Promising Anode Material Research Articles

Theoretical prediction of two-dimensional metallic AM2B8 (AM = K, Rb, Cs) as anode materials for Na-ion batteries

The development of two-dimensional anode materials with superior performance is becoming a critical undertaking for the advancement of Na-ion battery technology. Using isoelectronic substitution strategies, we predicted three alkali metal borides AM2B8 (AM = K, Rb, Cs) based on the SrB8 monolayer. Ab initio molecular dynamics simulations and phonon dispersion relationship calculations demonstrated their stability. Using density functional theory, we predict the feasibility of these three new metal nanosheets as anodes for Na-ion batteries. The AM2B8 monolayer retains its metallicity after the insertion of Na ions, ensuring that the anode has good electrical conductivity. In addition, AM2B8 has a low diffusion barrier and open circuit voltage (K2B8 is 0.08 eV and 0.26 V) during charge/discharge. In the voltage range that inhibits dendrite growth, K2B8 can reach the maximum theoretical specific capacity (326 mAh/g). These results indicate that AM2B8, especially K2B8, is a promising anode material for Na-ion batteries.

Understanding the Effect of Lithium Nitrate as Additive in Carbonate-Based Electrolytes for Silicon Anodes

Due to its high specific capacity, silicon is one of the most promising anode materials for next-generation lithium-ion batteries. However, its large volumetric changes upon (de)lithiation of ∼300% lead to a rupture/re-formation of the solid-electrolyte interphase (SEI) upon cycling, resulting in continuous electrolyte consumption and irreversible loss of lithium. Therefore, it is crucial to use electrolyte systems that form a more stable SEI that can withstand large volume changes. Here, we investigate lithium nitrate (LiNO3) and lithium nitrite (LiNO2) as electrolyte additives. Linear scan voltammetry on carbon black working electrodes in a half-cell configuration with LiNO3-containing 1 M LiPF6 in EC/DEC (1/2 v/v) revealed a two-step reduction mechanism, whereby the first reduction peak could be attributed to the conversion of LiNO3 to LiNO2, while X-ray photoelectron spectroscopy on harvested electrodes suggests the formation of Li3N during the second reduction peak. On-line electrochemical mass spectrometry (OEMS) on carbon black electrodes showed that N2O gas is evolved upon the reduction of LiNO3- and LiNO2-containing electrolytes but that the gassing associated with EC reduction is significantly reduced. Furthermore, OEMS and voltammetry were used to examine the redox chemistry of LiNO2 additive. Finally, LiNO3 and LiNO2 additives significantly improved the cycle-life of Si||NCM622 full-cells.

Multi boron-doping effects in hard carbon toward enhanced sodium ion storage

Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs). The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na+ storage capability, however, a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly desirable. Herein, we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry. A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree, which provides more Na+ storage sites. In-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC3 and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI, which leads to facilitated charge transfer and excellent rate performance. As a result, the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling performance. In general, this work unravels the critical role of boron doping in optimizing the pore structure, interface chemistry and diffusion kinetics of hard carbon, which enables rational design of sodium-ion battery anode with enhanced Na+ storage performance.

Enhancing micro-scale SiOx anode durability: Electro-mechanical strengthening of binder networks via anchoring carbon nanotubes with carboxymethyl cellulose

With the increasing prevalence of lithium-ion batteries (LIBs) applications, the demand for high-capacity next-generation materials has also increased. SiOx is currently considered a promising anode material due to its exceptionally high capacity for LIBs. However, the significant volumetric changes of SiOx during cycling and its initial Coulombic efficiency (ICE) complicate its use, whether alone or in combination with graphite materials. In this study, a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiOx blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker. In addition, a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiOx. The combination of these two strategies increased the CE of SiOx from 74% to 87% and effectively mitigated its volume expansion in the graphite/SiOx blended electrode, resulting in an efficient electron-conductive binder network. This led to a remarkable capacity retention of 94% after 30 cycles, even under challenging conditions, with a high capacity of 550 mA h g−1 and a current density of 4 mA cm−2. Furthermore, to validate the feasibility of utilizing prelithiated SiOx anode materials and the conductive binder network in LIBs, a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used. This cell demonstrated a ∼27.3% increase in discharge capacity of the first cycle (∼185.7 mA h g−1) and exhibited a cycling stability of 300 cycles. Thus, this study reports a simple, feasible, and insightful method for designing high-performance LIB electrodes.

