WO2007104177A1 - Procédé de production d'une pile ion-lithium cylindrique du type fournissant de la puissance - Google Patents

Procédé de production d'une pile ion-lithium cylindrique du type fournissant de la puissance Download PDF

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WO2007104177A1
WO2007104177A1 PCT/CN2006/000375 CN2006000375W WO2007104177A1 WO 2007104177 A1 WO2007104177 A1 WO 2007104177A1 CN 2006000375 W CN2006000375 W CN 2006000375W WO 2007104177 A1 WO2007104177 A1 WO 2007104177A1
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electrode
carbon black
negative electrode
positive electrode
lithium ion
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PCT/CN2006/000375
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English (en)
French (fr)
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Xinguo Zhuang
Xinhe Zhang
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Li, Zhongyan
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Priority to PCT/CN2006/000375 priority Critical patent/WO2007104177A1/zh
Publication of WO2007104177A1 publication Critical patent/WO2007104177A1/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/043Processes of manufacture in general involving compressing or compaction
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to the field of electrochemistry, and more particularly to a method for preparing an organic electrolyte-powered cylindrical lithium ion battery.
  • Background Art Currently, in the field of electronic devices, lithium ion secondary batteries of high energy density have attracted attention as power supply problems for portable electronic instruments, electric tools, electric vehicles, and the like.
  • Early rechargeable battery devices including lead-acid batteries, nickel-cadmium batteries, etc., have achieved considerable success in the market; however, due to environmental pollution caused by lead and cadmium metal elements, the European Union has established restrictions on harmful environments and human bodies.
  • a primary object of the present invention is to provide a method for preparing a dynamic cylindrical lithium ion battery having stable performance, safe use, and environmental protection.
  • the method of preparing a power-type cylindrical lithium ion battery comprising a method for preparing a positive electrode, which is 51%-57. 1% spinel lithium manganate, 0.6%-6% carbon black, 0. 06%- 3% white carbon black, 1. 2%- 2. 4% polyvinylidene fluoride (PVDF) and 35% -45% N-methylpyrrolidone (Li P) mixed positive electrode current collector, the resulting set The fluid is coated on the aluminum foil, and then pressed to form a positive electrode; a negative electrode preparation method, 54% - 57% natural graphite powder, 1. 2% - 3% carbon black, 0.3% by weight - 1.
  • PVDF polyvinylidene fluoride
  • Li P N-methylpyrrolidone
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • the separator paper is made of a single layer of PE or PP-PE-PP; the outer diameter of the cylindrical casing is between 15 mm and 28 rara.
  • the utility model has the beneficial effects that the dynamic cylindrical lithium ion battery manufactured by the above method has the effects of stable performance and safe use, and also effectively avoids environmental pollution, and is beneficial to environmental protection effects.
  • Lithium hexafluoride LiPFj is dissolved in ethylene carbonate (EC), diethyl carbonate (DEC) mixed solvent (mixing volume ratio: 50:50) in an amount of 1. 05mol/L, at the positive electrode and the negative electrode Separated by a separator paper, and the current collectors on the electrodes are connected to the lead electrodes, and then the positive electrode and the negative electrode prepared above are inserted into the cylindrical casing, and the electrolyte is contained in the cylindrical casing.
  • the solution is lithium hexafluorophosphate (LiPF 6) in an amount L 1. 0 5 mol / dissolved in ethylene carbonate (EC), diethyl carbonate (DEC) mixed solvent (mixing volume ratio: 50: 50) manufactured by Thus, a cylindrical lithium ion secondary battery was obtained.
  • the lithium ion battery fabricated in Example 1 was obtained by the following test:
  • styrene butadiene rubber 4wt. % styrene butadiene rubber (SBR) mixed with 40.% water Form a fluid.
  • the resulting current collector was coated on an electrolytic copper foil (18 ⁇ M) and then pressurized to obtain a negative electrode. Separating the positive electrode and the negative electrode with a separator paper, the separator paper is made of a single layer of PE or PP-PE-PP, and the current collectors on each electrode are connected to lead the ear, and then the above The obtained positive electrode and the negative electrode are inserted into the cylindrical casing, and the electrolyte is a solution of lithium hexafluorophosphate (LiPF 6 ) in an amount of 1.05 mol / L.
  • a mixture of an ester (EC) and a diethyl carbonate (DEC) (mixing volume ratio: 50:50) was prepared, whereby a cylindrical lithium ion secondary battery was obtained.
  • the lithium ion battery fabricated in the second embodiment can be known by the following test: The battery 1C is charged to 4. 2V, and the constant voltage is charged until the current is less than 0.01C, and then the needle test is performed, and the battery is safe and does not ignite. Battery 1C is charged to 4. 2V, constant voltage is charged until the current is less than 0. 01C, and (60 ⁇ ) temperature is stored for 3 weeks, and the battery discharge capacity is kept unchanged.
  • the power type cylindrical lithium ion battery obtained by the preparation method of the present invention obtained by the implementation 1 and the implementation 2 has the effects of stable performance and safe use, and is effective in avoiding the use of lead metal elements and cadmium metal elements. Guarantee the purpose of environmental protection.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

