磷酸铁锂正极材料与电解液的相容性研究

在锂离子电池使用过程中磷酸铁锂正极材料会与电解液发生许多副反应,导致铁的溶解,造成正极材料与电解液相容性差。为了研究磷酸铁锂正极材料与电解液的相容性及其对电池搁置性能的影响,先利用电感耦合等离子发射光谱对不同磷酸铁锂正极材料在不同电解液中的溶铁量进行了表征,后又对制备的电池进行了常温及高温搁置性能测试。结果表明：磷酸铁锂正极材料对电解液具有选择性,并且正极材料在电解液中的溶铁量越大,其相容性越差,对锂离子电池性能影响越大。     

动力电池正极材料LiFePO_4的产业化应用展望

磷酸铁锂正极材料兼具安全性好、容量高且对环境友好等优点,成为目前最具潜力的动力电池正极材料之一。但其较低的电子导电率及离子电导率等缺点也十分明显。主要从磷酸铁锂正极材料本身的性能,包括倍率性能、能量密度、循环寿命和高低温性能方面分析了其实际应用于动力电池的潜力,以及结合国内外锂离子电池正极材料供应商情况简述了目前国内外磷酸铁锂产业化现状和趋势。     

磷酸铁锂高温循环性能的改善

磷酸铁锂结构稳定、循环性能优异,但是随着主机厂家对质保要求的不断提升,磷酸铁锂仍面临着高温循环性能不能满足客户要求的情况。以磷酸铁锂正极锂离子电池为研究对象,分别对比了基础电解液体系和改善电解液体系[在基础电解液中添加二氟二草酸硼酸锂（LiODFB）]对电池高温循环性能的影响。对循环后的电池采用直流内阻（DCIR）、电化学交流阻抗谱（EIS）、d Q/d U（恒定的电压间隔内电池容量的变化）曲线等无损分析方式进行数据对比,结果表明改善电解液体系电池的电荷转移阻抗进一步降低。通过对电池进行解剖,对两种电解液体系的电池极片进行了厚度分析、X射线衍射（XRD）分析、扫描电镜（SEM）分析、电感耦合等离子体发射光谱（ICP）元素分析等,结果表明改善电解液体系的电池在抑制负极表面副反应、减少正极铁溶出方面具有明显的效果,因此电池的高温循环性能更好。     

锂离子电池正极材料磷酸铁锂研究进展

与氧化钴锂（LiCoO₂）、氧化镍锂（LiNiO₂）相比,橄榄石结构磷酸铁锂(LiFePO₄)具有安全、环保、比容量高、循环性能优异、高温特性好等优点,被誉为最具发展前景的锂离子电池正极材料。长的循环寿命、优良的高倍率放电性能、高的放电平台、大的能量密度以及良好的热稳定性能,也使得磷酸铁锂成为高功率动力电池正极的首选材料。但是,磷酸铁锂也存在电子电导率相对较低、锂离子扩散系数小、振实密度不高、低温特性不好等缺点,因而制约着它的应用和发展。从磷酸铁锂结构、性能、制备和改性等方面综述了近年来磷酸铁锂的研究进展。     

磷酸铁锂正极材料的制备及性能强化研究进展

橄榄石型磷酸铁锂是目前应用十分广泛的锂离子电池正极材料之一,具有成本低、安全性高、环境友好、循环寿命长和工作电压稳定的特点。近年来,随着CTP技术、刀片电池技术等取得的突破性进展,磷酸铁锂的商业化程度得到了大幅提高。但磷酸铁锂存在电子导电性较差和离子扩散系数低的缺陷,严重限制了锂离子电池的电化学容量,因此开展磷酸铁锂制备工艺和性能强化研究对磷酸铁锂的性能提升具有重要意义。对比了磷酸铁锂电池与其他正极材料锂离子电池的性能差异和发展现状,系统总结了磷酸铁锂正极材料制备与强化的改性方法及相关研究进展与挑战,并提出了未来的发展方向与研究思路。     

磷酸铁锂正极材料的合成与表征技术

橄榄石型磷酸铁锂正极材料具有原料来源丰富、价廉、无毒、环境友好、理论容量高、热稳定性和循环性能好等特点,有望成为新一代锂离子电池正极材料.综述了高温固相反应法、溶胶-凝胶法、微波合成法、水热合成法和共沉淀法制备磷酸铁锂的方法.并详细说明了磷酸铁锂的红外光谱、扫描电镜、X射线衍射和电化学性能研究等表征技术.     

