemical performance, with a Coulombic efficiency (CE) of 97.14% after 450 cycles at 1 mA cm-2. The symmetric cell showed an ultralong lifespan of 3400 h at 1 mA cm-2 for 1 mAh cm-2. This study provides a facile and cost-effective strategy to design an advanced 3D framework for the preparation of a stable dendrite-free Li metal anode.

Synergistic Engineering of CoO/MnO Heterostructures Integrated with Nitrogen-Doped Carbon Nanofibers for Lithium-Ion Batteries.

The integration of heterostructures within electrode materials is pivotal for enhancing electron and Li-ion diffusion kinetics. In this study, we synthesized CoO/MnO heterostructures to enhance the electrochemical performance of MnO using a straightforward electrostatic spinning technique followed by a meticulously controlled carbonization process, which results in embedding heterostructured CoO/MnO nanoparticles within porous nitrogen-doped carbon nanofibers (CoO/MnO/NC). As confirmed by density functional theory calculations and experimental results, CoO/MnO heterostructures play a significant role in promoting Li+ ion and charge transfer, improving electronic conductivity, and reducing the adsorption energy. The accelerated electron and Li-ion diffusion kinetics, coupled with the porous nitrogen-doped carbon nanofiber structure, contribute to the exceptional electrochemical performance of the CoO/MnO/NC electrode. Specifically, the as-prepared CoO/MnO/NC exhibits a high reversible specific capacity of 936 mA h g-1 at 0.1 A g-1 after 200 cycles and an excellent high-rate capacity of 560 mA h g-1 at 5 A g-1, positioning it as a competitive anode material for lithium-ion batteries. This study underscores the critical role of electronic and Li-ion regulation facilitated by heterostructures, offering a promising pathway for designing transition metal oxide-based anode materials with high performances for lithium-ion batteries.

Enhancing the lithium storage properties of SiO@NC anode by MnNb2O6 decoration

The scalable application of SiO anode in lithium ion batteries is still limited by its low initial Coulombic efficiency and inferior cycle stability. Compositing SiO with other substances that own high structural stability, fast Li ion diffusion rate and good Li ion storage capacity has been proven of effectiveness to tackle the aforementioned problems. Herein, manganese niobate (MnNb2O6) that possesses 3-dimensional Li ion diffusion channels is used to modify SiO anode in conjunction with N-doped carbon coating to improve the Li-ion storage performance. Ex situ XRD measurements reveal that the orthorhombic MnNb2O6 is converted to amorphous LixMnNb2O6 during lithiation and reversed back to MnNb2O6 in the following delithiation process. The crystal structure of MnNb2O6 is well preserved after a long-term cycle test, suggesting its high structural stability. With such stable structure and ultrafast Li ion diffusion kinetics, the optimized SiO@MnNb2O6@NC composite anode exhibits obviously improved rate performance and cycle stability as compared to SiO@NC. A reversible capacity of 835 mAh g−1 is maintained at a relatively high current density of 3.0 A g−1, and a discharge capacity of 799 mAh g−1 is preserved after 200 cycles at 1.0 A g−1. This work provides a facile and promising strategy to modify SiO-based anode with Columbite-type Nb-based metal oxides towards better Li-ion storage properties.

Cellulose derived fibrous vanadium-sulfide/carbon composite with enhanced lithium storage properties

Vanadium-sulfides are considered as promising anodic materials for lithium-ion batteries (LIBs) due to their unique layered structures and high theoretical capacities. However, the main challenge of vanadium-sulfide as an electrode material is still faced with slow Li-ion diffusion kinetics and inevitable structural damage during charging/discharging processes. Herein, a series of bio-inspired hierarchical fibrous VS4/C composites were designed based on cellulose substance as the scaffold and carbon source via simple hydrothermal method. The resultant fibrous VS4/C composites possessed a three-dimensional porous network structure consisting of carbon fibers coated with VS4 nanosheets. As a consequence, the optimized VS4/C anodic materials exhibit high reversible capacities (953 mAh g−1 at 0.1 A g−1), good rate features (420 mAh g−1 at 2 A g−1), and fast diffusion kinetics. The superior electrochemical properties of the VS4/C composites are mainly attributed to the three-dimensional porous network structures combined with the carbon fibers matrix, which promotes the contact between the electrode and electrolyte, alleviates the structural damage of VS4, as well as facilitates the electron transfer and Li-ion diffusion during the cycling processes.

