锂离子电池电解液过充添加剂的行为

制备了3种1 mol/L LiPF6电解液,溶剂组成分别为:1)碳酸乙烯酯,碳酸二甲酯和碳酸甲乙酯;2)碳酸乙烯酯,碳酸二甲酯,碳酸甲乙酯和4%联苯;3)碳酸乙烯酯,碳酸二甲酯,碳酸甲乙酯和4%环己基苯.采用线性电压扫描法、锂循环效率法、锂离子电池的循环性能法和3 C倍率过充的方法测试了联苯与环己基苯电解液过充添加剂的行为.结果表明:环己基苯是一种较实用的锂离子电池电解液过充添加剂,环己基苯的电化学稳定性比联苯的高,环已基苯的氧化电势为4.72 V(vs Li/Li ),联苯的为4.54 V(vs Li/Li );以1 mA电流循环20次后,联苯的铂电极锂循环效率为15.7%,环己基苯的为59.3%;锂离子电池以1 C循环150次后,环己基苯的容量保持率为88%,联苯的为76.3%.环己基苯与联苯添加剂都改善了锂离子电池的耐过充性能,且两者的效果十分接近.     

Electrochemical properties of rechargeable organic radical battery with PTMA cathode

The electrochemical properties of the organic radical battery (ORB) having a lithium metal anode and a cathode consisting of a nitroxide radical polymer poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) with 1M LiPF₆ as an electrolyte in ethylene carbonate (EC)/dimethyl carbonate (DMC) have been evaluated at room temperature. The cell, with a thin cathode of 17 μm thickness incorporating 40 wt.% of PTMA, exhibited the full theoretical specific capacity at current densities up to 10 C (∼1 mA/cm²). However, a decrease in the specific capacity and an increase in the ohmic resistance were observed at higher current densities. The cell performance was good even on repeated charge-discharge cycles as an excess of 85 % retention of the initial discharge capacity was observed. This was true even after 400 cycles. However, a gradual decrease in capacity, an increase in charge-discharge voltage separation, and an electrode/electrolyte interfacial resistance have been observed after a large number of cycles. The examination of the scanning electron micrographs of the cathode material revealed that prolonged cycling resulted in the agglomeration of PTMA particles. These in turn increased the resistance and decreased the capacity of the cell.     

Electrochemical performance of tris(2-chloroethyl) phosphate as a flame-retarding additive for lithium-ion batteries

We studied tris(2-chloroethyl) phosphate (TCEP) as a potential flame-retarding additive and its effect on the electrochemical cell performance of lithium-ion battery electrolytes. The electrochemical cell performance of additive-containing electrolytes in combination with a cell comprised of a LiCoO₂ cathode and a mesocarbon microbeads anode was tested in coin cells. The cyclic voltammetry results show that the oxidation potential of TCEP-containing electrolyte is about 5.1 V (vs. Li/Li⁺). A cell with TCEP has a better electrochemical cell performance than a cell without TCEP in an initial charge and discharge test. In a cycling test, a cell containing a TCEP-containing electrolyte has a greater discharge capacity and better capacity retention than a TCEP-free electrolyte after cycling. The results confirm the promising potential of TCEP as a flame-retarding additive and as a means of improving the electrochemical cell performance of lithium-ion batteries.     

Surface composition and electrochemical behavior of LiNi1/3Co1/3Mn1/3O2 cathode material with copper additive

LiNi_1/3Co_1/3Mn_1/3O₂（NCM） cathode material containing copper was prepared by co-precipitation method.The material was characterized by X-ray photoelectron spectroscopy（XPS） and galvanostatic cycling.XPS data indicate that surface compositions of the samples containing copper are different from the bare NCM.Copper on surface of particles was enriched,while nickel and lithium content was reduced.The electrochemical performance of NCM was affected by the change of surface compositions.Cycling performance charged to the cutoff voltage of 4.6 V was improved by introducing copper into the material.The effects of copper content on electrochemical behaviors of NCM at 4.5 V were discussed.     

