High performance Si/MgO/graphite composite as the anode for lithium-ion batteries

The Si/MgO/graphite composite was synthesized by high energy ball-milling and evaluated as a durable anode for lithium-ion batteries. EDX mapping indicated that Si was dispersed homogeneously in the MgO matrix. The composite delivered an initial capacity of ~ 700 mAh/g and maintained a capacity of 630 mAh/g after 74 cycles at 0.5 mA/cm²; even at 8 mA/cm² it delivered more than 85% of its capacity. Its volumetric capacity is double that of carbon. The coulombic efficiency climbed from 77% in the first cycle to above 99.5% after 20 cycles, and retained that value.     

Goethite nanorods as anode electrode materials for rechargeable Li-ion batteries

Although various transition metal oxides have been reported to act as low potential Li insertion hosts, the oxyhydroxides have remained unexplored to date. We show here that the hydroxide ions present in transition metal oxyhydroxides do not interfere with the lithium uptake and extraction, permitting very good reversibility of the reduction/oxidation reactions. Goethite (α-FeOOH) nanocrystals can uptake and extract large amount of Li via the conversion reaction mechanism, providing a reversible capacity of 500 mA h g⁻¹ at an average potential of 0.85 V vs. Li/Li⁺. The mechanism was examined using a combination of X-ray diffraction, electron microscopy, and the corresponding selected area electron diffractions (SAEDs). The α-FeOOH is reduced into nanoparticles of metallic Fe⁰ embedded in an amorphous matrix of Li₂O and LiOH in the first discharge; the subsequent cyclings are redox reactions between metallic Fe⁰ and Fe₂O₃ clusters.     

Carbon anode materials from polysiloxanes for lithium ion batteries

Three kinds of silicon-containing disordered carbons have been prepared by pyrolysis of polysiloxanes with different amounts of phenyl side groups. X-ray powder diffraction, X-ray photoelectron spectroscopy and electrochemical capacity measurements were performed to study their behaviors. Graphite crystallites, micropores, and silicon species affect their electrochemical performances. All of them present high reversible capacities, >372 mAh/g. Since the graphite crystallites are very small, they contribute very little to reversible capacity. The number of micropores produced by gas emission during the heat-treatment process decides whether they exhibit reversible capacity. Si mainly exists in the form C–Si–O and influences the irreversible capacity. There is no evident capacity fading in the first ten cycles, indicating promising properties for these disordered carbons.     

Anode materials for lithium ion batteries obtained by mild and uniformly controlled oxidation of natural graphite

Modification of natural graphite for anode materials has been a recent focus of research and development. Here we report that a common natural graphite, whose electrochemical performance is very poor, can be modified by solutions of (NH₄)₂S₂O₈, concentrated nitric acid solution, or green chemical solutions such as aqueous solutions of hydrogen peroxide and ceric sulfate. All treatments result in marked improvement of the electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior. The main reason is the effective removal of active defects in natural graphite, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. As a result, these changes inhibit the decomposition of electrolytes, prevent the movement of graphene planes along the a-axis direction, and provide more passages and storage sites for lithium. They are mild and the uniformity of the product can be well controlled. Pilot experiments show economic promise for their application in industry to manufacture anode materials for lithium ion batteries.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Sol–gel derived nano-crystalline CaSnO3 as high capacity anode material for Li-ion batteries

CaSnO₃ with the distorted-perovskite structure was prepared by sol–gel and high temperature solid-state reaction and electrochemical properties were studied in cell with Li as counter electrode. The sol–gel method gave uniform nano-crystallites (200–300 nm) of CaSnO₃ and was shown to deliver a reversible capacity of 380 mAh/g (0.005–1.0 V; 60 mA/g) with good cycling stability up to 45 cycles. The observed capacity involved in the first-discharge and the reversible capacity values during subsequent charge–discharge cycles show that the electrochemical process in CaSnO₃ is similar to other Sn-containing mixed oxide systems, viz., an initial structural reduction with Sn-metal formation followed by reversible Li–Sn alloy formation. The performance with respect to the attainable capacity, its retention on charge–discharge cycling and rate capability is better than the previously reported best-performing bulk Sn-oxide or ATCO starting materials which reveals that the perovskite structure and Ca-ion play a beneficial role.     

Carbon–fluorine compounds as battery materials

Historical aspects on the syntheses and structure models of carbon–fluorine compounds, discharge reaction and characteristics of Li/(CF)_n batteries, and syntheses and electrochemical behavior of new alternating cathode materials have been reviewed.     

Electrochemical properties and structures of surface-fluorinated graphite for the lithium ion secondary battery

Surface modification of graphite powder has been performed by elemental fluorine and radiofrequency (rf) plasma fluorination. Both methods give rise to an enlargement of the surface areas of graphite samples and a change of the pore volume distribution. The capacities of surface-fluorinated graphite samples are higher than those of original samples and even more than the theoretical capacity of graphite, 372 mAh g⁻¹, without any reduction of the first colombic efficiencies. The increments of the capacities are ∼5, 10, and 15% for graphite samples with average particle diameters of 7, 25 and 40 μm, respectively.     

