A novel composite negative electrode consist of multiphase Sn compounds and mesophase graphite powders for lithium ion batteries

A modified electroless plating technique was adopted to prepare the Sn compounds/mesophase graphite powders (MGP) composite electrode. Characterization of the composite material showed that multiphase Sn compounds were uniformly deposited on MGP. The multiphase composition which contained metallic Sn, SnP₃ and SnP₂O₇ were expected to provide a higher spectator to Sn ratio for improved cycleability. During cycling between 0.001 and 1.5 V, the charge capacity was greatly enhanced without appreciable fading. From the voltage profiles and cyclic voltammetry (CV) curves, it was revealed that the capacity fading was caused by either the formation of insulated LiP in the early stage or by aggregation of metallic Sn after prolonged cycling. For improving the cycleability, the cut-off voltage was lowered from 1.5 to 0.9 V. Adjusting the voltage range was manifested to be an effective way for obtaining superior cycling performance in the Sn–P–O/MGP composite negative electrode. The capacity retention was as high as 96% of the highest capacity after charge/discharge between 0.001 and 0.9 V for 45 cycles.     

Characteristics of carbon-coated graphite prepared from mixture of graphite and polyvinylchloride as anode materials for lithium ion batteries

A carbon-coated graphite is investigated as the negative electrode for Li-ion batteries. The carbon-coated graphite particles are prepared by simple heat-treatment of mixtures of graphite and poly(vinyl chloride), PVC, at 800–1000°C in an argon flow. The carbon coating reduces significantly the initial irreversible capacity of the graphite in a propylene carbonate-based electrolyte, by suppressing the solvated lithium ion intercalation, and also improves the initial charge–discharge coulombic efficiency. By carbon coating, the specific surface area of graphite particles is greatly increased. These findings can be explained by assuming that a turbostratic structure of PVC-carbon resists irreversible side-reactions which are controlled predominantly by active, edge surface sites.     

Preparation and characterization of tin-based three-dimensional cellular anode for lithium ion battery

A three-dimensional cellular Sn-based anode has been prepared by electrodepositing tin onto 3D copper matrix under different current conditions and characterized by means of scanning electron microscope (SEM), X-ray diffraction (XRD), electrochemical cycling test. The properties of tin layer, such as particle size, porosity and shape, greatly affect cycling behavior of electrodes. Beside this, two additional factors including large bonding force and three-dimensional stress-alleviated environment are also important to the dimensional stability of electrodeposited layer. In order to improve cycling performance, a composite anode configuration is designed by casting inactive carbon black into the “valley-ridge” tin-coated architecture. Capacity fading of both anodes is remarkably suppressed with the help of mechanical compression coming from stuffing. Taking advantage of the 3D electrode configuration, CTA with stuffing experiences a more uniform diffusion process to form an intermetallic layer of Cu₆Sn₅ when heated and shows better cyclicity than 2D annealed anode.     

Electrolytic Sn/Li2O coatings for thin-film lithium ion battery anodes

Sn/Li₂O composite coatings on stainless steel substrate, as anodes of thin-film lithium battery are carried out in SnCl₂ and LiNO₃ mixed solutions by using cathodic electrochemical synthesis and subsequently annealed at 200 °C. Through cathodic polarization tests, three major regions are verified: (I) O₂ + 4H⁺ + 4e⁻ → 2H₂O (∼0.25 to −0.5 V), (II) 2H⁺ + 2e⁻ → H₂, Sn²⁺ + 2e⁻ → Sn, and NO₃⁻ + H₂O + 2e⁻ → NO₂⁻ + 2OH⁻ (−0.5 to −1.34 V), and (III) 2H₂O + 2e⁻ → H₂ + 2OH⁻ (−1.34 to −2 V vs. Ag/AgCl). The coated specimens are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and charge/discharge tests. The nano-sized Sn particles embedded in Li₂O matrix are obtained at the lower part of region II such as −1.2 V, while the micro-sized Sn with little Li₂O at the upper part, such as −0.7 V. Charge/discharge cycle tests elucidated that Sn/Li₂O composite film showed better cycle performance than Sn or SnO₂ film, due to the retarding effects of amorphous Li₂O on the further aggregation of Sn particles. On the other hand, the one tested for cut-off voltage at 0.9 V (vs. Li/Li⁺) is better than those at 1.2 and 1.5 V since the incomplete de-alloy at lower cut-off voltage may inhibit the coarsening of Sn particles, revealing capacity 587 mAh g⁻¹ after 50 cycle, and capacity retention ratio C50/C2 81.6%, higher than 63.5% and 49.1% at 1.2 and 1.5 V (vs. Li/Li⁺), respectively.     

