锂离子电池固态聚合物电解质研究进展

电解质是制备高功率密度和高能量密度、长循环寿命的锂离子电池的重要材料之一,而聚合物电解质是实现全固态锂离子电池的关键技术.总结近几年来为提高聚合物电解质电导率所作研究的新进展,并提出了今后的研究方向.     

一种新型的锂离子二次电池的电解质

本文介绍了氟烷基膦酸锂盐的一种Li[PF3(C2F5)3]的制备做了介绍，并将Li[PF3(C2F5)3]的电解液和六氟磷酸锂(LiPF6)的电解液在对水的稳定性，电化学稳定性，离子导电性以及热稳定性方面做了比较。     

Synthesis and electrochemical characterization of a new Se-doped spinel material for lithium secondary batteries

A new Se-doped spinel material, LiAl_0.18Se_0.02Mn_1.8O₄ powder with a phase-pure polycrystalline was synthesized by a sol–gel method. The material in the 3 V region (2.4 3.5 V) and both the 3 and 4 V region (2.4 4.4 V) initially deliver a discharge capacity of 81 and 178 mA h g^–1 which increase with cycling to reach 110 and 204 after 50 cycles, respectively. The material shows excellent cycleability in the 4 V region (3.0 4.4 V) with almost no capacity loss. The structural integrity of the Se-doped spinel was characterized by charge–discharge cycling tests and X-;ray diffraction.     

Cycling of lithium/metal oxide cells using composite electrolytes containing fumed silicas

The effect on cycle capacity is reported of cathode material (metal oxide, carbon, and current collector) in lithium/metal oxide cells cycled with fumed silica-based composite electrolytes. Three types of electrolytes are compared: filler-free electrolyte consisting of methyl-terminated poly(ethylene glycol) oligomer (PEGdm, M_w=250)+lithium bis(trifluromethylsufonyl)imide (LiTFSI) (Li:O=1:20), and two composite systems of the above baseline liquid electrolyte containing 10-wt% A200 (hydrophilic fumed silica) or R805 (hydrophobic fumed silica with octyl surface group). The composite electrolytes are solid-like gels. Three cathode active materials (LiCoO₂, V₆O₁₃, and Li_xMnO₂), four conducting carbons (graphite Timrex® SFG 15, SFG 44, carbon black Vulcan XC72R, and Ketjenblack EC-600JD), and three current collector materials (Al, Ni, and carbon fiber) were studied. Cells with composite electrolytes show higher capacity, reduced capacity fade, and less cell polarization than those with filler-free electrolyte. Among the three active materials studied, V₆O₁₃ cathodes deliver the highest capacity and Li_xMnO₂ cathodes render the best capacity retention. Discharge capacity of Li/LiCoO₂ cells is affected greatly by cathode carbon type, and the capacity decreases in the order of Ketjenblack>SFG 15>SFG 44>Vulcan. Current collector material also plays a significant role in cell cycling performance. Lithium/vanadium oxide (V₆O₁₃) cells deliver increased capacity using Ni foil and carbon fiber current collectors in comparison to an Al foil current collector.     

Binder effect on cycling performance of silicon/carbon composite anodes for lithium ion batteries

The cycling performance of a silicon/carbon composite anode has been significantly enhanced by using acrylic adhesive and modified acrylic adhesive as binder to fabricate the electrodes for lithium ion batteries. The capacity retentions of Si/C composite electrodes bound by acrylic adhesive and modified acrylic adhesive are 79% and 90% after 50 cycles, respectively. These two binders are electrochemically stable in the organic electrolyte in the working window. They also show larger adhesion strength between the coating and the Cu current collector as well as smaller solvent absorption in the electrolyte solvent than polyvinylidene fluoride (PVDF). Furthermore, sodium carboxyl methyl cellulose (CMC) plays an important role on improving the properties of acrylic adhesive, which increases the adhesive strength of acrylic adhesive and improves the activation of the electrodes.     

Advanced Sn/C composite anodes for lithium ion batteries

Metallic tin was deposited in fine particulate form on the surface of carbonaceous mesophase spherules (CMS) and in the pores of porous carbon by the decomposition and reduction of tin(II) 2-ethylhexanoate at 450 °C. The Sn/C composite powders obtained were used as anode materials for lithium ion cells. Electrochemical cycling tests of coin cells show that the dispersion of tin into the carbonaceous materials enhances the reversible capacity of the electrodes. The capacity retention at the 50th cycle is 91 % for Sn/CMS composite containing 22% tin, against 428 mAh g^–1 at the first cycle. With further increase in tin content, the capacity fade upon cycling is more rapid.     

