WO2013091281A1 - 无汞锌锰和锌银扣式电池 - Google Patents

无汞锌锰和锌银扣式电池 Download PDF

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Publication number
WO2013091281A1
WO2013091281A1 PCT/CN2012/001701 CN2012001701W WO2013091281A1 WO 2013091281 A1 WO2013091281 A1 WO 2013091281A1 CN 2012001701 W CN2012001701 W CN 2012001701W WO 2013091281 A1 WO2013091281 A1 WO 2013091281A1
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Prior art keywords
zinc
cathode
indium
current collector
mercury
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PCT/CN2012/001701
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English (en)
French (fr)
Inventor
肖秀华
肖雅文
Original Assignee
Xiao Xiuhua
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Publication of WO2013091281A1 publication Critical patent/WO2013091281A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H01M50/188—Sealing members characterised by the disposition of the sealing members the sealing members being arranged between the lid and terminal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the utility model relates to a mercury-free zinc-manganese and zinc-silver button battery. Background technique
  • the existing mercury-free zinc-manganese and zinc-silver-type electric production technology adopts an electroplating method to plate a surface of the negative electrode cover with a metal indium, tin or indium tin, indium zinc, copper tin alloy, etc., which can improve hydrogen evolution overpotential.
  • a metal indium, tin or indium tin, indium zinc, copper tin alloy, etc. which can improve hydrogen evolution overpotential.
  • the plating of the above-mentioned metal or alloy may result in uneven plating or voiding of the plating layer, which may cause the anode zinc paste to contact with the copper plating layer or the nickel plating layer inside the negative electrode cover.
  • the size of the button battery is small, and there is no space inside the battery to accommodate the gas, which causes the battery to expand, leak, and explode.
  • the existing mercury-free zinc-manganese and zinc-silver button-type battery structures have insufficient sealing performance, which easily causes the negative electrode electrolyte to leak from between the negative electrode cover and the sealed apron, causing alkali and liquid leakage.
  • the mercury-free zinc-manganese and zinc-silver button battery negative electrode caps produced by the prior art need to be deplated on the outer surface after electroplating, which is complicated and cumbersome to operate, and electroplating and deplating may cause environmental pollution and waste of resources. Therefore, there is an urgent need for a method that is both environmentally friendly and effective in overcoming the shortcomings of existing mercury-free zinc-manganese and zinc-silver button cell technologies.
  • the purpose of the utility model is to provide a mercury-free zinc-manganese and zinc-silver button battery.
  • the mercury-free zinc-manganese and zinc-silver button type battery prepared by the method has a negative electrode current collector and a sealing film on the concave surface of the battery negative electrode cover, and the negative electrode current collector separates the negative electrode zinc paste from the inner surface of the negative electrode cover, thereby avoiding the negative electrode zinc paste.
  • the chemical reaction between the inner side of the negative electrode cover and the gas generation causes the battery to expand, overcoming the shortcomings of the existing mercury-free zinc-manganese and zinc-silver battery technology.
  • the utility model is provided with a negative current collector and a sealing film on the concave surface of the negative electrode cover of the battery, and the negative current collector is made of metal indium, tin or indium tin alloy, indium zinc alloy sheet with a thickness of 0.005 mm or more, and is made of plastic and nylon. Or the sealing film made of rubber is integrated, and the negative current collector adopts metal indium, tin or indium tin alloy and indium zinc alloy which can increase the hydrogen evolution overpotential of the zinc powder, effectively preventing the self-discharge hydrogen evolution of the battery, and the negative current collector will be the negative electrode.
  • the zinc paste is separated from the negative electrode cover, effectively preventing the chemical reaction between the negative zinc paste and the inner side of the negative electrode cover, and causing gas to cause the battery to swell and explode.
  • the sealing film separates the negative zinc paste from the negative electrode cover and the sealing rubber ring to avoid the negative electrode.
  • the electrolyte leaks from between the negative electrode cover and the sealing rubber ring, effectively preventing the battery from climbing alkali and leaking liquid.
  • FIG. 1 is a cross-sectional view of a mercury-free zinc-manganese and zinc-silver button battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing a negative electrode current collector and a sealing film of a mercury-free zinc-manganese and zinc-silver battery according to an embodiment of the present invention.
  • the anode current collector is made of metal indium, tin or indium tin alloy, indium-zinc alloy sheet with a thickness of 0.005 mm or more, and is integrated with a sealing film made of plastic, nylon or rubber, and the ordinary buckle produced by a conventional process is integrated.
  • the negative electrode cover for the battery (the outer surface of the negative electrode cover is not deplated) and the sealing rubber ring are combined into a negative electrode cover assembly of the battery, and then the negative electrode current collector and the sealing film integrated component are mounted on the concave surface of the negative electrode cover assembly, and then conventionally
  • the process can be made into mercury-free zinc-manganese and zinc-silver button batteries.
  • the positive electrode material is made of electroless manganese dioxide to make a mercury-free zinc smash-type battery, and silver oxide is used instead of electrolytic manganese dioxide to form a mercury-free zinc-silver button type battery.
  • the mercury-free zinc-manganese and zinc-silver button type battery comprises the integrated assembly of the anode current collector 3 and the sealing film 4 according to the embodiment, the negative electrode cover 1 and the sealant.
  • Circle 2 negative electrode zinc paste 5, separator 6, positive electrode material 7, positive electrode shell 8, negative electrode current collector 3 separates the negative electrode zinc paste 5 from the inner surface of the negative electrode cover 1, effectively preventing the negative electrode zinc paste 5 from contacting the inner side of the negative electrode cover 1
  • a chemical reaction produces a gas that causes the battery to swell, leak, and explode.
  • the sealing film 4 separates the negative electrode zinc paste 5 from the negative electrode cover 1 and the sealing rubber ring 2 to prevent leakage of the negative electrode electrolyte from between the negative electrode cover 1 and the sealing rubber ring 2, thereby effectively preventing the battery from climbing and leaking.
  • the mercury-free zinc-manganese-zinc and zinc-silver-battery battery as described in the embodiment of the present invention the anode current collector and the sealing film integrated component, the anode current collector is more than 0. 005mm thick metal indium, tin or indium It is made of tin alloy and indium zinc alloy sheet 1, and is integrated with sealing film 2 made of plastic, nylon or rubber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