Fluorine-doped nanocrystalline SnO2 powders prepared via a single molecular precursor method as anode materials for Li-ion batteries

Fluorine-doped nanocrystalline tin dioxide materials (F:SnO₂) have been successfully prepared by the sol-gel process from a single molecular precursor followed by a thermal treatment at 450-650 °C. The resulting materials were characterized by FTIR spectroscopy, powder X-ray diffraction, nitrogen adsorption porosimetry (BET) and transmission electron microscopy (TEM). The mean particle size increased from 5 to 20 nm and the specific surface area decreased from 123 to 37 m²/g as the temperature of heat treatment was risen from 450 to 650 °C. Fluorine-doped nanocrystalline SnO₂ exhibited capacity of 560, 502, and 702 mA h/g with 48%, 50%, and 40% capacity retention after 25 cycles between 1.2 V and 50 mV at the rate of 25 mA/g, respectively. In comparison, commercial SnO₂ showed an initial capacity of 388 mA h/g, with only 23% capacity retention after 25 cycles.     

Nickel foam-supported porous NiO/polyaniline film as anode for lithium ion batteries

Nickel foam-supported porous NiO film was prepared by a chemical bath deposition technique, and the NiO/polyaniline (PANI) film was obtained by depositing the PANI layer on the surface of the NiO film. The NiO film was constructed by NiO nanoflakes, and after the deposition of PANI, these nanoflakes were coated by PANI. As an anode for lithium ion batteries, the NiO/PANI film exhibits weaker polarization as compared to the NiO film. The specific capacity after 50 cycles for NiO/PANI film is 520 mAh g⁻¹ at 1 C, higher than that of NiO film (440 mAh g⁻¹). The improvement of these properties is attributed to the enhanced electrical conduction and film stability of the electrode with PANI.     

用于锂离子电池的国产天然石墨性能研究

选用国产山东天然石墨 ,比较系统地研究了其材料的结构、物理和电化学性能 .X射线衍射分析结果表明 ,国产天然鳞片微粉石墨由六方结构 (2H)和菱方结构 (3R) (含 30 %的菱方结构 )组成 ,是结晶完整性好的石墨 .作为锂离子电池负极材料 ,天然石墨具有高电压、高容量的特点 .但因自身结构的局限性 ,不能与含碳酸丙烯酯 (PC)的电解质相匹配     

Novel composite anode materials for lithium ion batteries with low sensitivity towards humidity

Graphitic anode materials for lithium ion batteries processed under high humidity conditions show severe performance losses. The sensitivity of these materials towards humidity can be significantly reduced by adsorbing metal ions like silver or copper ions, with subsequent heat treatment of these composites. Results of X-ray photoelectron spectroscopy, high-resolution electron microscopy, thermogravimetry, and differential thermal analysis indicate that the deposited metals exist in metallic and carbide, M_xC (M=Cu or Ag), forms. They remove or cover (i.e. deactivate) active hydrophilic sites at the surface of the graphite. These composites absorb less water during processing. The electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior, is markedly improved. This approach provides a potentially powerful method to manufacture lithium ion batteries under less demanding conditions.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Achieving high-performance Li2ZnTi3O8 anode for advanced Li-ion batteries by molybdenum doping

The Li₂ZnTi_3-xMo_xO₈ (x = 0, 0.05, 0.1 and 0.15) anode materials are successfully synthesized through a simple solid-state method, and few Li₂MoO₄ phase can be found in Li₂ZnTi_3-xMo_xO₈ (x = 0.1 and 0.15). All samples are composed of nanocrystalline particles and irregular micron-sized particles with a relatively uniform particle size of 100–200 nm Li₂ZnTi_2.9Mo_0.1O₈ shows the best electrochemical properties among all samples. The Li₂ZnTi_2.9Mo_0.1O₈ delivers a charge/discharge capacity of 188.1/188.2 mA h/g at 1 A/g after 400 cycles, but the corresponding capacity of pristine Li₂ZnTi₃O₈ is only 104.5 (102.2) mA h/g. The Mo⁶⁺ doping enhances the reversible capacity, rate performance, and cycling stability of Li₂ZnTi₃O₈, especially at large current densities. The improved electrochemical performance of Li₂ZnTi_3-xMo_xO₈ can be ascribed to the enhanced electrical conductivity, improved intercalation/de-intercalation reversibility of Li ions, increased lithium-ion diffusion coefficients, and reduced charge-transfer resistance. This work provides an effective strategy to construct high-performance anode materials for advanced lithium-ion battery; this effective design strategy may be used to enhance the reversible specific capacity, and rate the performance and cycle stability of other insertion-host anode materials.     

Impact of selected supramolecular additives on the initial electrochemical lithium intercalation into graphite in propylene carbonate

Impact of silicon tripodand-type electrolyte additives and graphite pre-treatment agents on the electrochemical intercalation of lithium cations into graphite was investigated. Addition of Si-tripodand-type silanes to propylene carbonate-based electrolytes was found to suppress detrimental solvent co-intercalation and graphite exfoliation. Similar effects were observed for graphite pre-treated with the reported silane agents. It was observed that the presented supramolecular additives allow for the formation of effective passive layers on graphite during first charging, and thus can be considered as novel low-cost film-forming components for rechargeable lithium batteries.      