Unlocking the potential of Mg-ion batteries: Cu2C MXene anode with ultrahigh storage and energy density with rapid Mg diffusion

Magnesium-ion batteries hold immense promise for the future of electrical energy storage due to the abundant availability of magnesium metal and the efficient energy storage capacity of divalent magnesium ions which has the potential to revolutionize both large-scale stationary applications and portable devices. MXenes, encompassing transition metal carbides/nitrides/carbonitrides, are still considered newcomers in the domain of 2D nanomaterials, especially regarding their utilization in energy storage applications. In this work, we employed first principles based DFT calculations to comprehensively evaluate the electrochemical behavior of 2H phase Cu-based MXene (Cu2C) monolayer as promising anode material for Mg-ion batteries. The stability of the Cu2C monolayer was assessed through calculations of negative cohesive energy, positive phonon frequencies, and AIMD simulations to confirm stability at room temperature along with superior mechanical strength. The simulation outcomes show that strong affinity for Mg ions to the Cu2C monolayer, which is attributed to metallic character, suggesting good electronic conductivity and aslo, the calculated negative adsorption energy of −1.25 eV, indicating a favorable interaction for potential battery applications. The Cu2C monolayer emerges as a compelling candidate for anode materials due to its exceptional combination of high theoretical specific capacity (1541.36 mAh/g) and a low average operating voltage (0.50 V). This translates to a remarkable energy density of 2882.34 mWh/g (referenced against the standard hydrogen electrode potential), making it a strong contender for next-generation battery technologies. Furthermore, our investigation revealed rapid diffusion barriers for Mg-ion migration with exceptional properties with robust compatibility with electrolytes, makes it anode materials for Mg-ion batteries, attracting significant interest in the near future.

Electrochemical sodium storage properties in monolayer VOPO4: A density functional theory prediction

The unique structural properties of two-dimensional materials make them promising for energy storage applications. This work theoretically predicts for the first time that Monolayer VOPO4 (MNL VOPO4), exfoliated from the delithiated phase of tetragonal LiVOPO4, is stable at room temperature, exhibiting excellent thermodynamic and kinetic stability, thus making it a promising high-capacity anode material for sodium-ion batteries (SIBs). Compared to bulk VOPO4, the monolayer structure significantly reduces the sodium ion migration energy barrier from 1.006 to 0.0795 eV, thereby markedly enhancing sodium ion migration kinetics. MNL VOPO4 can adsorb up to 32 sodium ions, corresponding to a theoretical capacity of 634.88 mA h g−1 and an energy density of 895.18 Wh kg−1. Furthermore, the excellent structural stability of MNL VOPO4 favors its cycling performance during charge and discharge processes. This work provides theoretical insights for better utilizing and developing multi-atomic phosphate compounds as electrode materials for secondary batteries.

Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries.

Transition metal oxides are considered to be highly promising anode materials for high-energy lithium-ion batteries. While carbon matrices have demonstrated effectiveness in enhancing the electrical conductivity and accommodating the volume expansion of transition metal oxide-based anode materials in lithium-ion batteries (LIBs), achieving an optimized utilization ratio remains a challenging obstacle. In this investigation, we have devised a straightforward synthesis approach to fabricate CuO nano powder integrated with carbon matrix. We found that with the use of a sodium carboxymethyl cellulose (CMC) based binder and fluoroethylene carbonate additives, this anode exhibits enhanced performance compared to acrylonitrile multi-copolymer binder (LA133) based electrodes. CuO@CMC electrodes reveal a notable capacity ~1100 mA h g-1 at 100 mA g-1 following 170 cycles, and exhibit prolonged cycling stability, with a capacity of 450 mA h g-1 at current density 300 mA g-1 over 500 cycles. Furthermore, they demonstrated outstanding rate performance and reduced charge transfer resistance. This study offers a viable approach for fabricating electrode materials for next-generation, high energy storage devices.

