Anode Material For Lithium-ion Batteries Research Articles

Novel metal-organic anode material by in-situ chelating Ni2+ with tannic acid on carbon nanotube for high-performance Li storage

Lithium-ion batteries (LIBs) with natural organic anode are attracting intensive interest for application owing to their structural diversity, cost-effectiveness, eco-friendliness, and high specific capacity. However, directly usage of natural organic materials as anode materials usually encounters poor electrochemical properties such as low reversible capacity and short cycling life. Thus, developing high-performance organic electrode materials for LIBs remains a great challenge. Herein, we present a rational design and fabrication of TA-Ni@CNTs by in-situ coating TA-Ni polymers onto the surface of carbon nanotubes (CNTs) as a superior anode material for LIBs. Specifically, the highly conductive CNTs can effectively relieve the aggregation of TA-Ni and improve the electronic conductivity. Meanwhile, the strong chelation among nickel irons and catechol groups enhances the structure stability and inhibits the dissolving property. Consequently, as an anode material for LIBs, the resulting TA-Ni@CNTs achieves a high reversible capacity of 1418.8 mAh·g−1 at 0.1 A·g−1 after 216 cycles and an outstanding cycling stability with 951.1 mAh·g−1 at 0.5 A·g−1 after 323 cycles. The presented design strategy holds great promise for developing more-efficient electrode materials for LIBs.

Constructing a 3D Li[sbnd]Mg alloy skeleton through mechanical rolling for high-rate Li anodes

Li is a promising anode material for lithium-ion batteries owing to its low redox potential (−3.04 V vs. standard hydrogen electrode) and exceptionally high theoretical specific capacity (3860 mAh g−1). However, considerable volume changes and uncontrolled dendrite growth reduce coulombic efficiency during charge/discharge cycles, limiting its practical application. This research introduces a straightforward method to fabricate a two-phase intertwined composite electrode featuring a LiMg phase as a three-dimensional (3D) skeleton structure aimed at high-rate Li-metal batteries. With its mixed electronic and ionic conducting networks, the 3D alloy structure offers abundant interfaces with pure Li and exhibits strong lithium affinity, enhancing Li+ diffusion throughout the electrode and enabling dendrite-free deposition. Results demonstrate a long cycle life exceeding 80 h at 30 mA cm−2 in symmetric cells. Coin- and pouch-type full cells with cathodes also show excellent rate capacity and cycling stability. The exceptional performance of this material makes it a highly desirable anode for high-rate lithium-metal batteries.

Large-Scale Synthesis of N,S Codoped Carbon-Modified Fe0.975S Composites as a Novel Anode for Lithium/Sodium Ion Batteries with Enhanced Performance.

To overcome obstacles hindering the commercialization of lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs), we introduce a cost-effective single-step sulfurization strategy for synthesizing iron sulfide (Fe0.975S) nanohybrids, augmented by N,S codoped carbon. The resulting N,S codoped carbon-coated Fe0.975S (Fe0.975S@NSC) electrode exhibits exceptional potential as a highly reversible anode material for both LIBs and SIBs. With impressive initial discharge and charge capacities (1658.2 and 1254.9 mAh g-1 for LIBs and 1450.9 and 1077.1 mAh g-1 for SIBs), the electrode maintains substantial capacity retention (900 mA h g-1 after 1000 cycles for LIBs and 492.5 mA h g-1 after 600 cycles for SIBs at 1.0 A g-1). The LiMn2O4//Fe0.975S@NSC and Na3V2(PO4)3//Fe0.975S@NSC full batteries can maintain excellent reversible capacity and robust cycling stability. Ex situ and in situ X-ray diffraction, density functional theory (DFT) calculations, and kinetics analysis confirm the promising energy storage potential of the Fe0.975S@NSC composite.

A Bifunctional Carbon-LiNO3 Composite Interlayer for Stable Lithium Metal Powder Electrodes as High Energy Density Anode Material in Lithium Batteries

Lithium metal remains a promising candidate for high-energy-density rechargeable batteries due to its exceptional specific capacity and low reduction potential. However, practical implementation of lithium metal anodes faces challenges such as dendrite formation, limited cycle life, and safety concerns. This study introduces a novel approach to enhance the performance of lithium metal powder (LMP)-based electrodes by embedding a LiNO3-carbon composite interlayer between the LMP electrode and the copper foil current collector. The N-rich carbon interlayer acts as a reservoir for LiNO3, enabling its gradual release to maintain prolonged stability of the interfacial reactions of the Li-metal and providing additional Li nucleation sites. Our findings demonstrate that the LiNO3-carbon composite effectively suppresses dendrite formation, improves reversible capacity, and stabilizes the solid electrolyte interphase. Additionally, we validated the fast-charging capabilities of the Li/NCM622 half-cell employing the LiNO3-carbon-coated Cu foil with LMP electrodes. Our results highlight the significant synergistic effect of the LiNO3 additive and carbon interlayer in enhancing the performance of lithium metal-based batteries.

