Preparation of carbon encapsulated Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium ion battery through pre-coating method

Carbon encapsulated Li₄Ti₅O₁₂ (C/Li₄Ti₅O₁₂) anode material for lithium ion battery was prepared by using the pre-coat method of two steps, and the TiO₂ was pre coated before the reaction with Li₂CO₃. The structure and morphology of the resultant C/Li₄Ti₅O₁₂ materials were characterized by X-ray diffraction (XRD) and scanning microscopy (SEM). Electrochemical tests showed that at 0.1 C, the initial discharge capacity was 169.9 mAh g^?1, and the discharge capacity was 80 mAh g^?1 at 5 C. After 100 cycles at 2 C, the discharge specific capacity was 108.5 mAh g^?1. Compare with one step coating method, results showed the C/Li₄Ti₅O₁₂ prepared by pre-coat method can reduce the particle’s size and effectively improve the electrochemical performance.     

Electrospinning preparation of one-dimensional Co<Superscript>2+</Superscript>-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers for high-performance lithium ion battery

One-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofibers with a diameter of approximately 500 nm have been synthesized via a one-step controllable electrospinning method. The Co²⁺-doped Li₄Ti₅O₁₂ nanofibers were systematically characterized by XRD, ICP, TEM, SEM, BET, EDS mapping, and XPS. Based on the cubic spinel structure and one-dimensional effect of Li₄Ti₅O₁₂, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers exhibit the enlarged lattice volume, reduced particle size and enhanced electrical conductivity. More importantly, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers as a lithium ion battery anode electrode performs superior electrochemical performance than undoped Li₄Ti₅O₁₂ electrode in terms of electrochemical measurements. Particularly, the reversible capacity of Co²⁺-doped Li₄Ti₅O₁₂ electrode reaches up to 140.1 mAh g^?1 and still maintains 136.5 mAh g^?1 after 200 cycles at a current rate of 5 C. Therefore, one-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofiber electrodes, showing high reversible capacity and remarkable recycling property, could be a potential candidate as an anode material.     

Nano Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> as sulfur host for high-performance Li-S battery

S/Li₄Ti₅O₁₂ cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li₄Ti₅O₁₂ is used as sulfur host and fast Li⁺ conductor, which can adsorb effectively polysulfides and improve remarkably Li⁺ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li₄Ti₅O₁₂ cathode has a stable discharge capacity of 616 mAh g^?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g^?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li₄Ti₅O₁₂ cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li₄Ti₅O₁₂ as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.     

Pr-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers as an anode material for lithium-ion batteries with outstanding cycling performance and rate performance

Pr-doped Li₄Ti₅O₁₂ in the form of Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0, 0.01, 0.03, 0.05, and 0.07) was synthesized successfully by an electrospinning technique. ICP shows that the doped samples are closed to the targeted samples. XRD analysis demonstrates that traces of Pr³⁺ can enlarge the lattice parameter of Li₄Ti₅O₁₂ from 8.3403 to 8.3765 Å without changing the spinel structure. The increase of lattice parameter is beneficial to the intercalation and de-intercalation of lithium-ion. XPS results identify the existence form of Ti is mainly Ti⁴⁺ and Ti³⁺ in minor quantity in Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) samples due to the small amount of Pr³⁺. The transition from Ti⁴⁺ to Ti³⁺ is conducive to the electronic conductivity of Li₄Ti₅O₁₂. FESEM images show that all the nanofibers are well crystallized with a diameter of about 200 nm and distributed uniformly. The results of electrochemical measurement reveal that the 1D Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) nanofibers display enhanced high-rate capability and cycling stability compared with that of undoped nanofibers. The high-rate discharge capacity of the Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) samples is excellent (101.6 mAh g^?1 at 50 °C), which is about 58.48 % of the discharge capacity at 0.2 °C and 4.3 times than that of the bare Li₄Ti₅O₁₂ (23.5 mA g^?1). Even at 10 °C (1750 mA g^?1), the specific discharge capacity is still 112.8 mAh g^?1 after 1000 cycles (87.9 % of the initial discharge capacity). The results of cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS) illustrate that the Pr-doped Li₄Ti₅O₁₂ electrodes possess better dynamic performance than the pure Li₄Ti₅O₁₂, further confirming the excellent electrochemical properties above.     