动力型圆柱裡离子电池制备方法 技术领域 本发明涉及电化学领域,特别是指一种有机电解质动力型圆柱锂 离子电池的制备方法。 背景技术 目前,在电子装置领域中, 高能量密度的锂离子二次电池作为便 携式电子仪器、 电动工具、 电动汽车等的电源问题引 们的关注。 早期的可充电的电池装置包括铅酸电池、镍镉电池等, 它们在市场上 取得了相当大的成功; 但由于铅、 镉金属元素对环境的污染, 欧洲联 盟已经制定了限制有害环境和人体的物质使用的 RoHS 规则,故铅酸 电池、镍镉电池由于含有铅金属元素与镉金属元素是难进入市场, 不 利市场竟争; 当今, 市场上也出现了一些含锰酸锂等成份的高能量密 度锂离子电池, 但实际使用过程中, 若在高温(60度) 下存在不稳 定性之隐患, 电池放电容量不足, 并且可能会造成爆炸、 起火等现象 发生。 发明内容 本发明主要目的在于提供一种具有性能稳定、 安全使用、 环保的 动力型圆柱锂离子电池之制备方法。
为实现上述之目的, 本发明采取如下技术方案:
一种动力型圆柱锂离子电池制备方法, 包括一正极电极制备方 法, 按重量百分比计, 将 51%-57. 1%尖晶石锰酸锂、 0. 6%- 6%碳黑、 0. 06%- 3%白碳黑、 1. 2%- 2. 4%聚偏二氟乙烯(PVDF)与 35 % -45%N-甲基 吡咯烷酮(丽 P)混合而成正极集流体, 所得集流体涂覆在铝箔上, 然 后加压制成正极电极; 一负极电极制备方法, 按重量百分比计, 将 54%- 57%天然石墨粉、 1. 2%- 3%碳黑、 0. 3%- 1. 2%羧甲基纤维素(CMC)、 0. 6%-1. 8%丁苯橡胶(SBR)与 35 % -45%水混合而成负极集流体, 所得 负极集流体涂覆在电解铜箔上,然后加压制成负极电极; 在正极电极 和负极电极之间用一隔膜纸隔开,且各电极上集流体上连接引出导电 极耳, 然后将上述制得的正极电极与负极电极插入圆柱型壳体内, 该 圆柱型壳体内具有非水性电解液, 该电解液是将 0. 8-1. 5mol/L的六 氟磷锂溶于按重量百分比计的 20%- 60%碳酸亚乙脂、 40%- 80%碳酸二 乙脂中制成。 所述隔膜纸的材质为单层 PE或 PP- PE- PP三层;所述圆柱型壳体 外围直径为 15mm-28rara之间。
本发明有益效果是通过上述方法所制的动力型圆柱锂离子电池 具有性能稳定及安全使用之效果, 还有效地避免了环境污染现象发 生, 有利于环保之功效。 具体实施方式 下面结合实施例对本发明进一步说明。
实施例 1
将 55. 2wt. %尖晶石锰酸锂 ( LiMnA )粉、 1. 8wt. %碳黑、 0. 6wt. % 白炭黑、 2. 4wt. %聚偏二氟乙烯(PVDF 761EA )与 40 wt. % N -曱基 吡咯烷酮(NMP)混合而成集流体,所得集流体涂覆在铝箔( 18 μ m )上, 然后加压, 得到正极电极。 将 56wt. %包覆天然石墨(AMG-18/BTR ) 粉、 1. 8wt. %碳黑( SUPER-P ), 0. 7wt. %羧曱基纤维素(CMC)、 1. 5wt. % 丁苯橡胶(SBR)与 40 wt. %水混合成集流体。 所得集流体涂覆在电解 铜箔 (18 μ ηι )上, 然后加压, 得到负电极。