The Impact of Structural Pattern Types on the Electrochemical Performance of Ultra-Thick NMC 622 Electrodes for Lithium-Ion Batteries

An increase in the energy density on the cell level while maintaining a high power density can be realized by combining thick-film electrodes and the 3D battery concept. The effect of laser structuring using different pattern types on the electrochemical performance was studied. For this purpose, LiNi0.6Mn0.2Co0.2O2 (NMC 622) thick-film cathodes were prepared with a PVDF binder and were afterward structured using ultrafast laser ablation. Eight different pattern types were realized, which are lines, grids, holes, hexagonal structures, and their respective combinations. In addition, the mass loss caused by laser ablation was kept the same regardless of the pattern type. The laser-structured electrodes were assembled in coin cells and subsequently electrochemically characterized. It was found that when discharging the cells for durations of less than 2 h, a significant, positive impact of laser patterning on the electrochemical cell performance was observed. For example, when discharging was performed for one hour, cells containing laser-patterned electrodes with different structure types exhibited a specific capacity increase of up to 70 mAh/g in contrast to the reference ones. Although cells with a hole-patterned electrode exhibited a minimum capacity increase in the rate capability analysis, the combination of holes with lines, grids, or hexagons led to further capacity increases. In addition, long-term cycle analyses demonstrated the benefits of laser patterning on the cell lifetime, while cyclic voltammetry highlighted an increase in the Li-ion diffusion kinetics in cells containing hexagonal-patterned electrodes.

Building oxygen-rich vacancy coating for fast Li-ion diffusion kinetics and stable cycling of lithium-rich layered oxide cathode at wide-temperature

As a cathode with a high energy density for Li-ion batteries, Li-rich layered oxide (LLO) cathodes suffer from short lifespans and poor rate performance, mainly due to their irreversible lattice oxygen evolution leading to severe structural degradation and oxygen release. Herein, we propose the use of Zn-doped SnO2 coated with LLO cathode to tackle these issues. Compared to the traditional method of coating oxides on the surface of lithium-rich cathodes, Zn doping of SnO2 coating can artificially create abundant oxygen vacancies for LLO cathode, which can provide a buffer boundary for active oxygen generated by lithium-rich cathode during circulation, effectively promoting the reversible reaction of oxygen redox couple and stabilizing lattice oxygen. The experimental results show that the surface of the LLO cathode's Zn-doped SnO2 is rich in oxygen vacancies could significantly boost the kinetics of lithium ion transfer, and effectively inhibit layer-to-spinel phase transition, and lattice oxygen release. By taking advantage of the Zn-doped SnO2 coating, the capacity stability of LLO cathode is raised from 58.1 % to 86.7 % at 1C after 500 cycles and also obtains outstanding rate performance and cycling durability at wide-temperature (−10 to 55 °C).

A Promising Solid-State Synthesis of LiMn1- yFeyPO4 Cathode for Lithium-ion Batteries.

LiMn1-yFeyPO4 (LMFP) is a significant and cost-effective cathode material for Li-ion batteries, with a higher working voltage than LiFePO4 (LFP) and improved safety features compared to layered oxide cathodes. However, its commercial application faces challenges due to a need for a synthesis process to overcome the low Li-ion diffusion kinetics and complex phase transitions. Herein, a solid-state synthesis process using LFP and nano LiMn0.7Fe0.3PO4 (MF73) is proposed. The larger LFP acts as a structural framework fused with nano-MF73, preserving the morphology and high performance of LFP. These results demonstrate that the solid-state reaction occurs quickly, even at a low sintering temperature of 500 °C, and completes at 700 °C. However, contrary to the expectations, the larger LFP particles disappeared and fused into the nano-MF73 particles, revealing that Fe ions diffuse more easily than Mn ions in the olivine framework. This discovery provides valuable insights into understanding ion diffusion in LMFP. Notably, the obtained LMFP can still deliver an initial capacity of 142.3 mAh g-1, and the phase separation during the electrochemical process is significantly suppressed, resulting in good cycling stability (91.1% capacity retention after 300 cycles). These findings offer a promising approach for synthesizing LMFP with improved performance and stability.