Hard carbon/graphene microfibers as a superior anode material for sodium-ion batteries

Hard carbon is one of the most promising anode materials for sodium-ion batteries (SIBs). However, it still suffers from low specific capacity and poor rate capability, which impede its practical application. Herein, one-dimensional hard carbon/graphene microfibers are synthesized by encapsulating hard carbon particles in graphene nanosheet using a wet-spinning technique followed by pyrolysis treatment. Benefiting from the unique structure, when used as the anode material for SIBs, the as-obtained hard carbon/graphene microfibers not only exhibit a high reversible capacity of 321 mAh g−1 at 0.1 C but also deliver long cycling stability and excellent rate capability, maintaining its capacity as 203 mAh g−1 even after 350 cycles at 1 C. In addition, the sodium storage mechanism of the as-prepared hard carbon/graphene microfibers is investigated by in-situ Raman technique. Moreover, a full cell adopting the hybrid microfiber as the anode and Na3V2(PO4)3 as the cathode exhibits high specific capacities of 291 mAh g−1 and 204 mAh g−1 at 0.2 C and 4 C (vs. anode), respectively. This work provides a sustainable and cost-effective strategy for the synthesis of high-capacity and stable hard carbon anode materials.

Reveal the capacity loss of lithium metal batteries through analytical techniques

AbstractHigh energy density and stable long cycle are the basic requirements for an ideal battery. At present, lithium (Li) metal anode is regarded as one of the most promising anode materials, but it still faces major problems in terms of capacity fading and safe and stable long‐term cycle. The reason for the continuous fading of Li anode capacity is mainly due to the loss of active Li source, and the loss of Li source is mainly due to the continuous generation of dead Li. At the same time, the unstable interface and dendrite growth of Li anodes during the Li plating/delithiation process eventually lead to battery safety issues. In fact, recent studies have shown that the disordered expansion of dendrites is the main reason for the infinite generation of dead Li. Therefore, here we take different detection techniques as clues, review the exploration process of qualitative and quantitative research on the source and mechanism of Li capacity loss, and summarize the strategies to reduce dead Li generation and capacity fading by inhibiting dendrite formation. In particular, we give suggestions on the development of advanced testing methods on how to further study the problem of dead Li, and also give relevant strategy suggestions on how to completely solve the problem of capacity loss in the future, with the main goal of suppressing dendrites.

Exploring the potential of carbon and boron nitride integrated biphenyl frameworks as promising anode materials for high-performance Li-ion and Na-ion batteries: A comprehensive first-principles investigation

A protocol of evaluating 2D anode materials that was applied in our previous study has been refined. With the updated Li/Na potential profiles, the two-dimensional biphenyl network (BPN_C) and its isoelectronic structure, boron nitride (BPN_BN), were comprehensively investigated as potential anode materials. The electronic properties, the mechanic strength and the storage capacities were computed accordingly. The band structure results show that the BPN_C and BPN_BN exhibit the nature of conductor and wide-band semi-conductor, respectively. The calculated mechanic strengths of BPN_BN and BPN_C are competent for anode materials. The storage capacities of BPN_C and BPN_BN were addressed by means of the stepwise binding energies (Ead2) and ab initio molecular dynamic simulations. Higher storage capacities were identified as compared with those of the graphene structure. Furthermore, the calculated open-circuit voltages (OCVs) for both BPN_C and BPN_BN can meet the requirements of adequate anode materials. Finally, the diffusivities of Li/Na atoms on the surface of BPN_C and BPN_BN were investigated and found to be suitable for the application as anodes. Our results suggest that the BPN structures can be used as potential anode materials for both LIBs and SIBs.