废旧锂电池中有价金属回收及三元正极材料的再制备

探讨了磷酸体系下不同因素对废旧锂电池正极材料中有价金属浸出效率的影响，结果表明：在浸出时间60min，反应温度60℃，磷酸浓度2mol/L，液固比20mL/g，还原剂(H₂O₂)体积分数为4%时，可得最佳浸出效果，Co、Li、Mn、Ni浸出效率分别可达96.3%、100%、98.8%和99.5%；浸出液添加相应比例金属离子，采用草酸共沉淀法制备前体材料(Ni_1/3Co_1/3Mn_1/3)C₂O₄，并得到相应再生磷酸溶液。再生磷酸进行循环浸出实验，实验研究结果表明：循环浸出5次之后Li的浸出率仍可保持在90.1%，而Co、Mn和Ni的浸出率在75.0%以上。前体添加锂源Li₂CO₃煅烧合成Li(Ni_1/3Co_1/3Mn_1/3)O₂材料，考察了不同温度对Li(Ni_1/3Co_1/3Mn_1/3)O₂材料合成的影响，结果显示，当合成温度为800℃时，得到的材料性能最优良，初次放电容量可达136.4mA·h/g。在0.2C下经过50圈循环后容量保持率为97.2%。     

(S)-(+)-5-羟甲基-2-吡咯烷酮的合成方法改进

通过实验证明在(S)-( )-5-羟甲基-2-吡咯烷酮合成中，以硼氢化钠为还原剂时，所得产品产率和纯度都有大幅度提高；且实验操作简单方便，适合工业化。     

Electrochemical investigation of LiNi0.5Mn1.5O4 thin film intercalation electrodes

This work provides kinetic and transport parameters of Li-ion during its extraction/insertion into thin film LiNi_0.5Mn_1.5O₄ free of binder and conductive additive. Thin films of LiNi_0.5Mn_1.5O₄ (0.2 μm thick) were prepared on electronically conductive gold substrate utilizing the electrostatic spray deposition technique. High purity LiNi_0.5Mn_1.5O₄ thin film electrodes were observed with cyclic voltammetry, to exhibit very sharp peaks, high reversibility, and absence of the 4 V signal related to the Mn³⁺/Mn⁴⁺ redox couple. The electrode subjected to 100 CV cycles of charge/discharge delivered a capacity of 155 mAh g⁻¹ on the first cycle and sustained a good cycling behavior while retaining 91% of the initial capacity after 50 cycles. Kinetics and mass-transport of Li-ion extraction at LiNi_0.5Mn_1.5O₄ thin film electrode were investigated by means of electrochemical impedance spectroscopy. The apparent chemical diffusion coefficient (D_app) value determined from EIS measurements changed depending on the electrode potential in the range of 10⁻¹⁰-10⁻¹² cm² s⁻¹. The D_app profile shows two minimums at the potential values close to the peak potentials of the corresponding cyclic voltammogram.     

不同Li/Nb摩尔比In∶Fe∶LiNbO_3晶体的生长及其光学性能

在Li NbO3(LN)中掺摩尔分数为1%的In和掺质量分数为0.03%的Fe,用提拉法技术生长具有不同n(Li)/n(Nb)[n(Li)/n(Nb)=0.94,1.05,1.20,1.38]的In∶Fe∶LN晶体。测试不同n(Li)/n(Nb)的In∶Fe∶LN晶体的吸收光谱、抗光致散射能力和指数增益系数,并计算晶体的有效载流子浓度。结果表明晶体样品随着n(Li)/n(Nb)增加,吸收光谱的吸收边发生紫移,抗光致散射能力增加,指数增益系数和有效载流子浓度增大。采用n(Li)/n(Nb)=1.38的In∶Fe∶LN晶体作记录介质,n(Li)/n(Nb)=1.05的In∶Fe∶LN晶体作位相共轭镜进行全息关联存储实验。实验表明存储系统具有实时处理,成像质量好,信噪比高和能反复使用等优点。