CN103915647B - 一种低温锂离子电池 - Google Patents

一种低温锂离子电池 Download PDF

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CN103915647B
CN103915647B CN201410128352.5A CN201410128352A CN103915647B CN 103915647 B CN103915647 B CN 103915647B CN 201410128352 A CN201410128352 A CN 201410128352A CN 103915647 B CN103915647 B CN 103915647B
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phosphorus pentoxide
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张波
林道松
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Guangzhou manganese light lithium battery technology Co., Ltd.
Shen Guopei
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SHAOXING ANKA AUTO PARTS Co Ltd
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    • H01M10/052—Li-accumulators
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    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02E60/10—Energy storage using batteries

Abstract

本发明提供一种低温锂离子电池，包括正极材料、负极材料和电解液，正极材料表面包覆金属氧化物或金属氟化物、且掺杂金属离子，用以下结构表示：Li1.2Co0.3Mn0.4NxV0.3O4；N为Al和／或Zr，x为0.2‑0.4；负极材料用以下结构式表示：LiNi(1‑x‑y‑z)CoxMyFezO2，其中M选自金属元素Zn，Cr中的至少一种，0＜x≤0.2，0＜y≤0.2，0＜z＜0.3；电解液包括85‑90％有机溶剂，8‑15％锂盐和1‑5％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的1‑4％，锂盐为LiBF4、LiPF4C2O4、LiCF3SO2中的至少一种，添加剂为N‑乙烯基吡啶、N‑乙烯基咔唑、2‑硫苯基噻吩、3‑(苯基硫代)噻吩或者它们的混合物。

Description

一种低温锂离子电池
技术领域
本发明属于电池技术领域，涉及锂离子电池，具体涉及低温锂离子电池。
背景技术
锂离子电池由于具有能量密度高、循环性能好、工作电压高、无记忆效应等优点而成为最广泛的二次电池之一，随着电子技术的飞速发展，人们对锂离子电池的性能要求越来越高。
锂电池包含活性阴极材料、活性阳极材料和隔膜。用于锂离子电池正极材料目前商品化的主要为层状的LiCoO2，但是由于钴资源越来月匮乏，导致成本升高，另外，其安全性能较差，不适合制作高容量电池；用于锂电池的活性阴极材料如LiCoO2、LiMnO2、LiNiO2和二元或三元化合物(LiCo(1-x-y）NixMnyO2)、硫属元素化合物如MoS2、和金属磷酸盐如LiFePO4。由于这些化合物具有层状晶体结构，锂离子可以可逆地嵌入这些结构中／从这些结构中解脱。为此，常常使用这些化合物作为用于锂电池的活性阴极材料。而目前商品化锂离子电池的负极材料均为碳材料，主要是石油焦炭和石墨，其中具有代表性的是Sony公司的石油焦炭负极材料，但容量较低，而循环性能较差的A&T公司的负极材料为高容量石墨化介稳相沥青基炭纤维。目前高放电容量和高电压平台的正极材料越来越多，但是与其匹配的电解液研究相对较少，传统的电解液的持续分解影响了高电压正极材料的电化学性能，因而电解液的研究也同样重要。
发明内容
本发明提供的锂离子电池通过优化电解液，合理调整正负极材料的组分及含量，在保障锂离子电池循环使用寿命的前提下，增大了低温下电池工作的放电容量及电压平台，同时能够促进电荷传递，改善放电性能。
为了解决上述技术问题，本发明采用如下技术方案：包括正极材料、负极材料和电解液。
正极材料表面包覆金属氧化物或金属氟化物、且掺杂金属离子，用以下结构表示：Li1.2Co0.3Mn0.4NxV0.3O4；N为Al和／或Zr，x为0.2-0.4；
负极材料用以下结构式表示：LiNi(1-x-y-z)CoxMyFezO2，其中M选自金属元素Zn，Cr中的至少一种，0＜x≤0.2，0＜y≤0.2，0＜z＜0.3；
电解液包括85-90％有机溶剂，8-15％锂盐和1-5％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的1-4％，锂盐为LiBF4、LiPF4C2O4、LiCF3SO2中的至少一种，添加剂为N-乙烯基吡啶、N-乙烯基咔唑、2-硫苯基噻吩、3-(苯基硫代)噻吩或者它们的混合物。
在一种优选的实施方式中，正极材料的结构式为Li1.2Co0.3Mn0.4Al0.1Zr0.1V0.3O4。
在一种优选的实施方式中，所述负极材料的结构式为LiNi0.5Co0.1Cr0.2Fe0.2O2。
在一种优选的实施方式中，所述电解液包括88％有机溶剂，10％锂盐和2％添加剂.
在一种优选的实施方式中，所述链状碳酸酯为碳酸二乙酯、碳酸甲乙酯、碳酸乙丙酯中的至少一种。
在产业应用中，电池的低温性能与容量等电学性能或循环寿命等电化学性能不同，难以通过正极材料、负极材料或电解液单一性能的提升而获得显著提升，必须是多种材料或组件配套提升，因此本发明通过多组正交实验，以及结合锂离子电池电极材料的最新发展趋势，探索出了适合于低温应用的电极材料，并从现有技术中大量应用的不同种类电解液中得到与之匹配的电解液，使本发明的电池在极低的温度下仍维持了可观的放电容量及电压平台，扩展了电池的应用范围。
具体实施方式
实施例1
锂离子电池包括正极材料、负极材料和电解液。正极材料表面包覆TiO2，结构式为Li1.2Co0.3Mn0.4Al0.1Zr0.1V0.3O4。负极材料用以下结构式表示：LiNi0.5Co0.1Cr0.2Fe0.2O2。电解液包括85％有机溶剂，12％锂盐和3％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的3％，链状碳酸酯为碳酸二乙酯，锂盐为LiBF4，添加剂为N-乙烯基吡啶和N-乙烯基咔唑的混合物。
本实施例所得的锂离子电池经过活化及化成后，通过以下方法测试：
1、0.2C恒流恒压充电至4.2V；
2、分别在-10℃、-20℃下搁置5h；
3、0.5C放电到3.0V，记录放电容量及中值电压。
通过上述方法测得实施例1的各项指标如下表所示：
实施例2
锂离子电池包括正极材料、负极材料和电解液。正极材料表面包覆Al2O3用以下结构表示：Li1.2Co0.3Mn0.4Zr0.3V0.3O4；负极材料用以下结构式表示：LiNi0.5Co0.1Zn0.1Fe0.3O2；电解液包括90％有机溶剂，8％锂盐和2％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的4％,链状碳酸酯为碳酸甲乙酯，锂盐为LiPF4C2O4，添加剂为2-硫苯基噻吩和3-(苯基硫代)噻吩的混合物。
本实施例所得的锂离子电池经过活化及化成后，通过以下方法测试：
1、0.2C恒流恒压充电至4.2V；
2、分别在-10℃、-20℃下搁置5h；
3、0.5C放电到3.0V，记录放电容量及中值电压。
通过上述方法测得实施例2的各项指标如下表所示：
实施例3
锂离子电池包括正极材料、负极材料和电解液。正极材料表面TiO2，用以下结构表示：Li1.2Co0.3Mn0.4Al0.2V0.3O4；负极材料用以下结构式表示：LiNi0.3Co0.2Zn0.2Fe0.3O2；电解液包括85％有机溶剂，10％锂盐和5％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的4％,链状碳酸酯为碳酸甲乙酯和碳酸乙丙酯，锂盐为LiCF3SO2，添加剂为2-硫苯基噻吩、3-(苯基硫代)噻吩的混合物。
本实施例所得的锂离子电池经过活化及化成后，通过以下方法测试：
1、0.2C恒流恒压充电至4.2V；
2、分别在-10℃、-20℃下搁置5h；
3、0.5C放电到3.0V，记录放电容量及中值电压。
通过上述方法测得实施例3的各项指标如下表所示：
可，本发明提供的锂离子电池通过优化电解液，合理调整正负极材料的组分及含量，在保障锂离子电池循环使用寿命的前提下，增大了低温下电池工作的放电容量及电压平台，同时能够促进电荷传递，改善放电性能。
以上内容是结合具体的优选实施方式对本发明所作的进一明，不能本发明的具体实施于这些明。对于本发明所属技术领域的通技术人来，在不脱离本发明构的前提下出代或明显，而且性能或用相同，应为属于本发明的保范围。