Insights into the kinetics–morphology relationship of 1-, 2-, and 3D TiNb2O7 anodes for Li-ion storage

Understanding the influence of electrode material’s morphology on electrochemical behavior is of great significance for the development of rechargeable batteries, however, such studies are often limited by the inability to precisely control the morphology of electrode materials. Herein, nanostructured titanium niobium oxides (TiNb2O7) with three different morphologies (one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D)) were synthesized via a facile microwave-assisted solvothermal method. The influence of the morphological dimension of TiNb2O7 as electrode material on the electrochemical performance in Li-ion batteries (LIBs) and the underlying correlation with the electrochemical kinetics were studied in detail. 2D TiNb2O7 (TNO-2D) shows a superior rate capability and cycling stability, associated with improved kinetics for charge transfer and Li-ion diffusion, compared to the 1D and 3D materials. Operando X-ray diffraction measurements reveal the structural stability and crystallographic evolution of TNO-2D upon lithiation and delithiation and correlate the Li-ion diffusion kinetics with the lattice evolution during battery charge and discharge. Moreover, carbon-coated TNO-2D achieves enhanced rate capability (205 mAh·g−1 at 50 C) and long-term cycling stability (87% after 1000 cycles at 5 C). This work provides insights into the rational morphology design of electrode materials for accelerated charge transfer and enhanced fast-charging capability, pushing forward the development of electrode materials for high-power rechargeable batteries in future energy storage.

Superb Li-Ion Storage of Sn-Based Anode Assisted by Conductive Hybrid Buffering Matrix.

Although Sn has been intensively studied as one of the most promising anode materials to replace commercialized graphite, its cycling and rate performances are still unsatisfactory owing to the insufficient control of its large volume change during cycling and poor electrochemical kinetics. Herein, we propose a Sn-TiO2-C ternary composite as a promising anode material to overcome these limitations. The hybrid TiO2-C matrix synthesized via two-step high-energy ball milling effectively regulated the irreversible lithiation/delithiation of the active Sn electrode and facilitated Li-ion diffusion. At the appropriate C concentration, Sn-TiO2-C exhibited significantly enhanced cycling performance and rate capability compared with its counterparts (Sn-TiO2 and Sn-C). Sn-TiO2-C delivers good reversible specific capacities (669 mAh g-1 after 100 cycles at 200 mA g-1 and 651 mAh g-1 after 500 cycles at 500 mA g-1) and rate performance (446 mAh g-1 at 3000 mA g-1). The superiority of Sn-TiO2-C over Sn-TiO2 and Sn-C was corroborated with electrochemical impedance spectroscopy, which revealed faster Li-ion diffusion kinetics in the presence of the hybrid TiO2-C matrix than in the presence of TiO2 or C alone. Therefore, Sn-TiO2-C is a potential anode for next-generation Li-ion batteries.

Hybrid ionic/electronic interphase enabling uniform nucleation and fast diffusion kinetics for stable lithium metal anode

Lithium (Li) dendrite issue, which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase (SEI), impedes the further development of high-energy Li metal batteries. However, the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short. Herein, we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix. The generated Co and LiF both enable fast Li-ion diffusion kinetics, meanwhile, the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites, thereby contributing to uniform Li nucleation and non-dendritic growth. As a result, a dendrite-free Li deposition with a low overpotential (16.1 mV) is achieved, which enables an extended lifespan over 750 h under strict conditions. The full cells with high-mass-loading LiFePO4 (11.5 mg/cm2) as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4% after undergoing 180 cycles.

Stabilizing Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode by generating ion-conductive polymer coating layer with 1, 3-dioxolane introducing electrolyte for lithium-ion batteries

The employment of electrolyte-film forming additive is a facile and effective strategy to improve the cycling performance of aggressive Nickel-rich layered oxide cathode LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode for high energy lithium-ion batteries (LIBs). Here we report a homogeneous and dense polymer cathode-electrolyte-interface (CEI) film generated via in-situ electrooxidation polymerization of 1, 3-Dioxolane (DOL) in a conventional carbonate-based electrolyte. It is found that the electrolyte modification with 15% DOL is the most effective in balancing the interfacial stability and Li-ion diffusion kinetics of NCM811 cathode, while also achieving its comparable rate capability and greatly improving cycling performance. Morphological and elemental characterizations demonstrate that the 15% DOL-derived CEI layer not only alleviates the impacts of harmful interfacial reactions and hinders the particle disintegration, but also suppresses the irreversible lattice transition of the NCM811 cathode surface to the inactive rock salt phase. Moreover, it is proved that the F-rich interfacial layer displays excellent Li-ion transport kinetics. As a result, the cell exhibits high capacity retention of 85.2% and 78.1% after 200 cycles at cut-off voltages of 4.3 V and 4.5 V at 1 C in the 15% DOL-modified electrolyte. Therefore, creating a stable and effective Li-ion conductive interfacial protective film on the cathode surface by optimizing an electrolyte functional additive is an economical and available approach to develop the highly stabilized Ni-rich cathode for high-energy LIBs applications.

