A comparison of electrochemical performance of natural graphite sulfurized by ball-milling and heat-treating as an anode for lithium ion batteries

Natural graphite (NG) was sulfurized by heat-treating or by high energy ball-milling the blend of NG with sulfur powder. The effect of the surface functional groups, containing sulfur, on the performance of the NG anode for a lithium ion battery was then investigated. X-ray photoelectron spectroscopy revealed that the sulfur was introduced onto the surface of NG in both of these methods. The results of scanning electron microscopy and Raman spectroscopy showed that the surface disorder of NG increased after sulfurization. Charge/discharge tests showed that the reversible capacity of the first cycle was increased after surface sulfurization and that the coulombic efficiency of the first cycle increased for the heat-treated sample but decreased for the ball-milled one. The change in the electrochemical performance was due to a number of factors including an increase in new active sites for lithium storage and an increase in surface area and increased disorder of the sulfurized NG samples.     

Sn-Co-artificial graphite composite as anode material for rechargeable lithium batteries

Nanosized Sn-Co prepared by ultrasonic-assisted chemical reduction is milled with artificial graphite (AG) to form Sn-Co-AG composite. The as-prepared materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectrometry and Brunauer-Emmett-Telle (BET) surface area measurement. XRD patterns show that Sn-Co particles are poorly crystallized and artificial graphite has a typical hexagonal graphite structure phase. The diffraction peaks of Sn-Co particles remain the same but some of AG obviously change after milling Sn-Co with AG. BET areas of AG, Sn-Co and Sn-Co-AG are 1.569, 13.187 and 6.754 m² g⁻¹, respectively. SEM images display the as-prepared Sn-Co particles have a size distribution ranging from 20 to 70 nm in diameter. After milling Sn-Co with AG, Sn-Co particles keep similar morphology but there is a perceptible change in AG. Electrochemical tests show that Sn-Co-AG composite possesses much improved electrochemical performance than the state-of-the-art graphite. This composite has great potential as an alternative material for improving the energy density of a lithium ion secondary battery.     

Synthesis of porous hollow six-branched star-like MnO and its enhanced electrochemical properties as a lithium ion anode material

Novel structured porous hollow six-branched star-like MnO was synthesized via a facile, surfactant-free hydrothermal decomposition, which was followed by high-temperature heat treatment. Compared with the nonporous hollow six-branched star-like MnO₂, the porous hollow six-branched star-like MnO realized substantially higher electrochemical performance (844.8 mAh g⁻¹ at 0.5 A g⁻¹ after 200 cycles and 769.7, 741.7, 728.9, 713.2, and 704.4 mAh g⁻¹ at 0.1, 0.3, 0.5, 1, and 1.5 A g⁻¹, respectively, for porous star-like MnO, compared with 338.4 mAh g⁻¹ and 476.7, 392.4, 357, 303.4, and 269.9, respectively, under the same testing conditions for nonporous star-like MnO₂). The superior performance of the porous hollow six-branched star-like MnO is attributed to its enhanced electrode kinetics, which are due to an enlarged active contact area and shortened electron and Li⁺ conduction paths.     

Carbon-coated silicon as anode material for lithium ion batteries: advantages and limitations

Carbon coating of silicon powder was studied as a means of preparation of silicon-based anode material for lithium ion batteries. Carbon-coated silicon has been investigated at various cycling modes vs. lithium metal. Ex situ X-ray data suggest that there is irreversible reduction of crystallinity of the silicon content. Since carbon layer preserving the integrity of the particle, the reversibility of the structural changes in the amorphous state Li-Si alloy provides the reversible capacity. The progressively decreased Coulomb efficiency with cycling indicates that more and more lithium ions are trapped in some form of Li-Si alloy and become unavailable for extraction. This is the main factor for the capacity fading during cycling. Qualitative studies of the impedance spectra of the electrode material at the first cycle for the fresh anode and at the last cycle after the anode capacity faded considerably and provide further support for this model of fading mechanism.     

Pyrolytic polyurea encapsulated natural graphite as anode material for lithium ion batteries

Carbon encapsulated graphite was prepared by coating polyurea on the surface of natural graphite particles via interfacial polymerization followed by a pre-oxidation at 250 °C in air and a heat treatment at 850 °C in nitrogen. FT-IR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to investigate the structure of the graphite before and after the surface modification. Galvanostatic cycling, dc impedance spectroscopy, and cyclic voltammetry were used to investigate the electrochemical properties of the modified graphite as the anode material of lithium cells. The modified graphite shows a large improvement in electrochemical performance such as higher reversible capacity and better cycleability compared with the natural graphite. It can work stably in a PC-based electrolyte with the PC content up to 25 vol.% because the encapsulated carbon can depress the co-intercalation of solvated lithium ion. The initial coulombic efficiency of C-NG and NG in non-PC electrolyte is 74.9 and 88.5%, respectively.     