Microfluidic Shape Analysis of Non-spherical Graphite for Li-Ion Batteries via Viscoelastic Particle Focusing.

The size and shape of graphite, which is a popular active anode material for lithium-ion batteries (LIBs), significantly affect the electrochemical performance of LIBs and the rheological properties of the electrode slurries used in battery manufacturing. However, the accurate characterization of its size and shape remains challenging. In this study, the edge plane of graphite in a cross-slot microchannel via viscoelastic particle focusing is characterized. It is reported that the graphite particles are aligned in a direction that shows the edge plane by a planar extensional flow field at the stagnation point of the cross-slot region. Accurate quantification of the edge size and shape for both spheroidized natural and ball-milled graphite is achieved when aligned in this manner. Ball-milled graphite has a smaller circularity and higher aspect ratio than natural graphite, indicating a more plate-like shape. The effects of these differences in graphite shape and size on the rheological properties of the electrode slurry, the structure of the coated electrodes, and electrochemical performance are investigated. This method can contribute to the quality control of graphite for the mass production of LIBs and enhance the electrochemical performance of LIBs.

Hollow Cobalt Selenide-Carbon polyhedron sandwiched between reduced graphene oxide nanosheets: A superior anode material for lithium-ion batteries

In this work, a double carbon-confined sandwich-like CoSe/NCP/rGO composite was fabricated using an self-assembled method combined with a selenization treatment. In the composite, cobalt selenide (CoSe) nanoparticles were embedded in N‑doped hollow carbon polyhedrons (NCP) and sandwiched between reduced graphene oxide (rGO) nanosheets. The kinetics of electron/ion transport along with the structural stability of the composite were significantly enhanced by the layer-by-layer sandwiched hollow structure and the strong cohesive interface interaction between various components. The CoSe/NCP/rGO, when serving as LIB’s anode material, exhibited excellent performance. It demonstrated a high specific capacity with the value of 843 mAh/g at 1 A/g, superior high-rate capability with capacity remaining at 309 mAh/g at 10 A/g, long-term cycling stability with no noticeable capability fading over 1000 loops. More importantly, these results were achieved without additional conductive agents.

Towards practical Li-ion full batteries with glass anodes

Vanadium (V)-based glasses have recently garnered considerable attention as promising anode materials for lithium-ion batteries (LIBs) due to their abundance of Li+ storage sites, neglectable volume expansion upon lithiation/delithiation, and ease of preparation. However, the inherently low electrical conductivity and relatively low energy density of V-based glass anodes hinder its application in full LIBs. In this work, we tackled this challenge by optimizing the chemical composition of the V-based glass anode to achieve high-performance half and full batteries. We investigated the impact of partially substituting B2O3 for P2O5 in 50V2O5-(50-x)P2O5-xB2O3 (mol%) (VPB) glass series on its structure and electrochemical performances. The glass with 30mol% B2O3 (VPB30 glass) was found to deliver the highest electronic conductivity, an enhanced reversible capacity of 470mAh g−1 at 1Ag−1 after 500 cycles, and excellent rate capability. The optimized performances were ascribed to the boosted lithium-ion diffusivity and the increased lithium storage sites. We assembled a full cell by coupling a VPB30 glass anode with a LiCoO2 cathode to test its cycling performance. The VPB30//LiCoO2 cell exhibits the required power density, and hence, high practicality. Our work implied the practical application of glass anodes in high-performance LIBs.