Claims (3)

1.一种低温锂离子电池，包括正极材料、负极材料和电解液，其特征在于：正极材料表面包覆TiO2，结构式为Li1.2Co0.3Mn0.4Al0.1Zr0.1V0.3O4；负极材料用以下结构式表示：LiNi0.5Co0.1Cr0.2Fe0.2O2；电解液包括85％有机溶剂，12％锂盐和3％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的3％，链状碳酸酯为碳酸二乙酯，锂盐为LiBF4，添加剂为N-乙烯基吡啶和N-乙烯基咔唑的混合物。
2.一种低温锂离子电池，包括正极材料、负极材料和电解液，其特征在于：正极材料表面包覆Al2O3，用以下结构表示：Li1.2Co0.3Mn0.4Zr0.3V0.3O4；负极材料用以下结构式表示：LiNi0.5Co0.1Zn0.1Fe0.3O2；电解液包括90％有机溶剂，8％锂盐和2％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的4％，链状碳酸酯为碳酸甲乙酯，锂盐为LiPF4C2O4，添加剂为2-硫苯基噻吩和3-(苯基硫代)噻吩的混合物。
3.一种低温锂离子电池，包括正极材料、负极材料和电解液，其特征在于：正极材料表面包覆TiO2，用以下结构表示：Li1.2Co0.3Mn0.4Al0.2V0.3O4；负极材料用以下结构式表示：LiNi0.3Co0.2Zn0.2Fe0.3O2；电解液包括85％有机溶剂，10％锂盐和5％添加剂，有机溶剂是包含五氧化二磷的链状碳酸酯复合溶剂，五氧化二磷的含量占复合溶剂的4％，链状碳酸酯为碳酸甲乙酯和碳酸乙丙酯，锂盐为LiCF3SO2，添加剂为2-硫苯基噻吩和3-(苯基硫代)噻吩的混合物。
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