Electrochemical characteristics of copper silicide-coated graphite as an anode material of lithium secondary batteries

Copper silicide-coated graphite as an anode material was prepared by the sequential employments of plasma enhanced chemical vapor deposition (PECVD) and radio frequency magnetron sputtering (RFMS) method at 300 °C. The silicon-coated graphite exhibited an initial discharge capacity of 540 mAh/g with 76% coulomb efficiency, and the discharge capacity was sharply decreased down to 50% of initial capacity after 30 cycles, probably due to large volume changes during the charge-discharge cycling. Copper silicide-coated graphite, however, exhibited an initial discharge capacity of 480 mAh/g with higher retention capacity of 87% even after 30 cycles, probably due to the enhanced interfacial conductivity. The copper silicide film on the graphite surface played as the active anode material of lithium secondary batteries via the reduction of interfacial resistance and mitigation of volume changes during repeated cycles.     

Purification and carbon-film-coating of natural graphite as anode materials for Li-ion batteries

A process of modification of natural graphite materials as anode for lithium ion batteries was attempted. The process started with the treatment of natural graphite with concentrated hydrochloric acid and concentrated sulfuric acid in a thermal autoclave, followed by the in situ polymerization of resorcinol-formaldehyde resin to coat the graphite, then heat-treatment. SEM, XRD, Raman and electrochemical charge-discharge analysis showed that the surface defects and impurities on natural graphite were eliminated by purification of the concentrated acids, and carbon-film encapsulation modified the surface structure of the graphite and reduced its BET surface area. The as-obtained natural graphite sample presented an initial charge-discharge coulombic efficiency of 88.4% and a reversible capacity of 355.8 mAh g⁻¹. The proposed process paves a way to prepare a promising anode material with excellent performance with low cost of natural graphite for rechargeable lithium ion batteries.     

Beneficial effects of Mo on the electrochemical properties of tin as an anode material for lithium batteries

A simple, novel method for improving the electrochemical response of Sn in lithium cells is proposed that involves preparing Sn by a reduction procedure in the presence of Mo powders. Four different Mo_xSn_1 − x mixtures (0 < x < 0.26) were electrochemically tested and their structural and textural properties determined by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties of the resulting composites in lithium cells were studied by galvanostatic, step potential electrochemical spectroscopy (SPES) and electrochemical impedance spectroscopy (EIS) measurements. The mixtures were found to consist of crystalline Sn and Mo; however, the presence of the latter element modified the Sn habit in two ways, namely, by significantly decreasing particle size and increasing the reactivity towards oxygen. Although Mo is inert towards lithium, it increased both the discharge capacity and the capacity retention of the electrode in relation to pure Sn. The improved interparticle connectivity, reduced electrolyte decomposition and decreased charge-transfer resistance observed in the Mo-containing samples appear to be beneficial effects of the addition of Mo.     

Nanoscale SnS with and without carbon-coatings as an anode material for lithium ion batteries

SnS nanoparticles were mechnochemical synthesized and then co-heated with polyvinyl alcohol (PVA) at various temperatures to obtain carbon coating. All amorphous carbon-coated SnS particles had average particle size of about 20-30 nm, revealed by transmission electron microscopy (TEM). During discharge-charge, ex situ XRD results indicated that SnS firstly decomposed to Sn, then lithium ions intercalated into Sn. The reaction of Li⁺ and Sn was responsible for the reversible capacity in cycling process. The lithium ion insertion and extraction mechanism of SnS anode was similar to that of Sn-based oxide. Electrochemical capacity retention of carbon-coated SnS obtained at 700 °C was superior to that of other prepared SnS anodes and especially the rate capability was obviously enhanced due to good electric conductivity and buffering matrix effects of carbon coating.     

Effects of electrolytes on the electrochemical performance of Si/graphite/disordered carbon composite anode for lithium-ion batteries

The influences of LiBF₄, LiClO₄, lithium bis(oxalato) borate (LiBOB), LiPF₆ with VC and without VC, and the mixed electrolytes composed of different ratios of LiBOB and LiPF₆ or LiClO₄ on the electrochemical properties of Si/graphite/disordered carbon (Si/G/DC) composite electrode were systematically investigated by constant current charge-discharge and electrochemical impedance spectra (EIS) techniques. Scanning electron microscopy (SEM) was used to observe the change of electrodes in morphology after given cycle numbers. X-ray photoelectron spectroscopy (XPS) was employed to understand the influences of different mixed electrolytes on the composition of SEI layers. The results showed that Si/G/DC composite electrode in the mixed electrolytes presented better electrochemical performance than in single electrolyte. The compactness and compositions of SEI layers intensively influenced the cycle performance of Si/G/DC composite materials. LiBOB and additive VC had a good synergistic effect on the formation of the dense SEI layers. In particular, Si/G/DC in 0.5 M LiBOB + 0.38 M LiPF₆ electrolytes containing VC exhibited a high reversible capacity and excellent cycle performance.     