Enhanced electrochemical performance of Cu<Subscript>2</Subscript>O-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium-ion batteries

Li₄Ti₅O₁₂/Cu₂O composite was prepared by ball milling Li₄Ti₅O₁₂ and Cu₂O with further heat treatment. The structure and electrochemical performance of the composite were investigated via X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. Li₄Ti₅O₁₂/Cu₂O composite exhibited much better rate capability and capacity performance than pristine Li₄Ti₅O₁₂. The discharge capacity of the composite at 2 C rate reached up to 122.4 mAh g^?1 after 300 cycles with capacity retention of 91.3 %, which was significantly higher than that of the pristine Li₄Ti₅O₁₂ (89.6 mAh g^?1). The improvement can be ascribed to the Cu₂O modification. In addition, Cu₂O modification plays an important role in reducing the total resistance of the cell, which has been demonstrated by the electrochemical impedance spectroscopy analysis.     

Enhanced high-rate performance of sub-micro Li4Ti4.95Zn0.05O12 as anode material for lithium-ion batteries

Zn-doped Li₄Ti₅O₁₂ was prepared by a ball milling-assisted solid-state method, and the characters were determined by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, cyclic voltammetry, and galvanostatic charge–discharge testing. The results show that Li₄Ti_5?x Zn _x O₁₂ (x?=?0, 0.05) exhibits the pure phase structure, and Zn doping does not change the electrochemical reaction process and basic spinel structure of Li₄Ti₅O₁₂. The particle size of both samples is about 300–500 nm. The prepared Li₄Ti_4.95Zn_0.05O₁₂ presents an excellent rate capability and capacity retention. At the charge–discharge rate of 1C, the initial discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is 268 mAh g^?1. After 90 cycles at 5C, the discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is obviously higher than that of Li₄Ti₅O₁₂. The excellent electrochemical performance of the Li₄Ti_4.95Zn_0.05O₁₂ electrode could be attributed to the improvement of reversibility by doping zinc and the sub-micro particle size.     

Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres and their lithium storage properties

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo₂O₄ microspheres have been fabricated by calcinating the Zn_1/3Co_2/3CO₃ precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo₂O₄ microspheres exhibit an initial discharge capacity of 1,369 mAh g^?1 (3,244.5 F cm^?3) and retain stable capacity of 800 mAh g^?1 (1,896 F cm^?3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo₂O₄ 3D hierarchical structures provide a large number of active surface position for Li⁺ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.     

Synthesis and performance of Li2NiTi3O8 as a new anode material for lithium-ion batteries

The titanate spinel Li₂NiTi₃O₈ is proposed for the first time as a new anode for lithium-ion batteries and successfully synthesized via a facile ball-milling assisted solid-state reaction method. The sample is characterized by X-ray diffraction patterns (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, cyclic voltammetry (CV) tests, and electrochemical impedance spectroscopy (EIS). The results reveal that the Li₂NiTi₃O₈ nanoparticles have well-distributed morphology, and the particle size ranges between 100 and 300 nm. Although the initial coulombic efficiency is only 56.3 %, the Li₂NiTi₃O₈ electrode still exhibits a high rate capability and excellent cycling stability. The Li₂NiTi₃O₈ anode provides a large capacity of 212.3 mAh g^?1 at 0.1 A g^?1 after 10 cycle, which is close to its theoretical capacity (223.6 mAh g^?1). Even after 100 cycles, it still delivers a quite high capacity of 203.98 mAh g^?1, with no significant capacity fading. This indicates that the as-synthesized Li₂NiTi₃O₈ material is a promising anode material for lithium-ion batteries.     