Enhanced electrochemical performance of nanoscale single crystal NMC811 modification by coating LiNbO3

Single crystallization is an important strategy to resolve intergranular cracks and unnecessary side reactions with electrolytes in layered transition metal oxide cathodes LiNi0.8Mn0.1Co0.1O2 (NMC811). Due to the limitations of high-temperature sintering and multi-step calcination, single crystal NMC811 generally shows irregular particles with a size of 2–3 µm. However, the prolonged Li-ion diffusion pathway and the stress generated by the uneven de-/intercalation sluggish Li-ion diffusion kinetics, what is more, cause structural damage such as intragranular cracks. A slow Li extraction rate or particle size reduction will ameliorate the structural damage and improve the cycling stability. As the most promising cathodes for next-generation power batteries, NMC811 required fast charge performance and cycle stability. Particle size reduction appears to be the displacement option. Nanonization is an effective strategy to mitigate intragranular cracks of single crystal NMC811. However, the serious aggregation and increased specific surface area become new challenges. In this article, we synthesized monodisperse nanoscale single crystal NMC811 by molten salt method and modified the surface by LiNbO3 coating. The electrochemical performance shows that nanoscale single crystal NMC811 has faster kinetic and higher capacity retention, so the strategy of combining nanonization and surface coating is an alternative way to prepare high specific capacity and cycle stable single crystal NMC811.

强耦合氧化钼氮碳复合材料的制备及其锂离子存储性能研究

Molybdenum oxide (MoO3) is an attractive anode material for lithium-ion batteries (LIBs); however, its low electrical conductivity, large volume expansion after lithiation, and slow Li-ion diffusion kinetics severely limit its practical applications. Here, ultrafine MoO3 nanoparticles (NPs) (10–15 nm) are synthesized from heavily Mo/N-doped carbonaceous precursors, resulting in MoO3 NPs confined in an N-doped carbon network. This design allows fast electron conduction and short Li-ion diffusion paths; meanwhile, abundant N species and O vacancies on the MoO3 surface lower the Li-ion adsorption barrier and together contribute to the durable Li-ion storage at high current rates. Notably, the obtained nanocomposite NC-MoO3 exhibits a high capacity of 1362 mA h g−1 (0.1 A g−1) and maintains a reversible capacity of 394 mA h g−1 at 10.0 A g−1. A coin-type full LiFePO4//NC-MoO3-400 cell obtains a large specific capacity of 81 mA h g−1 at 5 C. Our work inspires the design and confinement synthesis of other transition metal oxides embedded in conducting carbon networks for practical LIB applications.

Accelerated Li+ Desolvation for Diffusion Booster Enabling Low‐Temperature Sulfur Redox Kinetics via Electrocatalytic Carbon‐Grazfted‐CoP Porous Nanosheets

AbstractLithium–sulfur (Li–S) batteries are famous for their high energy density and low cost, but prevented by sluggish redox kinetics of sulfur species due to depressive Li ion diffusion kinetics, especially under low‐temperature environment. Herein, a combined strategy of electrocatalysis and pore sieving effect is put forward to dissociate the Li+ solvation structure to stimulate the free Li+ diffusion, further improving sulfur redox reaction kinetics. As a protocol, an electrocatalytic porous diffusion‐boosted nitrogen‐doped carbon‐grafted‐CoP nanosheet is designed via forming the NCoP active structure to release more free Li+ to react with sulfur species, as fully investigated by electrochemical tests, theoretical simulations and in situ/ex situ characterizations. As a result, the cells with diffusion booster achieve desirable lifespan of 800 cycles at 2 C and excellent rate capability (775 mAh g−1 at 3 C). Impressively, in a condition of high mass loading or low‐temperature environment, the cell with 5.7 mg cm−2 stabilizes an areal capacity of 3.2 mAh cm−2 and the charming capacity of 647 mAh g−1 is obtained under 0 °C after 80 cycles, demonstrating a promising route of providing more free Li ions toward practical high‐energy Li–S batteries.