Enhanced electrochemical performance of ZrO2 modified LiNi0.6Co0.2Mn0.2O2 cathode material for lithium ion batteries

LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathode has been modified by incorporating ZrO₂ nanoparticles to improve its electrochemical performance. Compared to the pristine electrode, the cycling stability and rate capability of 0.5 wt% ZrO₂ modified-NCM622 have been improved significantly. The 0.5 wt% ZrO₂ modified-NCM622 cathode shows a capacity retention of 83.8% after 100 cycles at 0.1 C between 2.8 and 4.3 V, while that of the pristine NCM622 electrode is only 75.6%. When the current rate is set as 5C, the capacity retention of the 0.5 wt% ZrO₂-modified NCM622 is 10% higher than that of the pristine NCM622. Also, the rate capability of 0.5 wt% ZrO₂-modified NCM622 is better than that of the pristine NCM622 at various C-rates in a voltage range of 2.8–4.3 V. The enhanced electrochemical performances of the ZrO₂-modified NCM622 cathodes can be attributed to their high Li-ion conductivity and structural stability.     

Hydrazine hydrate-induced hydrothermal synthesis of MnFe2O4 nanoparticles dispersed on graphene as high-performance anode material for lithium ion batteries

Herein, a MnFe₂O₄/graphene (MnFe₂O₄/G) nanocomposite has been synthesized via a facile N₂H₄·H₂O-induced hydrothermal method. During the synthesis, N₂H₄·H₂O is employed to not only reduce graphene oxide to graphene, but also prevent the oxidation of Mn²⁺ in alkaline aqueous solution, thus ensuring the formation of MnFe₂O₄/G. Moreover, MnFe₂O₄ nanoparticles (5–20 nm) are uniformly anchored on graphene. MnFe₂O₄/G electrode delivers a large reversible capacity of 768 mA h g⁻¹ at 1 A g⁻¹ after 200 cycles and high rate capability of 517 mA h g⁻¹ at 5 A g⁻¹. MnFe₂O₄/G holds great promise as anode material in practical applications due to the outstanding electrochemical performance combined with the facile synthesis strategy.     

Spherical natural graphite coated by a thick layer of carbonaceous mesophase for use as an anode material in lithium ion batteries

A method for coating a thick layer of carbonaceous mesophase was developed to treat spherical natural graphite (SNG) for use as anodes in lithium ion batteries. The carbonaceous mesophase layer was fabricated by heat treatment of a mixture of SNG and coal tar pitch. The thickness of the carbonaceous mesophase on the surface of the SNG was approximately 2.5 μm, which is effective for enhancing the strength of the carbonaceous mesophase shell and for allowing the shell to maintain good integrity at a high anode density (1.6 g cm⁻³). The mesophase layer increased the initial columbic efficiency from approximately 90% to 95%, dramatically improved the capacity retention and reduced the irreversible capacity by greatly decreasing the SNG surface area. The initial efficiency, cycle life and rate capability for the SNG anode covered by a thick mesophase layer gave comparable results as the mesocarbon microbeads (MCMB) anode, while the SNG anode reversible capacity of 341 mAh g⁻¹ was higher than that of MCMB, 319 mAh g⁻¹. Electrochemical measurements showed that SNG particles coated by a thick carbonaceous mesophase layer are strong candidates for use as possible anode materials in high energy density lithium ion batteries.     

Effects of TiO2 starting materials on the synthesis of Li2ZnTi3O8 for lithium ion battery anode

Lithium zinc titanate (Li₂ZnTi₃O₈) anode materials have been successfully synthesized using rutile-TiO₂ with different particle sizes as titanium sources via a molten-salt method. Various physical and electrochemical methods are applied to characterize the effects of TiO₂ particle sizes on the structures and physicochemical properties of the Li₂ZnTi₃O₈ materials. When the particle size of TiO₂ is too small (10 nm), it is difficult to homogeneously mix TiO₂ with the other raw materials. Thus, the final product Li₂ZnTi₃O₈ has poor crystallinity, large particle size, small specific surface area, pore volume and average pore diameter, which are disadvantageous to its electrochemical performance. Using TiO₂ with the proper particle size of 100 nm as the titanium source, the Li₂ZnTi₃O₈ (R-100-LZTO) with excellent electrochemical performance can be obtained. At 1 A g⁻¹, 175.8 and 163.6 mA h g⁻¹ are delivered at the 1st and the 200th cycles, respectively. The largest capacities of 163, 133.3 and 122.5 mA h g⁻¹ are delivered at 2.5, 5 and 6 A g⁻¹, respectively. The good high-rate performance of the R-100-LZTO originates from the good crystallinity, small particle size, large specific surface area and average pore diameter, low charge-transfer resistance and high Li⁺ diffusion coefficient.     