Novel binder-free Vanadium-based molten salt (NMPV) with low-cost as anode materials of lithium-ion batteries

Molten salt NMPV material is synthesised using a one-step method and applied to binder-free anodes for lithium-ion batteries (LIBs). In this work, simple, low-cost and highly active coordination molten salt electrode materials (NMPV and NMPV-C) were prepared, which overcame the drawbacks of cumbersome and costly preparation of the existing electrode materials. NMPV is formed by the lone pair of electrons of N-methyl pyrrolidone (NMP) molecules coordinated with vanadium ion. The synergistic effect produced by these two and the excellent electrical conductivity and electrochemical properties of the molten salt material itself exhibits satisfactory lithium storage results. The discharge capacities of NMPV-C and NMPV in the second discharge cycle are 669 and 345 mAh g-1, respectively. After 100 cycles, the capacity is maintained at 923 and 549 mAh g-1, respectively. And the capacity retention is 137.97% and 159.13%, respectively. In addition, the NMPV-C electrode maintains a stable reversible capacity of 450 mAh g-1 at 2000 mAh g-1 after 220 cycles. Density-functional theory (DFT) calculations revealed that Li+ is more likely to attack H on methyl nitrogen, which is the optimal reaction site for NMPV since the lone pair of electrons of N effectively stabilises the carbon cation after the reaction of Li with H.

“Fast-charging” mechanism of Li3VO4 from the perspective of material science for lithium-ion battery

“Fast-charging” lithium-ion batteries enjoy extensive attention as energy storage devices for portable electronic devices and new energy vehicles. Regrettably, high safety could not be effectively ensured while the batteries undergo fast-charging process. Li3VO4 could be recognized as a high-safety “fast-charging” anode material considering its appropriate Li-insertion voltage and fast kinetic characteristics. Currently, notwithstanding the fact that Li3VO4 has been extensively investigated as an anode material for lithium-ion batteries and the encouraging research results have been accomplished, the distinction between ion diffusion mechanisms during fast-charging and slow-charging has not been well elucidated. Unlike previous reports, Li+ fast/slow diffusion mechanisms in Li3VO4 are investigated in detail in this work. Specifically, Li+ tends to diffuse along path a due to rather fast Li-insertion/deinsertion processes. Correspondingly, Li+ undergoes diffusion along path a and path b during slow-charging. Unlike the conventional view that Li+ prefers to diffuse along path a under all conditions. Additionally, the lattice changes of Li+ insertion into different sites are predicted. The findings could facilitate to comprehend the mechanism of doping, nanosizing, and other modification methods, and the fast-charging issue could be addressed in a targeted way. For instance, the optimal fast diffusion paths are modified at both atomic and lattice scales, inducing that Li+ could be inserted into the lattice of material faster during fast-charging and the power densities could be increased. Accordingly, understanding the fast diffusion mechanism of Li+ in Li3VO4 is crucial to addressing the “fast-charging” of these materials. Unfortunately, the inferior electronic conductivity restricts its Li-storage capacity in “fast-charging” devices. Herein, a Li3VO4 based anode material is prepared thorough a one-step hydrothermal method and liquid-phase dispersion technique in the existence of polyvinyl pyrrolidone, which demonstrates exceptional discharging and charging specific capacities, maintaining 273 mAh g−1 at 0.1 A g−1. It also presents considerably higher “fast-charging” performance even at 1.0–4.0 A g−1. Electrochemical kinetic studies indicate that the thin coating could improve the conductivity of Li3VO4. The Li-insertion sites and diffusion paths during fast-charging and slow-charging processes are predicted computationally. And the in-situ XRD is adopted to insight into the structural changes of composites during Li-insertion/deinsertion processes. The data furnishes a theoretical basis for comprehending the fast lithium storage mechanism of Li3VO4 and offers a new method for searching for “fast-charging” anode materials.

Controllable Synthesis and Growth Mechanism of Cracked Cowpea-Like NCNT Encapsulated with Fe3N Nanoparticles for High-Performance Anode Material in Lithium-Ion Batteries

Fe3N nanocrystals embedded in cracked N-doped carbon nanotubes (Fe3N@NCNT) with a cowpea-like shape are innovatively prepared by metal-catalyzed graphitization and nitridization processes based on melamine and FeC2O4 precursor. The new in-situ synthesis strategy is proved to be effective to open the NCNT using a migratory metal carbide nanocatalyst via expansion effect and fabricate a metal nitride embedded NCNT with fully active ingredients. The detailed tip-growth mechanism of cracked NCNT with latitudinal-longitudinal graphene layers is studied by in-situ XRD analysis of the phase evolution of melamine and FeC2O4, and ex-situ SEM/TEM investigation of the topography correlation of NCNT and Fe3C floating catalyst. The Fe3N@NCNT microclews based anodes have a moderate carbon content of 35.45 wt%, electroactive NCNT conductive network, abundant microcracks and an open short-cavity system, showing a stable discharge capacity of 667 mAh g−1 at 0.1C, outstanding rate capability of 448 mAh g−1 at 5C and remarkable long-term cycling stability of 546 mAh g−1 after 600 cycles at 1C. The combined good electronic/ionic conductivity of cracked NCNT and robust mechanical stability of geometrically confined Fe3N nanoparticles contribute to the excellent redox activities, stabilized solid-electrolyte-interphase film and cycling durability of Fe3N@NCNT.