无机有机复合材料Bi2Te3／PAn电化学嵌锂性能研究

采用机械共混法制备了复合材料Bi2Te3/PAn,并对其电化学嵌锂性能进行了研究.研究发现Bi2Te3/PAn快速充放电性能良好,在以100 mA·g-1的电流密度充放电时首次可逆容量为480 mAh·g-1,到第20个循环时容量保持在200mAh·g-1.通过非原位X射线衍射方法研究其嵌锂机理,发现Bi2Te3在首次放电时分解,在随后的循环中以Te和Bi为嵌锂中心进行可逆储锂.     

Enhancing cycle stability of Li metal anode by using polymer separators coated with Ti-containing solid electrolytes

The employment of lithium metal anode in rechargeable lithium batteries has been hindered by the safety concerns which are associated with the uncontrolled lithium dendrite growth and the unceasing side reactions with liquid electrolytes.In this work,we report that the use of Ti-containing solid electrolyte-coated separators can greatly enhance the cycle performances of lithium metal anode in cells using liquid electrolytes.The detailed morphologic studies indicate that more uniform lithium deposition is achieved in cells using Ti-containing solid electrolyte-coated separators than that using Al_2 O_3-coated separators,which is likely due to the modified anode and electrolyte interfacial properties induced by the reactive nature of Ti-containing solid electrolytes with metallic lithium.This work demonstrates an effective strategy to enhance the homogeneity of lithium deposition,which leads to the stable cycling of lithium metal anode in rechargeable lithium-ion batteries.     

PVdF-HFP-Based Gel Polymer Electrolyte with Semi-Interpenetrating Networks For Dendrite-Free Lithium Metal Battery

The safety issues and lower energy density of the lithium metal batteries are the two main challenges that hinder their applications in the fields of electric vehicles and portable devices.In this work,the semi-interpenetrated polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-based gel polymer electrolyte was synthesized through UV-curing method by employing the ethoxylated trimethylolpropane triacrylate (ETPTA) monomer.The semi-interpenetrating networks formed by polymerization of ETPTA and the high liquid absorption rate of the PVdF-HFP impart the as-prepared electrolyte with a high room temperature ionic conductivity of 3.17 × 10-3 s cm-1 and a high mechanical strength of 3.46 MPa.LiFePO4 was selected as cathode materials,and the active material loading of the cathode is about 4.2 mg cm-2.The electrolyte shows superior long-term cycling properties (127 mAh g-1 after 200 cycles at 0.5 C),excellent rate performance (113 mAh g-1 at 1 C,80 mAh g-1 at 2 C,and the discharge capacity of 135 mAh g-1 can be restored when the rate goes back to 0.1 C) as well as good ability to inhibit the growth of lithium dendrite (about 150 h).The facile synthesis strategy and great electrochemical performance of the electrolyte make it a potential candidate for lithium metal batteries.     

Effect of lithium or aluminum substitution on the characteristics of graphite for anode of lithium ion batteries

Modification of graphite for anode of lithium ion batteries is investigated. Results of X-ray diffraction shows lithium and aluminum exists as Li compound (CH3COOLi-2H2O) and Al compound (AID3) in the graphite, respectiovely. The Brunauer-Emmer-Teller (BET) surface area of the modified graphite increases. According to the electrochemical measurements of Li/C cell and prototype Li-ion batteries, the Li-doped graphite has large reversible capacity of 312.2 mA·h/g, low irreversible capacity of 52.9 mA·h/g, and high initial coulombic efficiency of 85.51 %. The 063448 size proto-type battery with Li-doped graphite anode has large discharge capacity of 845 mA·h and good cycling performance. The initial charge/discharge characteristic of Al-doped graphite is close to those of undoped graphite, but the prototype battery with Al-doped anode shows the best cycling performance with capacity retention ratio of 94.06% at the 200th cycle.     

Li2MnO3的电化学活性及脱嵌锂机理研究进展

富锂固溶体正极材料xLizMnO3·（1-x）LiMO2（M--Co,Ni,Mn…）,首次不可逆容量很大程度上与组分中的LizMnO3电化学过程有关。富锂固溶体正极材料4．5V区域充电平台是组分中Li2MnO3电化学活化过程;Li2MnO3首次循环不可逆容量较大,约在50～100mAhg-1,4．5V电位脱出Li＋同时脱出O2-,等效脱出不可嵌入的Li2O;Li2MnO3与分解的电解液发生离子交互反应后,H＋占据不可逆位置,阻碍了Li＋的嵌入;多周循环晶体结构改变,形成不可逆结构并有新相生成。本文综合介绍近几年关于Li2MnO3结构、常温脱嵌锂机理、高温下电解液分解及循环后结构变化等方面的研究现状。     

