WO2013031557A1 - 鉛蓄電池添加剤および鉛蓄電池 - Google Patents

鉛蓄電池添加剤および鉛蓄電池 Download PDF

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Publication number
WO2013031557A1
WO2013031557A1 PCT/JP2012/070948 JP2012070948W WO2013031557A1 WO 2013031557 A1 WO2013031557 A1 WO 2013031557A1 JP 2012070948 W JP2012070948 W JP 2012070948W WO 2013031557 A1 WO2013031557 A1 WO 2013031557A1
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WIPO (PCT)
Prior art keywords
polymer
lead
million
copolymer
formula
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PCT/JP2012/070948
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English (en)
French (fr)
Japanese (ja)
Inventor
俊三 間瀬
小沢　昭弥
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Priority to CN201280039575.3A priority Critical patent/CN103797637B/zh
Priority to US14/240,249 priority patent/US9312569B2/en
Publication of WO2013031557A1 publication Critical patent/WO2013031557A1/ja
Anticipated expiration legal-status Critical
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • 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 present invention relates to a long-life lead-acid battery additive that activates a lead-acid battery over a long period of time, and a lead-acid battery using the same.
  • polyvinyl alcohol is gradually oxidized on the surface of the positive electrode and loses its effectiveness, it is necessary to add polyvinyl alcohol to the electrolyte every year or every few years in order to maintain its effectiveness for a long time. Was cumbersome.
  • polyacrylic acid or an alkali salt thereof is used as an additive, although it has better oxidation resistance than polyvinyl alcohol, aqueous solutions of these compounds are very viscous and difficult to mix with the electrolyte.
  • when added as a powder it takes a long time to uniformly dissolve and disperse in the electrolytic solution, resulting in poor workability.
  • the present invention activates a lead storage battery over a longer period of time than conventional polyvinyl alcohol and polyacrylic acid, adds less lead during charging of the lead storage battery, and is extremely easy to add to the electrolyte.
  • An agent and a lead storage battery using the agent are provided.
  • the present invention is a polymer or copolymer containing one or more of the structural units represented by the following chemical formulas 1 to 6, wherein the polymer or copolymer is derived from the chemical formulas 1 to 6.
  • a lead battery additive containing a carboxyl group (—COOM) and a sulfo group (—SO 3 M), preferably a molar ratio of the carboxyl group to the sulfo group in the polymer or copolymer Is in the range of 1 to 9 to 8 to 2, preferably 2 to 8 to 6 to 4, and more desirably, the average molecular weight of the polymer or copolymer is 1 million to 10 million, preferably 3 million to It is a 7 million lead battery additive.
  • M and M * may be the same type of atom or different types of atoms.
  • M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • M and M * represent a hydrogen atom, an alkali metal atom or an ammonium group.
  • M and M * represent a hydrogen atom, an alkali metal atom or an ammonium group.
  • M and M * represent a hydrogen atom, an alkali metal atom or an ammonium group.
  • M and M * represent a hydrogen atom, an alkali metal atom or an ammonium group.
  • the present invention is a lead battery additive comprising a sulfonated acrylic acid polymer (a polymer containing any one of chemical formulas 1 to 3 as a structural unit), and the molar
  • the present invention also relates to a lead storage battery comprising a lead peroxide positive electrode, a metal lead negative electrode, and a dilute sulfuric acid electrolyte, and a polymer containing one or more structural units represented by the above chemical formulas 1 to 6. Or a lead containing an additive containing a carboxyl group and a sulfo group derived from the chemical formulas 1 to 6 in the polymer or copolymer in the electrolytic solution.
  • a storage battery desirably the molar ratio of the carboxyl group to the sulfo group in the polymer or copolymer is in the range of 1 to 9 to 8 to 2, preferably 2 to 8 to 6 to 4.
  • the present invention provides a lead acid battery comprising a lead peroxide positive electrode, a metal lead negative electrode, and a dilute sulfuric acid electrolyte, and a sulfonated acrylic acid polymer (a compound containing any one of chemical formulas 1 to 3 as a structural unit).
  • a lead acid battery containing the combination) in the electrolytic solution and desirably the molar ratio of carboxyl group to sulfo group in the sulfonated acrylic acid polymer is 1: 9 to 8: 2, preferably 2: 8.
  • the average molecular weight of the sulfonated acrylic acid polymer is 1 million to 10 million, preferably 3 million to 7 million, and the concentration of the sulfonated acrylic acid polymer in the electrolyte solution Is a lead-acid battery with 0.02 to 1% by weight, preferably 0.1 to 0.5% by weight.
  • the action of the additive of the present invention is as follows.