Interfacial Engineering of Polymer Membranes with Intrinsic Microporosity for Dendrite-Free Zinc Metal Batteries.

Metallic zinc has emerged as a promising anode material for high-energy battery systems due to its high theoretical capacity (820 mAh g-1), low redox potential for two-electron reactions, cost-effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial-engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron-thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+-ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm2 with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g-1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi-functional membranes that can advance the development of safe and stable zinc metal batteries.

Interfacial Engineering of Polymer Membranes with Intrinsic Microporosity for Dendrite‐free Zinc Metal Batteries

Metallic zinc has emerged as a promising anode material for high‐energy battery systems due to its high theoretical capacity (820 mA h g‐1), low redox potential for two‐electron reactions, cost‐effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial‐engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron‐thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+‐ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm² with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g‐1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi‐functional membranes that can advance the development of safe and stable zinc metal batteries.

Revealing the sodium storage mechanism of cellulose separator-derived hard carbon anode materials for sodium-ion batteries

Hard carbon (HC) shows significant promise as a material for sodium-ion batteries (SIB). Cellulose-derived carbon is considered one of the most promising high-performance anode materials for sodium-ion batteries. In this study, waste cellulose separator-derived HC anode materials were rationally developed using the pre-oxidation-carbonization pyrolysis method. The as-prepared HC possessed advantageous characteristics for Na+ storage, including a unique fibrous structure, a reasonable space layer, and a small specific surface area (SSA). The optimal sample demonstrated a substantial reversible capacity of 361.29 mAh/g at 0.1C, an impressive high-rate performance with a reversible capacity of 272.93 mAh/g at 10C, and an initial coulombic efficiency of 84.85 %. Following 500 cycles at 1C, the capacity retained 96.38 % of its initial value. The sodium storage process was identified as the “adsorption-insertion-pore filling mechanism” through ex-situ XRD and in-situ Raman experiments. Moreover, the as-prepared HCs demonstrated better rate and cycle capability when evaluated as anodes in full-cell sodium-ion batteries (SIBs). This research provides valuable insights into the rational design of high-performance HC anodes for SIBs and other applications.

Ultra-high areal capacity, ultra-long life, dendrite-free sodium metal anode enabled by antimony-based Na-ion conducting artificial SEI layers

Sodium metal (Na) is a promising anode material for Na metal batteries and solid-state sodium batteries, because of its high theoretical capacity, favorable electrochemical potential, and cost effectiveness. Nevertheless, practical applications of sodium metal anode are hindered by uncontrolled dendrite growth owing to chemical instability of the heterogeneous solid electrolyte interphase layer. In this work, we proposed a simple interface modification strategy employing several antimony-based Na-ion conducting solid electrolyte complexes as protective artificial SEI layer over Na metal. The Na-ion conducting interphases are robust and highly Na-ion conductive to attain uniform sodium ion flux with a small overpotential. Importantly, Na anode with antimony sulfide based solid electrolyte SEI layers exhibited the high-rate performance (10 mA cm−2) along with a remarkable capacity of 30 mAh cm−2, and life span of ∼ 1100 h. We observe that replacing the conventional artificial SEI layers, employing alloy type interface with Na-ion conducting solid electrolyte as artificial SEI components will improve the mechanical robustness at high current and high-capacity conditions. The sodium metal batteries employing modified metal anodes and high voltage Na1.2Mn0.8O1.5F0.5 cathode, exhibited excellent stability and high efficiency at 1C rate. Furthermore, the modified metal anodes are well-compatible with Na3SbS4 solid-state electrolyte, and the symmetrical solid-state battery exhibited a stable interface. Our strategy holds significant promise and has the potential for widespread application in theadvancement of high-energy sodium metal batteries and solid-state sodium batteries.