将六氟麟锂 ( LiPFj 以 1. 05mol/L 的量溶于碳酸亚乙酯(EC)、 碳酸 二乙酯(DEC )混合溶剂 (混合体积比: 50: 50 ), 在正极电极和负极 电极之间用一隔膜纸隔开, 且各电极上集流体上连接引出导电极耳, 然后将上述制得的正极电极与负极电极插入圆柱型壳体内,在圆柱型 壳体内具有电解液, 该电解液是将六氟磷锂(LiPF6 ) 以 1. 05mol/L 的量溶于碳酸亚乙酯(EC)、 碳酸二乙酯 (DEC ) 混合溶剂 (混合体积 比: 50: 50 )制成, 由此得到圆柱型锂离子二次电池。
由实施例 1 中制成的锂离子电池通过以下测试可知: 通过电池
1C充电至 4. 2V, 恒电压充电至电流小于 0. 01C, 然后进行针刺实验, 电池安全不爆炸, 不起火。 电池: LC充电至 4. 2V, 恒电压充电至电流 小于 0. 01C, 进行 ( 60°C )温度存贮 3周 , 电池放电容量保持初始容 量的 97%。 实施例 2
将 54. 6 t.。/«尖晶石锰酸锂 ( LiMn204 )粉、 1. 8wt. %碳黑、 1. 2wt. % 白炭黑和 2. ½t. %聚偏二氟乙晞(PVDF 761EA ) 与 40 wt. % N -曱基 吡咯烷酮(薩 P )混合成集流体, 所得集流体涂覆在铝箔( 18 μ m )上, 然后加压, 得到正极电极; 将 56wt. %包覆天然石墨 (AMG- 18/BTR ) 粉、 1. 8wt. %碳黑( SUPER- P )、 0. 7wt. %羧甲基纤维素(CMC)、 1. 5wt. % 丁苯橡胶(SBR )与 40 .%水混合成集流体。 所得集流体涂覆在电解 铜箔 (18 μ ΐϋ )上, 然后加压, 得到负极电极。 在正极电极和负极电极之间用一隔膜纸隔开,所述隔膜纸的材质 为单层 PE或 PP-PE-PP三层,且各电极上集流体上连接引出导电极耳, 然后将上述制得的正极电极与负极电极插入圆柱型壳体内,在圆柱型 壳体内具有电 ^液, 该电解液是将六氟磷锂(LiPF6 ) 以 1. 05mol /L 的量溶于碳酸亚乙酯(EC)、 碳酸二乙酯 (DEC )混合溶剂 (混合体积 比: 50: 50 )制成, 由此得到圆柱型锂离子二次电池。
由实施例 2中制成的锂离子电池通过以下测试可知: 电池 1C充 电至 4. 2V, 恒电压充电至电流小于 0. 01C, 然后进行针剌实验, 电池 安全不爆炸, 不起火。 电池 1C充电至 4. 2V, 恒电压充电至电流小于 0. 01C, 进行 ( 60Ό )温度存贮 3周, 电池放电容量保持初始容量不 变。
通过实施 1、 实施 2中得出通本发明之制备方法得出的动力型圆 柱锂离子电池具有性能稳定及安全使用之效果,并且由于避开了铅金 属元素与镉金属元素的使用, 有效地保证了环保之目的。
以上所述, 仅'是本发明动力型圆柱锂离子电池制备方法较佳实 施例而已, 并非对本发明的技术范围作任何限制, 故凡是依据本发明 的技术实质对以上实施例所作的任何细微修改、等同变化与修饰, 均 仍属于本发明技术方案的范围内。