Preparation and electrochemical properties of nitrogen-doped starch hard carbon anode materials for lithium-ion battery

Here, we report the synthesis of hard carbon materials (CSHs) made from corn starch and their application as an anode in lithium-ion batteries. The study shows that the microstructure and electrochemical properties of CSHs are affected by nitrogen doping. It is found that nitrogen is embedded in the carbon layer with graphite nitrogen, pyridyl nitrogen, and pyrrole nitrogen, so that the surface morphology was changed and reduced the disorder of the materials. The electrochemical test results show that the introduction of nitrogen elements can increase the reversible capacity of the material, with the first discharge capacity reaching above 426.35 mAh g−1, and the rate performance also improves. When melamine and pre-carbonized corn starch are carbonized at a mass ratio of 1:9, the obtained material has a reversible capacity of 122.04 mAh g−1 at a rate of 2 C. During the carbonization process, the nitrogen in melamine is doped into the carbon materials, improving the electrochemical performance of the material.

Magnesiothermic reduction SiO coated with vertical carbon layer as high-performance anode for lithium-ion batteries

Silicon monoxide (SiO), as one of the most competitive anode materials for lithium-ion batteries (LIBs), has received considerable attention. Nevertheless, poor initial Coulombic efficiency (ICE) and larger volume change are the main obstacles to the application of SiO. Here, we suggest a controllable route for the modification of micro-sized SiO via magnesiothermic reduction. To prevent the excessive growth of Si grains caused by the overheating reaction, the solid-state thermal reaction between Mg and SiO is achieved by mixing a certain proportion of NaCl at a suitable temperature, resulting in a loose surface and porous structure of SiO particles, which is conducive to the transportation of lithium ions and electrons. Combined with chemical vapor deposition (CVD), the carbon-coated SiOx composites (M-SiOx@C-R, where R is the molar ratio for Mg and SiO) exhibit unique morphology structure and remarkable electrochemical characteristics. As expected, the vertical carbon network improves the conductivity and alleviates the volume expansion of SiOx. Notably, the M-SiOx@C-0.75 electrode offers a large initial specific capacity of 2283.17 mAh g−1 with a higher ICE of 86.03 % at 100 mA g−1. Furthermore, the full cells using M-SiOx@C-0.75 composite as the negative electrode and LiNi0.8Co0.1Mn0.1O2 (NCM811) as the positive electrode were assembled. After 150 cycles, the full cell still delivers a high specific capacity of 72.22 mAh g−1 (with a retention rate of 47 %). This work provides a feasible route for the fabrication of applicable SiO-based anode materials.

In-situ assembly of 3D VS2/Reduced graphene oxide with superior lithium ion storage performance: The role of heterojunction

VS2 is a potential anode material for lithium-ion batteries (LIBs) due to its advantageous properties. Herein, a novel three-dimensional (3D) VS2/reduced graphene oxide (rGO) heterostructure (VS2-rGO) was fabricated by in-situ assembly of caterpillar-like VS2 nanosheets on rGO. This 3D VS2-rGO with a well-defined heterojunction interface is engineered to mitigate the volumetric expansion of VS2 during Li + intercalation/deintercalation cycles. This optimized design promotes enhanced conductivity across the heterojunction, facilitating efficient electron and ion transport. The VS2-rGO electrode shows higher reversible capacity and better rate performance (644.02 mA h g−1 at 0.1 A g−1 after 140 cycles, 526.66 mA h g−1 at 2 A g−1) as compared to the pure VS2 electrode (433.69 mA h g−1 at 0.1 A g−1 after 140 cycles, 63.91 mA h g−1 at 2 A g−1). Ex-situ XRD analysis suggests that the Li + storage mechanism in the VS2-rGO electrode involves the initial intercalation, followed by intercalation and conversion. The lower Li + diffusion barrier within the VS2-rGO heterojunction (0.183 eV) compared to the VS2 layers (0.225 eV), as predicted by first-principles calculations, resulting the enhanced Li + transport kinetics and improved cycling performance of the VS2-rGO electrode material. This work offers novel perspectives for the influence of heterojunctions on LIBs.