Tris(trifluoromethylsulfonyl)methide-doped polypyrrole as a conducting polymer actuator with large electrochemical strain

A free-standing polypyrrole (PPy) film actuator, prepared electrochemically from a methyl benzoate solution of 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide (DMPIMe), exhibited up to 36.7% electrochemical strain in a propylene carbonate (PC)/water solution of lithium bis(nonafluorobutylsulfonyl)imide, Li(C₄F₉SO₂)₂N (LiNFSI). The maximum electrochemical strain of Me-doped PPy film depended on the electrolyte used for driving the Me-doped PPy actuator. When a PC/water mixed solution of lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) was used as the driving electrolyte, the maximum electrochemical strain, measured by cycling between −0.9 and +0.7 V versus Ag/Ag⁺ at 2 mV s⁻¹, was 24.2%, smaller than that (30.0%) driven with LiNFSI. When a PC/water suspension of DMPIMe was used as the driving electrolyte, the maximum electrochemical strain was 31.9%. However, the response speed of Me-doped PPy actuator driven with DMPIMe was slower than those driven with Li(C_nF_2n+1SO₂)₂N, due presumably to the size and shape of the anions. The addition of CF₃COOH in electrolytic solutions for electropolymerization increased the maximum electrochemical strains (36.7% and 36.6%) of Me-doped PPy actuator driven by using a PC/water solution of LiNFSI and a PC solution of DMPIMe, respectively.     

Electrochemical Study of Monoclinic Li3V2(PO4)3 in the Voltage Range of 1.5~3.0 V

采用液相法合成了Li3V2(PO4)3(空间群P21/n)电活性材料。用XRD和恒流充放电对样品的微观结构和电化学性能进行了表征。结果表明,在1.5~4.3V电压范围内,样品在平均电压为1.81和3.77V时均发生了可逆的锂嵌入反应;锂嵌出和嵌入过程中均出现一系列复杂的相变。在1.5~3.0V电压范围内,以C/5倍率循环50周后,样品的容量衰减极小,表明锂脱嵌反应具有优良的循环稳定性。因此,Li3V2(PO4)3可以同时作为正极和负极而组成对称电池。另外,1.5~4.3V电压范围内进行的嵌锂反应可以充当一种内置的过充电安全阀。     

Preparation and characterization of high salts polymer electrolyte based on poly（lithium acrylate）

1　INTRODUCTIONWorldwide research and efforts are currentlyunderway to fabricate all solid state, rechargeableLi and Li ion batteries utilizing Li+ conductivepolymer electrolytes[1]. Solid polymer electrolytespossesses many advantages including high ionicconductivity, high specific surface energy, solventfree, wide electrochemical stability windows, lightand easy processability[2]. Apart from polyethy lene oxide ( PEO )[3], poly ( vinyl alcohol )(PAV)[4], …     

商品化石墨作为聚合物锂离子电池负极材料的性能表征

采用商品化中间相碳微球(MCMB)及人造石墨与中间相碳微球的混合体作为聚合物锂离子电池的负极材料,通过SEM、XRD对比研究了两种负极材料电化学循环前后的微观形貌和相结构,测试了两种聚合物锂离子电池的倍率放电性能和循环寿命,并通过交流阻抗谱分析了两种负极材料的电化学性能差异.结果表明:掺入人造石墨后,中间相碳微球的平均粒径和比表面积增大,电化学循环200次后的晶面间距减小、石墨化度增大,倍率放电性能降低,电荷转移电阻及锂离子扩散阻抗均增大,循环性能得到较大提高.     