Review on doping strategy in Li4Ti5O12 as an anode material for Lithium-ion batteries

Lithium-Ion Batteries (LIBs) as rechargeable energy storages play a key role in saving oil and decreasing exhaust emissions which are used for many applications including electric vehicles and electronic devices. Lithium titanate (LTO) as a promised anode material provides not only the Li-ion extraction and intercalation reversibility but also low volume changing during Li transmission. Nevertheless, LTO has some limitations which can be improved by some strategies such as doping. Dopants as a substation in the crystal structure of LTO could result in better performance in LIBs. In this report, doping of LTO with all kinds of dopants and with different fabrication methods is reviewed.     

整形和表面改性对人造石墨负极材料性能的影响

在对不同来源人造石墨原料进行理化性能分析的基础上,按照相同的工艺条件制成负极材料,比较了原料来源不同的人造石墨用作锂离子电池负极材料的性能。再以同一来源人造石墨为原料,采用不同设备、不同工艺、不同含量沥青进行整形、炭包覆及表面氧化改性处理,探讨了不同工艺处理对所制备的人造石墨负极材料的粒度分布、振实密度、比表面积和电化学性能的影响。结果表明,整形工艺与设备、炭包覆和表面氧化改性处理对提高负极材料的性能具有重要的作用。     

Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries

A composite anode material of silicon/graphite/multi-walled carbon nanotubes (MWNTs) for Li-ion batteries was prepared by ball milling. This composite anode material showed a discharge capacity of 2274 mAh/g in the first cycle, and after 20 charge-discharge cycles, a reversible capacity of 584 mAh/g was retained, much higher than 218 mAh/g for silicon/graphite composite. It was observed that silicon particles were homogeneously embedded into the “lamellar structures” of flaked graphite particles, and the silicon/graphite composite particles were further wrapped by a MWNTs network. The improvement in the electrochemical properties of the composite anode material was mainly attributed to the excellent resiliency and good electric conductivity of the MWNTs network.     

Ultrafine SnO2 nanoparticles as a high performance anode material for lithium ion battery

In this paper, the ultrafine tin oxides (SnO₂) nanoparticles are fabricated by a facile microwave hydrothermal method with the mean size of only 14 nm. Phase compositions and microstructures of the as-prepared nanoparticles have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the ultrafine SnO₂ nanoparticles are obtained to be the pure rutile-structural phase with the good dispersibility. Galvanostatic cycling and cyclic voltammetry results indicate that the first discharge capacity of the ultrafine SnO₂ electrode is 1196.63  mAh g⁻¹, and the reversible capacity could retain 272.63 mAh g⁻¹ at 100 mA g⁻¹ after 50 cycles for lithium ion batteries (LIBs). The excellent electrochemical performance of the SnO₂ anode for LIBs is attributed to its ultrafine nanostructure for providing active sites during lithium insertion/extraction processes. Pulverization and agglomeration of the active materials are effectively reduced by the microwave hydrothermal method.     

Effect of calcination temperature on morphology and electrochemical performance of PbLi2Ti6O14

As a promising anode material, PbLi₂Ti₆O₁₄ has attracted the attention of many researchers. In this work, a series of PbLi₂Ti₆O₁₄ are prepared by solid state method at five different calcination temperatures and used as anode materials in lithium ion batteries. Through a series of tests, the results show that the phase purity, morphology and electrochemical performance of PbLi₂Ti₆O₁₄ can be seriously influenced by calcination temperature. When the calcination temperature is 900?°C, the phase-pure PbLi₂Ti₆O₁₄ can be obtained with relatively small particle size, excellent cycle performance and outstanding lithium ion diffusion behavior. It provides an initial charge capacity of 151.3?mA?h?g^?1 at 100?mA?g^?1. After 100 cycles, it shows a reversible capacity of 142.0?mA?h?g^?1 with superior capacity retention of 93.85%. In contrast, PbLi₂Ti₆O₁₄ formed at 800?°C displays an unsatisfactory performance due to the presence of impurity, even though it has the smallest particle size and the largest lithium ion diffusion coefficient among the five samples. The reversible capacity is only 82.6?mA?h?g^?1 after 100 cycles with capacity retention of 53.9%. In order to further study the lithium ion diffusion behavior of PbLi₂Ti₆O₁₄, the in-situ X-ray diffraction technique is also implemented. It is found that during the lithiation/delithiation process, the stable framework can effectively inhibit the volume change and ensures the excellent electrochemical performance of PbLi₂Ti₆O₁₄.