Nitrogen doped secondary particle graphite anode for high capacity and high rate Li ion battery

本研究采用低成本易量产的方法制备了二次粒子黏接的石墨负极材料,并对其进行了氮掺杂,制备出具备高比容量和高倍率特性的锂离子电池负极材料。在扣式电池测试中,该材料表现出359.8 mA·h/g的可逆容量,组装的软包装全电池最小比能量可达230 W·h/kg,体积能量密度可达650 W·h/L。该软包装电池具备良好的3 C快速充电能力,充电容量可以在10 min内达到额定容量的51%,30 min即可充满电量,表现出极好的快速充电特性。在室温下进行3 C倍率充电和1 C倍率放电的循环测试中,循环1000次循环后容量保持率依然超过88%的初始容量,循环厚度膨胀率为10.1%,可满足大多数电子设备和电动汽车的需求。     

锂离子电池植入传感技术

电化学储能作为实现低碳电力系统的关键技术,近年来项目建设快速增长,其安全问题也日益突出。近10年间,全球至少发生30余起储能电站起火爆炸事故,提升运行效率、安全性、稳定性已刻不容缓。高安全高稳定的锂离子储能系统是电力行业发展的必然选择。现有基于模组层级的传感技术已不能完全满足有效预警的迫切需求,亟待发展新型智能传感技术。单体层级传感是破解储能锂电池高安全高稳定难题的有效途径。单体层级植入传感技术,可获得全寿命周期单体内部温度场、应变场、气压、气体等多传感信息,有望实现早预警、早隔离、早处置。本文将系统综述这一先进技术面临的诸多难题、挑战与最新进展,具体包括以下3个方面：植入传感器长寿命需求与单体内部电化学腐蚀条件的矛盾(测得准)、传感器植入需求与电池全寿命周期稳定服役的矛盾（埋得进）、传感信号高效传输需求与电池单体外壳电磁屏蔽的矛盾(传得出)。进一步,展望植入传感技术在锂离子电池早期热失控预警、全生命周期电化学特性方面的重要应用。     

Modularized battery management for large lithium ion cells

A modular electronic battery management system (BMS) is described along with important features for protecting and optimizing the performance of large lithium ion (LiIon) battery packs. Of particular interest is the use of a much improved cell equalization system that can increase or decrease individual cell voltages. Experimental results are included for a pack of six series connected 60 Ah (amp-hour) LiIon cells.     

Electrochemical behavior of plasma-fluorinated graphite for lithium ion batteries

Electrochemical properties of plasma-fluorinated graphite samples have been investigated in 1 mol dm⁻³ LiClO₄ ethylene carbonate (EC)/diethyl carbonate (DEC) solution at 25 °C. Fluorine contents in plasma-fluorinated graphite samples were in the range of 0–0.3 at.% by elemental analysis and surface fluorine concentrations obtained by X-ray photoelectron spectroscopy (XPS) were in the range of 3–12 at.%. Raman spectroscopy revealed that surface disordering of graphite was induced by plasma fluorination. Plasma treatment increased the surface areas of graphite samples by 26–55% and the pore volumes for the mesopores with diameters of 1.5–2 and 2–3 nm. Plasma-fluorinated graphites showed capacities higher than those of original graphites and even higher than the theoretical capacity of graphite, 372 mAh g⁻¹, without any change of the profile of charge–discharge potential curves. The increments in the capacities were approximately 5, 10 and 15% for graphites with average particle diameters, 7, 25 and 40 μm, respectively. Furthermore, the coulombic efficiencies in first cycle were nearly the same as those for original graphites or higher by several percents.     

Electrochemical properties of carbon-coated Si/B composite anode for lithium ion batteries

Carbon-coated Si and Si/B composite powders prepared by hydrocarbon gas (argon + 10 mol% propylene) pyrolysis were investigated as the anodes for lithium-ion batteries. Carbon-coated silicon anode demonstrated the first discharge and charge capacity as 1568 mAh g⁻¹ and 1242 mAh g⁻¹, respectively, with good capacity retention for 10 cycles. The capacity fading rate of carbon-coated Si/B composite anode decreased as the amounts of boron increased. In addition, the cycle life of carbon-coated Si/B/graphite composite anode has been significantly improved by using sodium carboxymethyl cellulose (NaCMC) and styrene butadiene rubber (SBR)/NaCMC mixture binders compared to the poly(vinylidene fluoride, PVdF) binder. A reversible capacity of about 550 mAh g⁻¹ has been achieved at 0.05 mAm g⁻¹ rate and its capacity could be maintained up to 450 mAh g⁻¹ at high rate of 0.2 mAm g⁻¹ even after 30 cycles. The improvement of the cycling performance is attributed to the lower interfacial resistance due to good electric contact between silicon particles and copper substrate.     