InSb: A Stable Cycling Anode Material Enables Fast Charging of Li-Ion Batteries at Sub-zero Temperatures

In this work we surprisingly find that the reaction mechanism, Li-ion diffusion kinetics, and polycrystalline sphalerite structure of the InSb anode materials remain unchanged during the charging and discharging process at both room and sub-zero temperatures. The sputtered pure InSb film anodes can stably cycle more than 800 times at 1 A/g and deliver a high capacity of 534.6 mAh/g at 30 °C. With a high current rate of 2 A/g at −40 °C, a capacity of 402.8 mAh/g can be maintained. For the ball-milled InSb/graphite composite, a capacity of 434.3 mAh/g at 1 A/g can remain very stable for more than 700 cycles at both 30 °C and −50 °C. The 2500 mAh soft pack cells, which are made entirely from the commercialization process and successfully run long-term at −30 °C, also demonstrate the potential of InSb anodes for commercial applications.

Concentration-Gradient Nb-Doping in a Single-Crystal LiNi0.83Co0.12Mn0.05O2 Cathode for High-Rate and Long-Cycle Lithium-Ion Batteries

Single-crystalline nickel-rich layered oxides are promising cathode materials for building high-energy lithium-ion batteries because of alleviated particle cracking and irreversible phase transitions upon cycling, compared with their polycrystalline counterparts. Under a high state of charge, parasitic reactions tend to occur at the cathode-electrolyte interface, which could result in sluggish Li-ion diffusion kinetics and quickly faded electrochemical performance of cathodes. In this work, a concentration-gradient niobium-doping strategy was applied to modify the single-crystal LiNi0.83Co0.12Mn0.05O2 cathode, with Nb concentration decreasing linearly from the surface to the core of the particle. As a result, the Nb-rich surface functions as an electrochemically active protective layer against electrolyte corrosion and transition metal dissolution, while the Nb-deficient core contributes to a higher capacity. The linear concentration gradient also minimizes structural transition from the surface to the core and helps to maintain structural integrity during repeated Li (de)intercalation. In addition, Nb-doping also assists to alleviate Li+/Ni2+ mixing and increases the interlayer distance to enable faster Li-ion diffusion kinetics. By taking these advantages, the Nb-doped cathode materials (containing 1.0 atom% Nb) demonstrate a high reversible capacity, a high capacity retention, and improved rate capabilities. This work provides a general and facile approach to improve the storage performance of layered-oxide cathode materials by rationally tuning the bulk structure and interface with the electrolyte.

Vacancy engineering in Co-doped CuS1-x with fast Electronic/Ionic migration kinetics for efficient Lithium-Ion batteries

Slow Li ion diffusion kinetics and disordered migration of electrons are two most crucial obstacles to be resolved in electrode material design for higher rate capability of Li-ion batteries. Herein, the Co-doped CuS1-x with abundant high active S vacancies is proposed to accelerate the electronic and ionic diffusion during the energy conversion process, because contraction of Co-S bond can cause the expansion of atomic layer spacing, thus promoting the Li ion diffusion and directional electron migration parallel to the Cu2S2 plane, and also induce the increasing of active sites to improve the Li+ adsorption and electrocatalytic conversion kinetics. Especially, the electrocatalytic studies and plane charge density difference simulations demonstrate that electron transfer near the Co site is more frequent, which is conducive to more rapid energy conversion and storage. Those S vacancies formed by Co-S contraction in CuS1-x structure obviously increase Li ion adsorption energy in Co-doped CuS1-x to 2.21 eV, higher than the 2.1 eV for CuS1-x and 1.88 eV for CuS. Taking these advantages, the Co-doped CuS1-x as anode of Li-ion batterie shows an impressive rate capability of 1309 mAh·g−1 at 1A g−1, and long cycling stability (retaining 1064 mAh·g−1 capacity after 500 cycles). This work provides new opportunities for the design of high-performance electrode material for rechargeable metal-ion batteries.