Electrochemical and interfacial properties of (PEO)<Subscript>10</Subscript>LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>−Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite polymer electrolytes using ball milling

Electrochemical and interfacial properties of (PEO)₁₀LiCF₃SO₃−Al₂O₃ composite polymer electrolytes (CPEs) prepared by either ball milling or stirring are reported. Ball milling was introduced into a slurry preparative technique utilizing PEO, lithium salt and Al₂O₃ powder ranging from 5 to 15 wt.%. The ionic conductivity was increased by ball milling over a range of temperatures. In particular, a significant increase at low temperature below the melting point of crystalline PEO was observed. Interfacial stability between lithium electrode and CPE was significantly improved by the addition of alumina as well as by ball milling. The electrochemical stability window produced by (PEO)₁₀LiCF₃SO₃−Al₂O₃ ball milling was higher than that of stirring, which was about 4.4 V. Charge/discharge performance of Li/CPE/S cells with (PEO)₁₀LiCF₃SO₃−Al₂O₃-12 hr ball milling was superior to that of a pristine polymer electrolyte due to the low interface resistance and high ionic conductivity.     

锂离子电池用聚合物电解质的制备与性能研究

通过原位复合法制备了PEO/LiClO4/SiO2聚电解质膜,采用TEM、XRD、交流阻抗法和充放电测试等研究了粒子的分布状态、聚合物电解质膜的结晶行为及组装成电池的充放电行为。结果表明,原位生成的SiO2粒子分布均匀,抑制了聚合物电解质的结晶,以此膜为电解质组装的全固态聚合物锂电池首次充电电压平台在4.2V左右,放电中值电压为3.6V,初始充电比容量为130mAh·g-1,50次循环后放电容量保持在84mAh·g-1。     

1,3-dioxolane pretreatment to improve the interfacial characteristics of a lithium anode

1,3-dioxolane （DOL） was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra （EIS） meastLrements revealed that, after the DOL pretreatment, the lithium electrode had better interfacial stability during immersion in electrolyte and as repeated charge/discharge cycles. It was proved by SEaM that the pretreated one has smoother morphology and less dendrite after repeated charge/discharge cycles. Consequentially, benefiting from the better interface characteristics of the lithium electrode, the rechargeable lithium cell with a DOL-pretreated lithium anode had the obviously enhanced discharging performance and better cyclability.     

Mesoporous Nanostructured Materials for the Positive Electrode of a Lithium–Oxygen Battery

Nanostructured carbon materials (CMs), the structure can vary widely, are promising materials for the positive electrode of a lithium–oxygen battery (LOB). The electrochemical characteristics of CMs studied in model conditions and their porous structure, as well as testing them as an active material for the positive electrode in an LOB sample, show that nanotubes (CNTs) and Super P carbon black possess the highest charge–discharge characteristics in an aprotic solvent (DMSO). Mono- and bimetallic systems containing Pt, Pd, and Ru and synthesized on CNT and Super P allow one to reduce discharge and charge overvoltage. In the presence of catalytic systems, an improvement in the energy-conversion efficiency of up to 73–76.7% is achieved for the LOB positive electrode. The possibility of achieving a stable cycling process in an LOB with a positive electrode on the basis of developed catalysts and with a LiClO₄/DMSO electrolyte is shown. For the first time, the positive influence of iodine (reducing the charge voltage to about 0.8–1.0 V as compared to the characteristics of an LOB using an electrolyte without additives) on the electrode characteristics of a Li–O₂ cell with the highly electron-donating solvent DMSO is demonstrated.     

Inkjet printed electrochemical organic electronics

A conventional desktop inkjet printer has been used as a combined deposition and patterning tool of electrochemical organic transistors on rough flexible carriers. The functionality of these devices rely upon redox reactions occurring at the interface between a conjugated polymer film and an electrolyte. Both the electrolyte and the conjugated polymer suspension (an aqueous dispersion of poly(3,4-ethylenedioxythiophene):poly(styrene sulphonic acid)) were additively patterned with the inkjet printer, making the electrochemical device all-inkjet printed. Basic implementations of the transistor in simple electrochemical logical circuitry have been produced. The printing technique can be anticipated to be used for the production of small series of devices based on the electrochemical technology discussed.     

Electrochemical investigation of the lithium-niobium disulphide organic electrolyte rechargeable cell

The reversibility of the Li_xNbS₂ electrode in organic electrolyte cells has been examined by polarization and cycling tests. The reversibility of the electrode appears to be influenced by lithium composition and diffusion, while the cycling life of complete Li/Li_xNbS₂ cells is limited by the poor cyclability of the lithium electrode.     

Synthesis and electrochemical performances of spherical LiFePO4 cathode materials for Li-ion batteries

Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g -1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g -1.The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.