One step for the construction of MnCO3-Mn3O4 composite for the high-performance lithium-ion batteries

In this work, MnCO3-Mn3O4 composite materials were prepared by one-step solvothermal method. The structure, morphology and chemical composition were characterized and analyzed. As the anode materials of lithium-ion batteries, the formed MnCO3-Mn3O4 composites on the basis of initial KMnO4/DMF weight ratio of 1:40 and 1:20 delivered the specific discharge capacities of 654.8 and 598.7 mA h g−1 after 100 cycles at a current density of 1.0 A g−1. The testing results indicate that MnCO3-Mn3O4 composite has significant advantage in electrochemical lithium storage capacity and can be utilized as one prospective anode material for the high performance lithium-ion batteries.

Electrospun three dimensional TiO2@N/P co-doped carbon nanofibers framework as high-performance anode materials for lithium-ion batteries

Electrospinning combined with heating treatment is employed to fabricate N/P co-doped carbon nanofibers encapsulating homogenous ultrafine TiO2 nanoparticles (TiO2@N/P-CNFs). Characterization results reveal that one-dimensional electrospun composite nanofibers with high electronic conductivity and structural integrity are interconnected with each other to construct a three-dimensional conductive nanofiber network as efficient ion/electron transport channels. Specifically, the Li//TiO2@N/P-CNFs coin cell delivers an initial discharge specific capacity of 754.9 mAh/g at 100 mA/g and maintains the reversible specific capacity of 486.1 mAh/g after 100 cycles. Moreover, the cell expresses the exceptional rate capability with discharge specific capacity of 272.2 mAh/g at 2000 mA/g, whose capacity can be restored to 474.3 mAh/g as soon as the current density is returned to 100 mAh/g. Furthermore, Li//TiO2@N/P-CNFs cell demonstrates a significant pseudocapacitive contribution of 78% at 1.0 mV/s. The excellent electrochemical performance can be explained by the fact that the N/P co-doping strategy is promising strategy for facilitating Li+ ions storage and transfer by broadening interlayer distance and increasing the distribution of defects and active sites. Besides, ultrafine TiO2 nanoparticles with diameter of about 7 nm harness excellent mechanical strength to maintain structural stability upon cycling. Therefore, easily fabricated TiO2@N/P-CNFs composite nanofibers with excellent electrochemical properties may be served as a promising option for advanced anode materials for lithium-ion batteries.

Novel design of Sn4P3@NxC electrodes and their electrochemical properties

Tin phosphide (SnxPy) is recognized as one of the most promising anode materials for lithium-ion batteries due to its exceptionally high theoretical capacity. However, its application is hampered by significant volume expansion during charge-discharge cycles and inferior electrical conductivity. Proper structural design plays a pivotal role in addressing these challenges, paving the way for high-performance anode materials. This study introduces a nitrogen-doped carbon-coated Sn4P3 nanosphere with a core-shell structure, employing dopamine as the nitrogen source. This innovative approach, utilizing template removal and solid-phase phosphorization, results in both the core and shell acting as active materials, thereby enhancing the volumetric energy density of the electrode. The internal voids within the shell layer mitigate volume expansion during charge-discharge cycles, while the presence of the nitrogen-doped carbon layer maintains the material's stability throughout cycling and improves its electrical conductivity. Electrochemical performance tests confirm this material's outstanding energy storage capability, with an initial Coulombic efficiency reaching up to 73.6 %. Furthermore, it maintains a stable capacity of 585 mAh g−1 after 1200 cycles at a current density of 2 A g−1. This research offers a design paradigm for developing novel energy storage materials.