Synergistic effect of magnesium and fluorine doping on the electrochemical performance of lithium-manganese rich (LMR)-based Ni-Mn-Co-oxide (NMC) cathodes for lithium-ion batteries

Mg-doped-LMR-NMC (Li_1.2Ni_0.15-xMg_xMn_0.55Co_0.1 O₂) is synthesized by combustion method followed by fluorine doping by solid-state synthesis. In this approach, we substituted the Ni²⁺ by Mg²⁺ in varying mole percentages (x = 0.02, 0.05, 0.08) and partly oxygen by fluorine (LiF: LMR-NMC = 1:50 wt%). The synergistic effect of both magnesium and fluorine substitution on electrochemical performance of LMR-NMC is studied by electrochemical impedance spectroscopy and galvanostatic-charge-discharge cycling. Mg-F-doped LMR-NMC (Mg 0.02 mol) composite cathodes shows excellent discharge capacity of ~300 mAh g^?1 at C/20 rate whereas pristine LMR-NMC shows the initial capacity around 250 mAh g^?1 in the voltage range between 2.5 and 4.7 V. Mg-F-doped LMR-NMC shows lesser Ohmic and charge transfer resistance, cycles well, and delivers a stable high capacity of ~280 mAh g^?1 at C/10 rate. The voltage decay which is the major issue of LMR-NMC is minimized in Mg-F-doped LMR-NMC compared to pristine LMR-NMC.     

Synthesis and characterization of Li4Ti5O12/graphene composite as anode material with enhanced electrochemical performance

The use of graphene as a conductive additive to enhance the rate capability and cycle stability of Li₄Ti₅O₁₂ electrode material has been demonstrated. Li₄Ti₅O₁₂ and its composite with graphene (1.86 wt%) are prepared by ball milling and simple chemical method, respectively. Among the as-synthesized composites, Li₄Ti₅O₁₂ particles uniformly clung to the graphene sheets. When used as an electrode material for lithium ion battery, the composite presents excellent rate performance and high cyclic stability. It is found that the composite displayed high-rate capacity of 118.7 mAh?g^?1 at 20 C. Furthermore, the composite exhibits good cycle stability, retaining over 96 % of its initial capacity after 50 cycles at 10 C. The excellent electrochemical performance is attributed to a decrease in the charge-transfer resistance.     

Enhanced lithium storage performance of a self-assembled hierarchical porous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/VGCF hybrid high-capacity anode material for lithium-ion batteries

A Co₃O₄/vapor-grown carbon fiber (VGCF) hybrid material is prepared by a facile approach, namely, via liquid-phase carbonate precipitation followed by thermal decomposition of the precipitate at 380 °C for 2 h in argon gas flow. The material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller specific surface area analysis, and carbon elemental analysis. The Co₃O₄ in the hybrid material exhibits the morphology of porous submicron secondary particles which are self assembled from enormous cubic-phase crystalline Co₃O₄ nanograins. The electrochemical performance of the hybrid as a high-capacity conversion-type anode material for lithium-ion batteries is investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic discharge/charge methods. The hybrid material demonstrates high specific capacity, good rate capability, and good long-term cyclability, which are far superior to those of the pristine Co₃O₄ material prepared under similar conditions. For example, the reversible charge capacities of the hybrid can reach 1100–1150 mAh g^?1 at a lower current density of 0.1 or 0.2 A g^?1 and remain 600 mAh g^?1 at the high current density of 5 A g^?1. After 300 cycles at 0.5 A g^?1, a high charge capacity of 850 mAh g^?1 is retained. The enhanced electrochemical performance is attributed to the incorporated VGCFs as well as the porous structure and the smaller nanograins of the Co₃O₄ active material.     