一种用于磷酸铁锂电极的水性黏结剂制备与性能研究

磷酸铁锂作为锂离子电池正极材料应用广泛。目前在其电极制备中仍采用PVDF油系黏结剂体系,可用于该电极的水性黏结剂仍需进一步研究。通过反应型乳化剂共聚苯乙烯（St）与丙烯酸异辛酯（2-EHA）制备了不同结构的磷酸铁锂正极水系黏结剂PSEHA,探讨了黏结剂对电池性能的影响。PSEHA黏结剂不含不饱和双键,抗氧化性好,较低的溶胀率可以有效防止过度溶胀导致的结构破坏,而反应型乳化剂可以解决乳化剂残留问题。采用所得最优结构黏结剂制备的磷酸铁锂电极表现出优异的电化学稳定性,扣式电池1 C循环100圈后容量保留率仍有96%,而SBR仅有93.9%;软包全电池在1 C倍率下循环170圈后容量保留率仍有98.9%。该新型水性黏结剂对促进磷酸铁锂水性体系制备有重要意义。     

磷酸铁锂优缺点及改性研究进展

橄榄石型磷酸铁锂(LiFePO_4)具有原料来源广泛、循环性能好、对环境无污染等特点,尤其是在高温下的安全性能,使其成为一种应用前景非常广阔的锂电池正极材料。但是,磷酸铁锂的电子导电率和锂离子扩散速率较低,限制了其进一步的市场化应用。介绍了磷酸铁锂的结构与性能之间的关系以及充放电机理,并对其改性方法进行了综述。     

高温固相法制备磷酸铁锂的原料专利技术分析

锂离子电池是目前应用最广的充电电池,磷酸铁锂是锂离子电池中占比最大的正极材料,高温固相法是制备磷酸铁锂最主要的方式,而原料对磷酸铁锂的性能具有很大的影响。通过对高温固相法制备磷酸铁锂的专利技术进行分析,具体分析了制备过程中所采用的原料种类和粒径,以期为后续研究者提供一些技术参考。     

表面活性剂优化酸铁锂正极材料的进展

磷酸铁锂因稳定的橄榄石结构、资源丰富、价格便宜、安全、无污染,比容量高、电压平稳等优点,成为目前应用广泛的锂离子电池正极材料之一。本论文简要介绍磷酸铁锂结构、合成方法、物质性能和化学性能,对比不同表面活性剂对磷酸铁锂正极材料的电化学性能的影响。     

Rechargeable lithium battery anodes: alternatives to metallic lithium

This review is concerned with alternatives to metallic lithium for use in rechargeable lithium batteries. Emphasis is placed on the use of various materials and combinations of materials in different types of electrodes rather than on the properties of the materials themselves. The review includes carbon based electrodes, alloys, conducting polymers and transition metal compounds. Special consideration is given to electrodes and materials used in organic liquid and polymer electrolytes, whereas liquid cathode and molten salt systems are excluded.     

尖晶石型锰酸锂锂离子筛的合成研究

为了比较不同合成方法对锰酸锂(Li4Mn5O12)锂离子筛的结构、饱和交换容量和分离因子的影响,采用低温固相反应法和溶胶-凝胶法合成了锰酸锂锂离子筛,并用X射线衍射(XRD)表征了所得材料的结构.结果表明,低温固相反应法和溶胶-凝胶法制备的锰酸锂及其离子筛均为尖晶石结构.低温固相反应法合成的锂离子筛,其锂离子饱和交换容量为16.06 mg/g(2.31 mmol/g)、分离因子αLiNa为23;溶胶-凝胶法合成的锰酸锂锂离子筛,其锂离子饱和交换容量为26.39 mg/g(3.80 mmol/g),分离因子αLiNa为216,优于低温固相反应法所得锂离子筛的性能.     

Graphene nanosheets for enhanced lithium storage in lithium ion batteries

Graphene nanosheets were synthesized in large quantities using a chemical approach. Field emission electron microscope observation revealed that loose graphene nanosheets agglomerated and crumpled naturally into shapes resembling flower-petals. High resolution transmission electron microscope analysis, Raman spectroscopy and ultraviolet-visible spectroscopy measurements confirmed the graphitic crystalline structure of the graphene nanosheets. The nanosheets exhibited an enhanced lithium storage capacity as anodes in lithium-ion cells and good cyclic performance.     

锂离子电池材料钛酸锂钠的研究进展

Na₂Li₂Ti₆O₁₄电池具有较低的电位平台（1.3 V）以及经济成本低的特点,对便携式电子设备、能源汽车、生态环境等领域具有重大意义。由于钛酸锂钠电池固有离子电导率低的特点,因此提高钛酸锂钠电池锂离子扩散系数是目前研究中的主流方向,为此综述了钛酸锂钠的结构特点以及合成方法对钛酸锂钠材料粒径、形貌及电池电化学性能的影响;对比了不同掺杂离子和表面包覆改性对钛酸锂钠电池的放电比容量、循环性能及离子扩散系数的影响。掺入适量元素铌具有更高的锂离子扩散系数;包覆碳纳米管有更大的容量保持率,更有助于进一步提高钛酸锂钠电池电化学性能。     

Extracting lithium from waste solutions of chemico-metallurgical lithium carbonate production

In order to reduce the loss of lithium in waste solutions of chemico-metallurgical lithium carbonate production, it is suggested to extract lithium from these solutions in the form of poorly soluble hydroxodialuminate under the action of sodium and potassium aluminates. Technological tests showed that the proposed method ensures almost complete isolation of lithium from waste solutions of lithium carbonate production.     