Hierarchical mesoporous Co3O4@C-N nanostructure rods derived from a metal-organic framework as high-performance anode for lithium-ion battery

A uniform hierarchical mesoporous Co3O4@C-N nanostructure rods were in situ fabricated successfully by developing a facile one-step strategy. Cobalt-based metal organic framework [Co3(ndc)(HCOO)3(μ-OH)(H2O)]n with special Co chine constructed framework structure treated as a precursor directly pyrolyzed in a mixed atmosphere of argon and oxygen (95:5) at 500 °C for 2 h. According to the XRD pattern, SEM, TEM, EDS mapping images and XPS spectrum analysis, the well-defined hierarchical mesoporous Co3O4@C-N nanostructure rods showed pure Co3O4 phase, are assembled from a large number of core–shell structured Co3O4@C-N spherical particles with an ultrasmall and uniform size (∼8 nm) which were further connected by N doped carbon net to form nanostructure rods. Using as anode material for lithium-ion batteries, these hierarchical mesoporous Co3O4@C-N nanostructure rods exhibit excellent electrochemical performance with high reversible capacity, rate capability and good cycling stability. They maintained a reversible specific capacity of more than 1000 mAh/g at 100 mA/g, and the discharge specific capacities at the 5 current density of 0.1, 0.2, 0.5, 1, 2, and 5 A/g reached 1123, 1094, 1044, 979, 879 and 688 mAh/g, respectively.

Hydrothermal synthesis of SnO2/MoO3-x/rGO ternary nanocomposites as a high-performance anode for lithium ion batteries

The theoretical specific capacity of tin dioxide (SnO2) as a lithium-ion batteries (LIBs) anode material is up to 1494 mAh·g−1, far exceeding that of graphite. However, the low conductivity, volume expansion, crushing failure and particles agglomeration during charge/discharge cycles limit its application in LIBs. In this work, the SnO2/MoO3-x/rGO composite material was synthesized by one-step hydrothermal method, with SnO2 and amorphous MoO3-x tightly and uniformly anchored at the surface of reduced graphene oxide (rGO). The results of structural characterization and electrochemical performance evaluation show that amorphous MoO3-x can increase the reactive active sites, inhibit Sn particles aggregation, and promote the reversible reaction of SnO2. rGO effectively improves the electrical conductivity of the composite and buffers the volume change of Li-Sn alloying/dealloying during cycles. In addition, due to introduction of MoO3-x and rGO a stable SEI film can be formed at the material's surface to improve the cycle stability. SnO2/MoO3-x/rGO exhibits excellent rate performance and cycle performance. When the rGO content is 10.9 wt%, the reversible capacity of the composite reach 813 mAh·g−1 after 800 cycles at current density of 1.0 A·g−1, and 450.6 mAh·g−1 after 1000 cycles at current density of 5.0 A·g−1, with the capacity retention rate of 96.9%.

Unraveling the impact of pore length on the conversion reaction of Fe3O4/carbon anodes in lithium-ion batteries

Despite numerous studies investigating Fe3O4/porous carbon anode materials for high-performance lithium-ion batteries (LIBs), the inherent limitations of the Fe3O4 conversion reaction, such as low reversibility and sluggish kinetics, continue to pose significant challenges. While modifying the porous structure of Fe3O4 anodes has demonstrated considerable promise in overcoming these limitations, the precise relationship between the porous structure and Fe3O4 conversion behavior still remains unclear. Here, we explore the impact of the pore length of the anode active material on the electrochemical performance of LIBs. Using two different composites of Fe3O4 and porous carbon with varying pore lengths as model materials, we conduct various in-depth electrochemical and ex-situ analyses. Our findings confirm that a shorter pore length facilitates higher Li+ ion diffusivity compared to longer pore length. Consequently, the conversion reaction of Fe3O4 to Fe and Li2O during lithiation process can be expedited, leading to a decrease in the resistance at the solid electrolyte interphase. As a result, we demonstrate that shortening the pore length of the porous anode composite materials can enhance the initial Coulombic efficiency (CE), reversible capacity, and rate capability of LIBs.

Study on the synthesis mechanism of new α-FeOOH@3DGF material and its lithium storage performance

A new self-supporting material contained nanorods α-FeOOH and three-dimensional skeleton graphene foam (3D Graphene Foam, 3DGF) was prepared by hydrothermal method. The growth mechanism and phase change rules of nanorods α-FeOOH@3DGF were studied to obtain the electrochemical lithium storage performance. The results showed that growth mechanism of nanorods α-FeOOH was accompanied by the consumption of nanoparticles β-FeOOH. If the hydrothermal time reached to 12 h, the nanoparticle β-FeOOH phase completely disappeared with only rod-shaped α-FeOOH@3DGF single phase obtained. Rod-shaped α-FeOOH@3DGF was used as anode material of lithium-ion batteries and the reversible specific capacity remained at about 305 mAh·g−1 after charging and discharging 250 times at 500 mA·g−1, with significantly cycling stability compared with that of the monomaterial α-FeOOH.