锂离子电池补锂技术

锂离子电池在化成过程中,负极SEI膜的形成会消耗大量活性锂,特别是在添加部分高容量硅基负极材料的情况下,导致电池首周库仑效率和电池容量低.补充活性锂是解决这一问题的有效手段,目前已报道的补充活性锂的途径很多,主要是负极补锂和正极极补锂两大类.负极补锂包括金属锂物理混合锂化,如在负极中添加金属锂粉或在极片表面辊压金属锂箔...     

纳米石墨化碳在锂离子电池中的应用进展

纳米石墨化碳因其优异的导电、导热及力学性能近年来备受重视,并在锂离子电池体系中得到广泛运用。纳米石墨化碳具有的优异电学性能及纳米尺度结构特征使其在解决锂离子电池中高导电性、导热性、充放电过程中的柔性及结构稳定性等方面发挥了重要作用。本文综述了近年来纳米石墨化碳在锂离子电池应用中的最新进展和研究热点,包括纳米石墨化碳在锂离子电池中直接充当高容量负极材料,纳米石墨化碳作为高性能骨架材料为电极提供导电及力学网络,与硅、金属氧化物等高容量电极材料复合形成同轴、核壳等结构的高容量电极材料甚至柔性电极等。如何进一步认识纳米石墨化碳储锂机制,发展其精确可控制备科学和工程技术,进而在三维尺度上构建高效的锂离子电池电极材料结构仍是未来的重点研究方向。     

Preparation of hierarchical porous carbon and its rate performance as anode of lithium ion battery

A hierarchical porous carbon with low oxygen content has been prepared by using polystyrene (PS) spheres as template and its structure, composition and performances as anode of lithium ion battery are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, element analysis (EA), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge test. The results obtained from SEM, TEM, XRD, FTIR, and EA indicate that the prepared sample has a well-interconnected pore structure with a pore size of 170 nm and has an oxygen content of 3.3 ± 0.2 wt.%. The low oxygen content of the prepared sample can be ascribed to the low decomposition temperature of the template that was determined by thermal analysis. EIS shows that the prepared sample has lower electrochemical impedance for the lithium insertion/de-insertion than commercial natural graphite and charge/discharge tests show that the battery using the prepared sample as anode exhibits better rate performance than that using the graphite.     

Development of long life lithium ion battery for power storage

With the aim of developing lithium ion batteries with a long life and high efficiency for power storage, we experimentally evaluated combinations of cathode and anode active materials, in which batteries are able to obtain over 4000 cycles or 10 years of life. An acceleration method was evaluated using coin cells. We found that changing the current density was effective for evaluating battery life, since the logarithm of the cycle life showed a linear relationship to current density. Based on the current density increasing method, various combinations of cathode and anode active materials were tested. The cell system of LiCoO₂/Li_4/3Ti_5/3O₄ clearly showed a long life of about 4000 cycles. The energy density of the cell using the Li_4/3Ti_5/3O₄ anode is obviously smaller than that using a graphite anode, the cell with Li_4/3Ti_5/3O₄ anode was thought to have some merit especially in the large-scale-layer-built type battery by the applicability of the Al anode collector and a light weight battery case.     

Interpretation of the electrode binder standard for lithium ion battery

电极黏结剂是锂离子电池的重要辅助功能材料之一,虽然本身没有容量,但却是维持电极完整性的关键,决定了电极涂层的附着力和电极的柔韧性,并会影响到电极浆料的流变特性等工艺性能。本文主要分析了与电极黏结剂相关的国内标准,对锂离子电池电极黏结剂的相关特性和测试方法进行了介绍,并对未来电极黏结剂标准的制定提出了建议。     

Safety test and evaluation method of lithium ion battery

对锂离子电池的机械滥用、热滥用和电滥用安全性测试与评价方法的原理进行了分析,对具有代表性的锂离子电池安全测试标准GB/T 31467.3/31485和SAE J2464/UN 38.3的相关试验方法进行了对比分析。应用X射线三维CT技术,测试了安全性试验前后锂离子电池内部结构的变化,对X射线三维CT应用于锂离子电池安全性测试分析的前景进行了展望。为锂离子电池安全失效模式分析指明了方向。     