The dynamic evolution of aggregated lithium dendrites in lithium metal batteries

Lithium (Li) metal anodes promise an ultrahigh theoretical energy density and low redox potential,thus being the critical energy material for next-generation batteries.Unfortunately,the formation of Li den-drites in Li metal anodes remarkably hinders the practical applications of Li metal anodes.Herein,the dynamic evolution of discrete Li dendrites and aggregated Li dendrites with increasing current densities is visualized by in-situ optical microscopy in conjunction with ex-situ scanning electron microscopy.As revealed by the phase field simulations,the formation of aggregated Li dendrites under high current den-sity is attributed to the locally concentrated electric field rather than the depletion of Li ions.More specif-ically,the locally concentrated electric field stems from the spatial inhomogeneity on the Li metal surface and will be further enhanced with increasing current densities.Adjusting the above two factors with the help of the constructed phase field model is able to regulate the electrodeposited morphology from aggregated Li dendrites to discrete Li dendrites,and ultimately columnar Li morphology.The methodol-ogy and mechanistic understanding established herein give a significant step toward the practical appli-cations of Li metal anodes.     

四氟硼锂和六氟砷锂的合成与拉曼光谱分析

介绍了合成高纯无水的ＬｉＢＦ４和ＬｉＡｓＦ６的新方法，并讨论了其合成条件，指出制备多孔状ＬｉＦ和控制反应温度是合成的关键。     

Structure and electrochemical behavior of lithium vanadate materials for lithium batteries

New vanadate compounds having the molecular structure Li_xMg_1−xV_2−xMo_xO₆ (0 ≤ x ≤ 1) were studied. Six samples were prepared by sol-gel process from precursor using the following ratios of x = 0, 0.2, 0.4, 0.6, 0.8 and 1, respectively. These samples were labeled S1, S2, S3, S4, S5 and S6. The final process of firing occurred at 750 °C for 18 h in air. The prepared materials were characterized by XRD, SEM, IR, electron spin resonance (ESR) and magnetic measurements. The morphologies of S1, S2, S5 and S6 are prismatic as they have monoclinic crystal structures. S3 and S4 differ in the crystal morphology from the other previous samples due to their triclinic crystal lattice structure. IR spectra revealed that the bond lengths of the vanadyl groups ν_VO, ν_{sy V-O} and σ_V-O increase in the same direction from S1 to S6. The data of the ESR explain the existence of V⁴⁺ beside V⁵⁺ in S1, S4 and S6 and also presence of Mo⁵⁺ with Mo⁶⁺ in S4 and S6. S4 exhibited better magnetic susceptibility and saturated magnetization than the other samples. The first specific discharge capacities of the samples were performed. S4 showed the maximum specific capacity of 265 mAh g⁻¹ in comparison with the other samples. Cyclic voltammogram of S4 exhibited the highest current intensity in comparison with the other samples. This sample showed two peaks at 0.53 and 1.3 V versus Li/Li⁺ characterizing double de-insertions of two lithium atoms from Li_1.6Mg_0.4V_1.4Mo_0.6O_6−x and Li_0.6Mg_0.4V_1.4Mo_0.6O₆, respectively. Also, two additional peaks were characterized for the oxidation of Mo⁵⁺ to Mo⁶⁺ and V⁴⁺ to V⁵⁺ at 3.5 and 4 V, respectively.     

锂离子电池正极材料锰酸锂的改性研究

用氟化锂对预先合成的锰酸锂(LiMn2O4)进行氟化处理,研究了处理温度对材料电化学比容量与高温下循环稳定性的影响.结果表明,氟化锂/锰酸锂混合体系在500 ℃以上开始反应,所形成材料的特性发生了明显的变化;氟化锂处理可以改善锰酸锂材料的结晶度,热处理温度越高,处理后材料的结晶度越好;随着处理温度的升高,锰酸锂材料经历了从"烧结型"到"结晶型"的转变,700 ℃以上烧结的材料形成了八面体的晶体颗粒;初始比容量与循环性能也随着处理温度的不同而变化,600 ℃条件下处理的材料初始比容量最低,但循环性能最好.     

Enhancement of ionic conductivity by mixing lithium borate with lithium aluminate

Several lithium borates (Salt A and Salt B) and a lithium aluminate (Salt C) with electron-withdrawing groups, OC₆F₅, OCOCF₃ or N(SO₂CF₃)₂, and oligoether chains (O(CH₂CH₂O)_nCH₃) directly bonded to the ate complex center, B or Al, were prepared. Lithium borate and lithium aluminate were mixed to get mix-salt electrolytes. Higher ionic conductivity was observed for the mix-salt than for the pure-salt. Conductivity as high as 1.1 × 10⁻⁴ S/cm at ambient temperature (25 °C) was achieved for the electrolyte in the optimized composition. The reason for such mixing effect on enhancement of ionic conductivity was discussed. Other electrochemical properties including electrochemical stability, compatibility with lithium anode and cyclic performance were also investigated for the mix-salt electrolytes.