Intercalation materials for lithium rechargeable batteries

An overview is given of intercalation materials for both the negative and the positive electrodes of lithium batteries, including the results of our own research. As well as lithium metal as a negative electrode, we consider insertion materials based on aluminium alloys. In the case of the positive electrode metal-oxides based on manganese, nickel and cobalt are discussed. Received: 27 May 1997 / Accepted: 30 July 1997     

Investigation of two-dimensional hf-based MXenes as the anode materials for li/na-ion batteries: A DFT study

Density functional theory calculations are performed to investigate electronic properties and Li/Na storage capability of Hf₃C₂ and its derivatives (uniform passivated: Hf₃C₂T₂ [T = F, O, OH] and hybrid passivated: Hf₃C₂F_xO_2-x and Hf₃C₂O_x(OH)_2-x [x = 1.0, 1.5]). For Hf₃C₂ monolayer, it has excellent performance, such as good conductivity, low diffusion energy barrier, low open circuit voltage, and high storage capacities (Li(1034.70 mAh g⁻¹), Na(444.90 mAh g⁻¹)), providing the most prospective as anode material. However, due to the unsaturated dangling bonds of surface Hf, so it is easily passivated. For the uniform passivated ones, Hf₃C₂T₂, show higher diffusion barriers and lower storage capacities than bare monolayer Hf₃C₂. Nevertheless, compared with uniform passivated ones, the hybrid passivated derivative, Hf₃C₂F_1.5O_0.5 and Hf₃C₂OOH possess a lower energy barrier and a better storage capacity. Therefore, Hf₃C₂F_1.5O_0.5 and Hf₃C₂OOH are deemed to be a suitable candidate as anode electrode material for Li-ion batteries. © 2019 Wiley Periodicals, Inc.     

低温等离子体在锂离子电池材料中的应用

综合评述了低温等离子体技术的基本原理、 常用方法及其在锂离子电池材料领域中的研究进展, 重点评述了等离子体技术在锂离子电池正极、 负极、 隔膜及固态电解质等重要组分中的材料制备与表面改性方面的主要研究结果和应用优势, 并对其所面临的挑战和未来的应用方向进行了展望.     

Lix(Al0.8Zn0.2) alloys as anode materials for rechargeable Li-ion batteries

The influence of the lithium content in the starting composition, depth of discharge, binder and electrolyte on the cycle stability was investigated. The structural changes in Li_x(Al_0.8Zn_0.2) electrodes during electrochemical lithium extraction and reinsertion were studied by in situ synchrotron diffraction. The crystal structure of the new compound Li₄Al_3.42Zn_11.58 was determined by single-crystal X-ray diffraction and can be described as combination of the CaCu₅ and MgFe₆Ge₆ structure types. The phase equilibria at 150 °C in the Li–Al–Zn system were investigated on six alloys, prepared along the lithium extraction–insertion line.     

Nanosized anatase titanium dioxide loaded porous carbon nanofiber webs as anode materials for lithium-ion batteries

Nanosized anatase titanium dioxide loaded porous carbon nanofibers (TiO₂/PCNFs) were prepared from electrospun TiO(OAc)₂/PAN/PMMA composite precursor fibers with different amount of PMMA porogen, which were sequentially heat-treated in different environments. Electrochemical measurement results show that these as-prepared TiO₂/PCNFs present higher cyclic reversible capacity than the TiO₂/CNFs counterpart (without PMMA porogen in its precursor fibers). Among the as-prepared TiO₂/PCNFs samples, the representative TiO₂/PCNFs (the mass ratio of PAN to PMMA is 3:1) exhibits the best high-rate performance with a high stable capacity retention about 200 mAhg^{− 1} at a current density as high as 800 mAg^{− 1}. This novel TiO₂/PCNFs composite material opens up a promising application in high-power lithium-ion batteries.     

改性石墨用于锂离子电池负极

石墨可用于锂离子电池负极材料，其改性方面的研究主要有：石墨的还原、氧化、表面包膜以及物理法处理。这些方法可以改变石墨的电子状态及表面结构，能够提高石墨的性能。本文介绍了改性石墨用于锂离子电池负极的研究概况。     

锂离子电池有机电解液材料研究进展

综述了锂离子电池有机电解液材料的研究现状。锂离子电池有机电解液主要由电解质锂盐、有机溶剂和添加剂三个部分组成,新型电解质锂盐的研究开发可分为三个方面：（1）LiTFSI及其类似物;（2）络合硼酸锂化合物;（3）络合磷酸锂化合物。有机溶剂的研究工作主要集中在新型有机溶剂的开发上。最重要的添加剂主要有三类：（1）主要用以改善碳负极SEI膜性能的添加剂;（2）过充电保护添加剂;（3）配体添加剂。