  • the acrylic or fumaric acid or maleic acid carboxyl group which is the structural unit of the polymer or copolymer of the present invention, acts on the negative electrode surface of the lead-acid battery to increase the hydrogen overvoltage of the negative electrode and lead sulfate electrolysis. By promoting the reduction, it is possible to prevent and recover sulfation which is the greatest cause of deterioration of the lead battery.
  • the higher the molecular weight of these polymers or copolymers the longer the life of the polymer or the copolymer is less likely to be oxidized at the positive electrode.
  • the higher the molecular weight the lower the dissolution rate in the electrolyte solution, and the higher the viscosity.
  • the sulfo group newly introduced in the present invention makes it very easy to dissolve the additive in the electrolyte, lowers the viscosity of the solution, reduces the decomposition due to the charge / discharge cycle of the battery, and makes the battery longer life. is there.
  • the introduction of the sulfo group does not impair the excellent oxidation resistance and low foaming property of the acrylic polymer, greatly improves the dissolution rate in the electrolytic solution, lowers the viscosity of the solution, and is durable. The property is further improved.
  • the amount of carboxyl group and sulfo group can be arbitrarily selected in consideration of the effect of increasing the hydrogen overvoltage of the negative electrode and the effect of increasing the solubility of the additive, but the molar ratio of carboxyl group and sulfo group Is preferably in the range of 1 to 9 to 8 to 2, preferably 2 to 8 to 6 to 4.
  • the average molecular weight is preferably in the range of 1 million to 10 million, preferably 3 million to 7 million.
  • the molecular weight is smaller than this, it tends to be oxidized at the positive electrode, and the effect disappears in a short period of time.
  • the molecular weight is larger than this, the viscosity becomes high and the addition work becomes difficult.
  • a sulfonated acrylic acid polymer having a well-established production method and stable quality can be suitably used.
  • 0.02 to 1% by weight, preferably 0.1 to 0.5% by weight of the additive of the present invention is added to the electrolytic solution. When the amount of the additive is less than this, the additive is completely decomposed in a short period due to oxidation at the positive electrode, so that the effect of the additive disappears in a short period.
  • the additive of this invention can also be used as a mixture with the conventionally used polyvinyl alcohol and polyacrylic acid.
  • an electrode deteriorated by sulfation is regenerated in an electrolytic solution to which these polyvinyl alcohols and polyacrylic acid are added in a short time, and the sulfone of the present invention is contained in the electrolytic solution in order to obtain a long life for the regenerated battery. It is effective to add an acrylic acid polymer.
  • the additive of the present invention has less foaming during charging, is easily dissolved in an electrolytic solution and water, and has an effect of maintaining the capacity of the battery even after many charging and discharging cycles.
  • Lead-acid batteries containing an additive in the electrolyte can have a life that is approximately twice that of conventional lead-acid batteries.
  • examples of the prior art are as follows: (1) additive-free, (2) polyvinyl alcohol 1 g / liter, ( 3) Polyacrylic acid 1 g / liter, as an example of the present invention, (4) Measurement of change in discharge capacity due to charge / discharge cycle when 1 g / liter of sulfonated polyacrylic acid is added to the electrolyte of each battery cell did. As a result, as shown in FIG. 1, when the additive of curve 1 was not added, the discharge capacity was greatly reduced after about 200 cycles.
  • the molecular weight of polyvinyl alcohol used in this example is 120,000, the molecular weight of polyacrylic acid is 5 million, and the sulfonated polyacrylic acid is a polymer composed of structural units of Chemical Formula 1 and Chemical Formula 2, and the molecular weight is 500
  • the molar ratio of carboxyl group to sulfo group is 3 to 7.
  • Example 1 For a lead storage battery having the same specifications as the lead storage battery used in Example 1, an additive comprising a polymer or copolymer of Chemical Formula 1 to Chemical Formula 6 is added to the electrolyte of the battery, and under the same conditions as in Example 1. Charging / discharging was performed and the number of charge / discharge cycles at which the discharge amount decreased to 8 Ah was determined. The results are shown in Table 1.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2012/070948 2011-08-29 2012-08-14 鉛蓄電池添加剤および鉛蓄電池 Ceased WO2013031557A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280039575.3A CN103797637B (zh) 2011-08-29 2012-08-14 铅蓄电池添加剂及其铅蓄电池
US14/240,249 US9312569B2 (en) 2011-08-29 2012-08-14 Additive for lead-acid battery and lead-acid battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-201137 2011-08-29
JP2011201137A JP5816961B2 (ja) 2011-08-29 2011-08-29 鉛蓄電池添加剤および鉛蓄電池