一种无汞锌锰和锌银扣式电池，包括负极集流体与密封膜、负极盖、密封胶圈、负极锌膏、隔膜、正极材料及正极壳，其特征在于：负极盖凹面带有负极集流体与密封膜，负极集流体由0.005mm以上厚的金属铟、锡或铟锡合金、铟锌合金片制成，并与塑料、尼龙或橡胶制成的密封膜连成一体化，负极集流体采用能提高锌粉的析氢过电位的金属铟、锡或铟锡合金、铟锌合金等材料制备，有效防止电池自放电析氢，负极集流体将负极锌膏与负极盖隔开，有效防止负极锌膏与负极盖内侧接触发生化学反应而产生气体导致电池气胀、爆炸，密封膜把负极锌膏与负极盖、密封胶圈隔开，避免负极电解液从负极盖与密封胶圈之间漏出，有效防止了电池爬碱、漏液。

Description

无汞锌锰和锌银扣式电池
技术领域
本实用新型涉及一种无汞锌锰和锌银扣式电池。 背景技术
现有的无汞锌锰和锌银扣式电^生产技术， 采用电镀方法在负极盖表面镀上一层可提高 析氢过电位的金属铟、 锡或铟锡、 铟锌、 铜锡合金等， 但是由于电镀上述金属或合金存在电 镀液离子浓度和 PH值难控制而造成镀层不均勾或镀层有孔洞等缺馅， 会导致负极锌膏与负 极盖内侧里面的镀铜层或镀镍层接触、 甚至与负极盖金属基体接触发生化学反应而产生气 体， 因纽扣电池尺寸很小， 电池内部不能留有空间容纳气体导致电池膨胀、 漏液、 爆炸。 现 有的无汞锌锰和锌银扣式电池结构， 存在密封性能不足， 容易导致负极电解液从负极盖与密 封胶圈之间漏出， 造成爬碱、漏液。另外， 现有技术生产的无汞锌锰和锌银扣式电池负极盖， 电镀后还需将外表面的镀层进行退镀， 操作复杂、 繁琐， 而且电镀、 退镀会造成环境污染及 资源浪费， 因此急需一种方法既环保又有效克服现有的无汞锌锰和锌银扣式电池技术的不 足。
发明内容
本实用新型的目的是提供一种无汞锌锰和锌银扣式电池。通过该方法制备的无汞锌锰和 锌银扣式电池， 其电池负极盖凹面带有负极集流体与密封膜， 负极集流体将负极锌膏与负极 盖内表面隔开， 避免了负极锌膏与负极盖内侧接触发生化学反应而产生气体导致电池膨胀， 克服了现有的无汞锌锰和锌银扣式电池技术的不足。
本实用新型是在电池负极盖的凹面带有负极集流体与密封膜， 负极集流体由 0. 005mm以 上厚的金属铟、 锡或铟锡合金、 铟锌合金片制成， 并与塑料、 尼龙或橡胶制成的密封膜连成 一体化， 负极集流体采用能提高锌粉的析氢过电位的金属铟、 锡或铟锡合金、 铟锌合金， 有 效防止电池自放电析氢， 负极集流体将负极锌膏与负极盖隔幵， 有效防止了负极锌膏与负极 盖内侧接触发生化学反应而产生气体导致电池气胀、 爆炸， 密封膜把负极锌膏与负极盖、 密 封胶圈隔开， 避免负极电解液从负极盖与密封胶圈之间漏出， 有效防止了电池爬碱、 漏液。 说 明 书
附图说明
图 1是本实用新型实施例所述的无汞锌锰和锌银扣式电池的剖面图。
图 2 是本实用新型实施例所述的无汞锌锰和锌银扣式电池负极集流体与密封膜的剖面 图。
具体实施方式
以下结合附图及实施例， 对本实用新型进行进一步详细说明。
实施方式
负极集流体由 0. 005mm以上厚的金属铟、 锡或铟锡合金、 铟锌合金片制成， 并与塑料、 尼龙或橡胶制成的密封膜连成一体化， 将常规工艺生产的普通扣式电池用的负极盖（负极盖 外表面不用退镀）与密封胶圈组合成电池负极盖组合件， 然后把负极集流体与密封膜一体化 组件安装在负极盖组合件凹面上， 再按常规工艺便可制成无汞锌锰和锌银扣式电池。 正极材 料用电解二氧化锰制成无汞锌猛扣式电池， 用氧化银代替电解二氧化锰制成无汞锌银扣式电 池。