The Green Synthesis of Nanostructured Silicon Carbides (SiCs) from Sugarcane Bagasse Ash (SCBA) as Anodes in Lithium-Ion (Li-Ion) Batteries: A Review Paper

Silicon is a promising anode material for the increased performance of lithium-ion batteries because of its high elemental composition and specific capacity. The application of silicon on a commercial scale is restricted due to the limitation of volume expansion. Silicon is also expensive, making it difficult for large-scale commercialisation. Different methods were used to address these issues, including a sintering process and the sol–gel method, to form silicon carbide (SiC), a hard chemical compound containing silicon and carbon. The silicon carbide anode not only acts as a buffer for volume expansion but also allows for better infiltration of the electrolyte, increasing charge and discharge capacity in the battery. Like silicon, silicon carbides can be costly. The development of renewable energy systems is very important, especially in the development of energy storage systems that are not only efficient but also cost-friendly. The cost of the energy storage devices is lowered, making them easily accessible. Silicon carbides can be synthesised from sugarcane, which is the fibrous waste that remains after juice extraction. This could be beneficial, as we could never run out of such a resource, and it offers low carbon with a high surface area. Silicon carbides can be synthesised by carbothermal reduction of silica from sugarcane bagasse. This review provides a comprehensive understanding of silicon carbides and synthetic processes. The innovative use of waste to synthesise materials would reduce costs and comply with Sustainable Development Goals (SDGs) 7 (affordable and clean energy) and 13 (climate action).

Synergistic effect of in-situ carbon-coated mixed phase iron oxides and 3d electrode architectures as anodes for high-performance sodium-ion batteries

Due to the high theoretical capacity, iron-oxide-based Fe2O3 (1007 mAh g−1) and Fe3O4 (926 mAh g−1) materials can be a promising conversion-type anode material for Sodium-ion batteries (SIBs). However, the low electronic conductivity (10−14 S cm−1) and 200% volume expansion of iron oxide lead to poor cycle life and capacity retention, limiting its commercial application. In this work, carbon-coated mixed-phase iron oxide C-Fe2O3-Fe3O4 (C-IO) was synthesized by pyrolysis using ferrocene precursor. Subsequently, a 3D carbon fiber (CF) network was introduced to improve the electrochemical performance of the material by resolving the volume expansion and pulverization issues. Both the CF network and Fe3O4 provide an electron transport pathway. The conventional Cu-C-IO electrodes deliver a 2nd cycle capacity of 335 mAh g−1 at 250 mA g−1 and exhibit 61.5% capacity retention after 500 cycles. In contrast, the 3D-CF-based IO electrodes show 2nd cycle capacity of 607 mAh g−1 at 50 mA g−1 with 96.4% capacity retention after 35 cycles and 420 mAh g−1 with ∼85.4% capacity retention after 500 cycles at 250 mA g−1 (w.r.t. CF and C-IO active mass, CF contribute ∼ 27% and C-IO ∼ 73% capacity), making it a potential anode for SIBs.

Facile preparation of MnO/Mn3O4 anode from commercial manganese(II) oxalate dihydrate and its advanced lithium storage performance

Manganese oxides are considered a highly promising anode material in lithium ion batteries (LIBs) because of their high theoretical capacity, abundant sources, relatively low voltage hysteresis, nontoxic and cost-effectiveness. Nevertheless, the practical application of these materials faces many challenges such as poor lifespan and serious volume variation during operation. Herein, MnO/Mn3O4–600 composite was obtained based on a single-step pyrolysis procedure from commercial manganese(II) oxalate dihydrate (MOD, C2H4MnO6). The MnO/Mn3O4–600 anode exhibits an exceptionally high reversible capacity of 1041.8 mAh g−1 at the current density of 200 mA g−1, and a remarkable lifespan at 1000 mA g−1. The outstanding performance benefits from the formation of porous structures on nanoparticles, which not only mitigate volume changes and prevent the aggregation of internal MnO/Mn3O4 nanoparticles, but also enhance the ion diffusion. The in-depth insights into the (de)lithiated mechanism of the electrode are investigated by in situ X-ray diffraction (XRD) technique. Moreover, when applied in a full cell, the MnO/Mn3O4–600 anode demonstrates exceptional electrochemical property.