Publications (1)

Publication Number Publication Date
WO2013031557A1 true WO2013031557A1 (ja) 2013-03-07

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US (1) US9312569B2 (https=)
JP (1) JP5816961B2 (https=)
CN (1) CN103797637B (https=)
WO (1) WO2013031557A1 (https=)

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Publication number Priority date Publication date Assignee Title
US20180062164A1 (en) * 2015-03-27 2018-03-01 Japan Exlan Company Limited Acrylonitrile-based fiber for electrodes, electrode containing the fiber, and lead-acid battery having the electrode
CN112421132B (zh) * 2020-10-27 2023-07-28 盐城工学院 一种铅酸电池修复液及其制备方法与应用
AU2021401542A1 (en) 2020-12-18 2023-07-13 Boris Ivanov MONAHOV Synthetic proton-conductive additives for battery electrolytes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001313064A (ja) * 2000-04-28 2001-11-09 Mase Shunzo 鉛蓄電池およびその添加剤
JP2004292649A (ja) * 2003-03-27 2004-10-21 Toyo Tire & Rubber Co Ltd ゲル状電解質用親水性重合体及びその製造方法並びにゲル状電解質
JP2004292648A (ja) * 2003-03-27 2004-10-21 Toyo Tire & Rubber Co Ltd ゲル状電解質用親水性重合体及びその製造方法、ゲル状電解質並びに鉛蓄電池

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Publication number Priority date Publication date Assignee Title
NL126911C (https=) * 1959-09-11
US5518630A (en) * 1994-03-22 1996-05-21 Betz Laboratories, Inc. Method for controlling scale formation and deposition
JP2000149981A (ja) * 1998-11-02 2000-05-30 Jec Service Kk 鉛蓄電池および鉛蓄電池用添加剤
JP2007073489A (ja) * 2005-09-08 2007-03-22 Mase Shunzo 鉛蓄電池添加剤ペレット
CN100583535C (zh) * 2007-12-21 2010-01-20 钱正新 蓄电池的电解质组合物及其制备方法
US8461758B2 (en) * 2008-12-19 2013-06-11 E I Du Pont De Nemours And Company Buffer bilayers for electronic devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001313064A (ja) * 2000-04-28 2001-11-09 Mase Shunzo 鉛蓄電池およびその添加剤
JP2004292649A (ja) * 2003-03-27 2004-10-21 Toyo Tire & Rubber Co Ltd ゲル状電解質用親水性重合体及びその製造方法並びにゲル状電解質
JP2004292648A (ja) * 2003-03-27 2004-10-21 Toyo Tire & Rubber Co Ltd ゲル状電解質用親水性重合体及びその製造方法、ゲル状電解質並びに鉛蓄電池

Also Published As

Publication number Publication date
US20140170477A1 (en) 2014-06-19
CN103797637B (zh) 2016-04-27
JP5816961B2 (ja) 2015-11-18
US9312569B2 (en) 2016-04-12
JP2013048074A (ja) 2013-03-07
CN103797637A (zh) 2014-05-14

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