Electrochemical lithium storage properties of desert sands

SiO₂ is one of the most promising lithium storage materials for lithium-ion batteries anodes due to its low cost, good environmental compatibility, low working voltage, and high-specific capacity. In this work, the desert sands, which are rich in SiO₂, are investigated as the anode material for lithium-ion batteries. The electrochemical activation, lithium storage capacity, and cycle properties are highly dependent on the particle size distribution of sands. As the average particle sizes of sands gradually decrease, the reversible lithium storage capacity increases from 137 mAh g^?1 (several microns) to 492 mAh g^?1 (several submicrons). The 72 h-milled sands (average particle size: ~1 μm) deliver a stable lithium storage capacity of ~400 mAh g^?1 over 400 cycles with the capacity retention as high as 95%. The reason for the electrochemical activation, lithium storage capacity, and cycle properties of sands associated with their particle size distribution is also discussed.     

Self-assembled 3D Co3O4-graphene frameworks with high lithium storage performance

Three-dimensional Co₃O₄-graphene frameworks (3D-CGFs) are prepared with a one-pot hydrothermal method. Co₃O₄ particles are in situ anchored on graphene sheets, and the resulting composite self-assembles into 3D architecture during the hydrothermal treatment. Scanning electron microscope, transmission electron microscope, powder X-ray powder diffraction, and Raman spectroscopy are employed to characterize the sample. When tested as anode materials for lithium-ion batteries, 3D-CGFs demonstrate remarkable electrochemical lithium storage properties, such as large and stable reversible capacity (>530 mAh g^?1 at 500 mA g^?1 over 300 cycles), good capacity retention (88 % retention after 300 cycles at 500 mA g^?1 compared with the 4th cycle), excellent high-rate performance (515 mAh g^?1 at 1 A g^?1), making it a promising candidate for high-performance anode materials, especially for high-rate lithium-ion batteries.     

Improvement electrochemical performance of Li1.5Ni0.25Mn0.75O2.5 with Li4Ti5O12 coating

Layered cathode Li_1.5Ni_0.25Mn_0.75O_2.5 has been synthesized and coated by Li₄Ti₅O₁₂. The pristine and coated Li_1.5Ni_0.25Mn_0.75O_2.5 powders are characterized by X-ray diffraction (XRD), indicating the materials remained the layered structure before and after coating. The coated Li₄Ti₅O₁₂ has been detected by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (DEX). The electrochemical performance, especially rate performance of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode, is improved effectively after Li₄Ti₅O₁₂ coating. The first discharge capacity, coulombic efficiency, and capacity retention of Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode are 244 mA h g^?1, 81.5 %, and 98.3 % after 50 cycles, respectively. The Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode exhibits 108 mA h g^?1 at 10 °C rate. Electrochemical impedance spectroscopy (EIS) results show that the charge transfer resistance (R _ct) of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode decreases after coating, which is due to the existence of Li₄Ti₅O₁₂ with high lithium ion diffusion coefficient and suppression of the solid electrolyte interfacial (SEI) layer development and is responsible for the excellent rate capability and cyclic performance.     

The intercalation/deintercalation kinetic studies on the structure-integrated cathode material 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2

A cathode material, 0.5Li₂MnO₃ 0.5LiNi_0.5Mn_0.5O₂, was prepared by citric acid-assisted sol–gel method and its electrochemical performance was investigated. It delivered a charge capacity of 270 mAh g^?1 and a discharge capacity of 189 mAh g^?1 in the first cycle. With the increase of current density from 14 to 28 mA g^?1, the discharge capacity dropped severely to 130 mA g^?1. Obviously, the rate capability of the material was inferior to most of the oxide cathode materials. The diffusion coefficient of this material was calculated to be 6.04?×?10^?12 cm² s^?1 from the results of cyclic voltammetry measurements. Moreover, diffusion coefficients between 3.13?×?10^?12 and 1.22?×?10^?10 cm² s^?1 in the voltage range of 3.8–4.7 V were obtained by capacity intermittent titration technique. This, together with the localized Li₂MnO₃ domains in the crystal structure, may validate the poor rate capability.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Improving the electrochemical performance of Li-rich Li<Subscript>1.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>O<Subscript>2</Subscript> cathode material by LiF coating