如图 1所示， 本实用新型实施例所述的无汞锌锰和锌银扣式电池， 包括本实施例所述的 负极集流体 3与密封膜 4一体化组件， 负极盖 1及密封胶圈 2、 负极锌膏 5、 隔膜 6、 正极材 料 7、正极壳 8， 负极集流体 3将负极锌膏 5与负极盖 1内表面隔开， 有效防止了负极锌膏 5 与负极盖 1内侧接触发生化学反应而产生气体导致电池气胀、 漏液、 爆炸。 密封膜 4把负极 锌膏 5与负极盖 1、 密封胶圈 2隔开， 避免负极电解液从负极盖 1与密封胶圈 2之间漏出， 有效防止了电池爬碱、 漏液。
如图 2所示， 本实用新型实施例所述的无汞锌锰和锌银扣式电池负极集流体与密封膜一 体化组件， 负极集流体由 0. 005mm以上厚的金属铟、 锡或铟锡合金、 铟锌合金片 1制成， 并 与塑料、 尼龙或橡胶制成的密封膜 2连成一体化。
以上所述仅为本实用新型的典型实施例， 但并不局限于此例， 凡在本实用新型的精神本 质和原理所作的任何修改、 等同替换和改进等， 均应包含在本实用新型的保护范围之内。

Claims

权 利 要 求 书
1、 一种无汞锌锰和锌银扣式电池， 包括负极集流体与密封膜、 负极盖、 密封胶圈、 负极锌 膏、 隔膜、 正极材料及正极壳， 其特征在于： 负极盖凹面带有负极集流体与密封膜。
2、 权利要求 1所述的无汞锌锰和锌银扣式电池， 其特征在于： 负极集流体由 0. 005瞧以上 厚的金属铟、 锡或铟锡合金、 铟锌合金片制成， 并与塑料、 尼龙或橡胶制成的密封膜连成一 体化。
3、 权利要求 1 2所述的无汞锌锰和锌银扣式电池， 其特征在于： 正极材料使用电解二氧化 錳制成无汞锌锰扣式电池； 用氧化银代替电解二氧化锰制成无汞锌银扣式电池。
PCT/CN2012/001701 2011-12-18 2012-12-12 无汞锌锰和锌银扣式电池 WO2013091281A1 (zh)

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CN202495486U (zh) * 2011-12-18 2012-10-17 肖秀华 无汞锌锰和锌银扣式电池
CN103545524B (zh) * 2013-09-23 2015-10-28 哈尔滨工业大学（威海） 锌-聚苯胺电池及其制备方法
CN106129379A (zh) * 2016-08-31 2016-11-16 广东力王新能源股份有限公司 一种使用超细合金锌粉的大电流碱性锌锰电池
WO2019153277A1 (zh) * 2018-02-09 2019-08-15 深圳前海优容科技有限公司 电池、电池电芯及集流体
CN110364645B (zh) * 2019-06-18 2022-10-18 深圳清华大学研究院 无汞纽扣电池负极盖材料及其制备方法和应用
CN116053398A (zh) * 2022-09-09 2023-05-02 北京胜能能源科技有限公司 一种负极片及其制备方法与锂离子电池

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