Chemical and structural instabilities of lithium ion battery cathodes

The chemical and structural stabilities of various layered Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes are compared by characterizing the samples obtained by chemically extracting lithium from the parent Li_1−xNi_1−y−zMn_yCo_zO₂ with NO₂BF₄ in an acetonitrile medium. The nickel- and manganese-rich compositions such as Li_1−xNi_1/3Mn_1/3Co_1/3O₂ and Li_1−xNi_0.5Mn_0.5O₂ exhibit better chemical stability than the LiCoO₂ cathode. While the chemically delithiated Li_1−xCoO₂ tends to form a P3 type phase for (1 − x) < 0.5, Li_1−xNi_0.5Mn_0.5O₂ maintains the original O3 type phase for the entire 0 ≤ (1 − x) ≤ 1 and Li_1−xNi_1/3Mn_1/3Co_1/3O₂ forms an O1 type phase for (1 − x) < 0.23. The variations in the type of phases formed are explained on the basis of the differences in the chemical lithium extraction rate caused by the differences in the degree of cation disorder and electrostatic repulsions. Additionally, the observed rate capability of the Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes bears a clear relationship to cation disorder and lithium extraction rate.     

Modified natural graphite as anode material for lithium ion batteries

A concentrated nitric acid solution was used as an oxidant to modify the electrochemical performance of natural graphite as anode material for lithium ion batteries. Results of X-ray photoelectron spectroscopy, electron paramagnetic resonance, thermogravimmetry, differential thermal analysis, high resolution electron microscopy, and measurement of the reversible capacity suggest that the surface structure of natural graphite was changed, a fresh dense layer of oxides was formed. Some structural imperfections were removed, and the stability of the graphite structure increased. These changes impede decomposition of electrolyte solvent molecules, co-intercalation of solvated lithium ions and movement of graphene planes along the a-axis direction. Concomitantly, more micropores were introduced, and thus, lithium intercalation and deintercalation were favored and more sites were provided for lithium storage. Consequently, the reversible capacity and the cycling behavior of the modified natural graphite were much improved by the oxidation. Obviously, the liquid–solid oxidation is advantageous in controlling the uniformity of the products.     

Transmission electron microscopy of lithium ion battery materials

理解材料的构-效关系是功能材料领域的永恒话题,在锂离子电池材料的研究中亦是如此。因此可以看到如X射线衍射、中子衍射、核磁共振、X射线电子能谱等结构表征手段被应用于锂离子电池材料的研究中。但是因上述方法对于微观局域结构并不敏感,而给出平均的结构信息。材料的性能往往随微观结构的不同而天差地别,因此获取锂离子电池材料的微观结构信息十分重要。透射电子显微镜具有原子尺度的空间分辨能力,可以获取原子尺度上的结构扭曲和电子结构变化,在锂离子电池材料的研究中起到了至关重要的作用。本文从电子显微学和锂离子电池材料的关系入手,从基本原理和实验方法出发,为相关领域科研人员提供便利。     

High-throughput quantum chemistry and virtual screening for lithium ion battery electrolyte additives

Advances in the stability and efficiency of electronic structure codes along with the increased performance of commodity computing resources has enabled the automated high-throughput quantum chemical analysis of materials structure libraries containing thousands of structures. This allows the computational screening of a materials design space to identify lead systems and estimate critical structure-property limits which should prove an invaluable tool in informing experimental discovery and development efforts. Here this approach is illustrated for lithium ion battery additives. An additive library consisting of 7381 structures was generated, based on fluoro- and alkyl-derivatized ethylene carbonate (EC). Molecular properties (e.g. LUMO, EA, μ and η) were computed for each structure using the PM3 semiempirical method. The resulting lithium battery additive library was then analyzed and screened to determine the suitability of the additives, based on properties correlated with performance as a reductive additive for battery electrolyte formulations.     

Vinylene carbonate and vinylene trithiocarbonate as electrolyte additives for lithium ion battery

Vinylene carbonate (VC) and vinylene trithiocarbonate (VTC) are studied as electrolyte additives in two kinds of electrolytes: (1) propylene carbonate (PC) and diethyl carbonate (DEC) (1:2 by weight) 1 mol dm⁻³ LiPF₆; (2) ethylene carbonate (EC) and DEC (1:2 by weight) 1 mol dm⁻³ LiPF₆. Characterization is performed by cyclic voltammetry, impedance spectroscopy, scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and half cell tests. Cyclic life is better in either electrolyte with VC than either electrolyte with/without VTC. SEM shows VC and VTC both form well developed passivation films on the graphite anode, but the films with VTC are thicker than with VC. EIS shows the VTC films have significantly higher charge transfer resistance. The VTC film in PC fails to protect against exfoliation. XPS indicates VTC has different reaction pathways in PC relative to EC. In EC/DEC, VTC forms polymeric C-O-C-like components and sulfide species (C-S-S-C, S and C-S-C). In PC/DEC, VTC does not form polymeric species, instead forming a film mainly containing LiF and Li₂S. It appears that a thinner polymeric film is preferential. The specific data herein are of interest, and the general conclusions may help development of improved additives for enhanced Li-ion battery performance.