Claims

权 利 要 求
1、 一种动力型圆柱锂离子电池制备方法, 其特征在于: 包括: 一正极电极制备方法, 按重量百分比计, 将 51%-57. 1%尖晶石锰 酸锂、 0. 6%-6%碳黑、 0. 06%-3%白碳黑、 1. 2%-2. 4%聚偏二氟乙烯与 35 % -45% N-甲基吡咯烷酮混合而成正极集流体, 所得集流体涂覆在 铝箔上, 然后加压制成正极电极;
一负极电极制备方法,按重量百分比计,将 54%- 57°/。天然石墨粉、 1. 2%- 3%碳黑、 0. 3%-1. 2%羧曱基纤维素、 0. 6%-1. 8%丁苯橡胶与 35 % -45%水混合而成负极集流体, 所得负极集流体涂覆在电解铜箔上,然 后加压制成负极电极;
在正极电极和负极电极之间用一隔膜纸隔开,且各电极上集流体 上连接引出导电极耳,然后将上述制得的正极电极与负极电极插入圆 柱型壳体内, 该圆柱型壳体内具有非水性电解液, 该电解液是将 0. 8-1. 5moL/L 的六氟磷锂溶于按重量百分比计的 20%- 60%碳酸亚乙 脂、 40%- 80%碳酸二乙脂混合溶剂中制成。 .
2、 根据权利要求 1所述的动力型圆柱锂离子电池制备方法, 其 特征在于: 所述隔膜纸的材质为单层 PE或 PP- PE- PP三层。
3、 根据权利要求 1所述的动力型圓柱型锂子电池制备方法, 其 特征在于: 所述圆柱型壳体外围直径为 15mm- 28醒之间。
PCT/CN2006/000375 2006-03-13 2006-03-13 Procédé de production d'une pile ion-lithium cylindrique du type fournissant de la puissance WO2007104177A1 (fr)

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Cited By (2)

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CN103811801A (zh) * 2014-03-17 2014-05-21 山东润峰集团新能源科技有限公司 一种液态软包装低温锂离子电池的制备方法
CN111725503A (zh) * 2020-04-30 2020-09-29 江西安驰新能源科技有限公司 一种锂离子电池负极合浆工艺

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JP2003045496A (ja) * 2001-07-31 2003-02-14 Shin Kobe Electric Mach Co Ltd リチウム二次電池の製造方法
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JP2003045496A (ja) * 2001-07-31 2003-02-14 Shin Kobe Electric Mach Co Ltd リチウム二次電池の製造方法
JP2003045428A (ja) * 2001-07-31 2003-02-14 Shin Kobe Electric Mach Co Ltd リチウム二次電池
JP2005005113A (ja) * 2003-06-11 2005-01-06 Toshiba Corp 非水電解質二次電池
CN1734825A (zh) * 2005-08-08 2006-02-15 河南环宇集团有限公司 高倍率磷酸基锂离子电池的制备方法及其制备的电池

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CN103811801A (zh) * 2014-03-17 2014-05-21 山东润峰集团新能源科技有限公司 一种液态软包装低温锂离子电池的制备方法
CN111725503A (zh) * 2020-04-30 2020-09-29 江西安驰新能源科技有限公司 一种锂离子电池负极合浆工艺

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