To suppress the capacity fade of Li-rich Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ material as cathode materials for lithium-ion battery, we introduce a LiF coating layer on the surface to improve the cycling performance of Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ material. The modified sample shows a capacity of 163.2 mAh g^?1 with a capacity retention of 95% after 100 cycles at a current density of 250 mA g^?1, while the pristine sample only delivers a capacity of 129.9 mAh g^?1 with a capacity retention of 82%. Compared with the pristine material, the LiF-modified sample exhibits an obvious enhancement in the electrochemical performance, which will be very beneficial for this material to be commercialized on the new energy vehicles and other related areas.     

New-type low-cost cathode materials for Li-ion batteries: Mikasaite-type Fe2(SO4)3

In the present work, a new-type low-cost lithium ion battery cathode material, the Mikasaite-type iron sulfate, has been studied. It can be prepared by heating the water-containing iron sulfate raw chemicals in air atmosphere. The experimental results have shown that the oxidation and the reduction peaks are 3.92 and 3.37 V in the cyclic voltammogram, respectively, when the scanning rate is 0.05 mV s^?1. The galvanostatic measurements have explored that the voltage plateau during charging is slightly less than 3.70 V and the discharge voltage plateau is 3.40 V for the first cycle and 3.50 V for the following cycles at 0.1 C rate. The discharge capacity in the first cycle can reach 116 mAh g^?1, about 87 % of the theoretical capacity (134 mAh g^?1). It is believed that the product in the fully discharged state is Li₂Fe₂(SO₄)₃. However, the insertion reaction is reversible only for the second lithium ion. During cycling, the reversible capacity remains about 60 mAh g^?1. Further capacity fade is not found in the 20 discharge–charge cycles. The electrochemical impedance measurements have shown that there are two compressed semicircles in the Nyquist plots and a Warburg impedance in the low-frequency domain. The high-frequency semicircle is related with the electrode’s structural factor and the intermediate-frequency semicircle corresponds to the charge-transfer process.     

Improved electrochemical properties of YF<Subscript>3</Subscript>-coated Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> as cathode for Li-ion batteries

Yttrium fluoride YF₃ layer with different coating contents is successfully covered on the surface of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ via a common wet chemical approach. The XRD, SEM, TEM, and charge-discharge tests are applied to investigate the influence of YF₃ layer on the micro-structural, morphology, and electrochemical properties of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂. And the electrochemical test results demonstrate that the YF₃-coated LMNCO samples exhibit the improved electrochemical properties. The 2wt.%YF₃-coated LMNCO delivers a discharge capacity of 116.6 mAh g^?1 at 5 C rate, much larger than that (95.6 mAh g^?1) of the pristine one. Besides, the electrochemical impedance spectroscopy (EIS) and cyclic voltammetric results indicate that the YF₃ coating layer can promote the optimization formation of SEI film and reversibility of the electrochemical redox.     

Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@C hollow microspheres with high capacity as an anode material for lithium-ion batteries

Three-dimensional hierarchical Co₃O₄@C hollow microspheres (Co₃O₄@C HSs) are successfully fabricated by a facile and scalable method. The Co₃O₄@C HSs are composed of numerous Co₃O₄ nanoparticles uniformly coated by a thin layer of carbon. Due to its stable 3D hierarchical hollow structure and uniform carbon coating, the Co₃O₄@C HSs exhibit excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs). The Co₃O₄@C HSs electrode delivers a high reversible specific capacity, excellent cycling stability (1672 mAh g^?1 after 100 cycles at 0.2 A g^?1 and 842.7 mAh g^?1 after 600 cycles at 1 A g^?1), and prominent rate performance (580.9 mAh g^?1 at 5 A g^?1). The excellent electrochemical performance makes this 3D hierarchical Co₃O₄@C HS a potential candidate for the anode materials of the next-generation LIBs. In addition, this simple synthetic strategy should also be applicable for synthesizing other 3D hierarchical metal oxide/C composites for energy storage and conversion.