Regulating the closed pore structure of biomass-derived hard carbons towards enhanced sodium storage

Hard carbon (HC) stands out as a promising anode material for sodium storage due to its unique structure. However, the pore structure regulation of HC still poses a significant challenge. Herein, we propose a combined method of hydrothermal pretreatment, freeze-drying, and high-temperature carbonization to regulate the pore structure of HC. During the hydrothermal processes, the assembly of graphene oxide (GO) with starch facilitates the formation of open pores, which are subsequently transformed into closed pores during high-temperature carbonization. Impressively, a hard carbon with a reversible capacity of 434 mA h g −1 at 30 mA g −1 has been prepared through the structure regulation. Compared to the sample without structural regulation, it demonstrates a remarkable increase of 184.21 mA h g−1, with an enhancement rate of 73.80 %. Simultaneously, the skeletal structure of GO serves as a conductive network and framework support, enabling favorable rate performance and excellent cycling stability. Furthermore, the sodium storage mechanism is deduced as “adsorption -- intercalation -- pore filling”. Overall, this study can offer valuable insights into pore structure regulation for anode materials and shed light on sodium storage mechanisms.

From Natural Fibers to High-Performance Anodes: Sisal Hemp Derived Hard Carbon for Na-/K-Ion Batteries and Mechanism Exploration.

Hard carbon (HC) is a promising anode material in alkali metal ion batteries owing to its cost-effectiveness, abundant sources, and low working voltage. However, challenges persist in achiving prolonged cycling stability and consistent capacity, and the sodium storage mechanism in HC is still debated. Herein, an unreported biomass precursor, "sisal," for deriving hard carbon is developed. A series of sisal hemp-derived hard carbon with natural 3D porous channels are prepared. Through phase characterization and electrochemical testing, the relationship between microstructure and sodium storage capacity is elucidated, further confirming the suitability of the "adsorption-insertion-filling" mechanism for sodium storage properties in hard carbon materials. Without the need for any additional modification strategies, this biomass-derived hard carbon demonstrates excellent electrochemical performance in both sodium-ion and potassium-ion batteries (SIBs and PIBs). The as-prepared HC-1300 demonstrates excellent ion storage capability, delivering a high reversible capacity of 345.2mAhg-1 in SIBs and 310mAhg-1 in PIBs at 0.1C. Moreover, it maintains a specific capacity of 237.3mAhg-1 over 1200 cycles at 1C when used in SIBs. The excellent cycling stability and superior rate performance are also presented in full cells, highlighting its potential for practical applications.

Hollow Ni/NiO@N-doped porous carbon for lithium ion battery anode based on dual-buffering strategy

As a promising anode material of lithium-ion batteries (LIBs), the poor electrical conductivity and severe volume expansion during cycling of nickel oxide (NiO) greatly limit its practical application. Here, a hollow nitrogen-doped porous carbon-loaded hollow Ni/NiO nanocomposite (Ni/NiO@HNC) was obtained by introducing Ni2+ into hollow covalent organic framework (HCOF) and then calcining the Ni2+/HCOF. The as-prepared Ni/NiO is nanoscale and hollow, which effectively accommodates the expanded volume of NiO. Hollow nitrogen-doped porous carbon (HNC) obtained from HCOF can further accommodate the expanded volume of NiO. The residual Ni and HNC can improve the electrical conductivity of Ni/NiO@HNC greatly. The regular pores of HNC inherited from HCOF facilitate the Li+ transfer. Thus, the Ni/NiO@HNC-2 composites exhibited outstanding cycle stability and rate performance when utilized as anode materials in LIBs. Even after 200 cycles at 0.1 A g−1, the capacity was still kept at 695.1 mAh g−1. The work provides an idea to prepare LIBs anodes based on dual-buffering strategy.