WO2011102409A1 - Batterie - Google Patents

Batterie Download PDF

Info

Publication number
WO2011102409A1
WO2011102409A1 PCT/JP2011/053353 JP2011053353W WO2011102409A1 WO 2011102409 A1 WO2011102409 A1 WO 2011102409A1 JP 2011053353 W JP2011053353 W JP 2011053353W WO 2011102409 A1 WO2011102409 A1 WO 2011102409A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
battery
water
active material
manganese dioxide
Prior art date
Application number
PCT/JP2011/053353
Other languages
English (en)
Japanese (ja)
Inventor
千慶 鈴木
Original Assignee
株式会社アクモ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社アクモ filed Critical 株式会社アクモ
Publication of WO2011102409A1 publication Critical patent/WO2011102409A1/fr

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a battery using water as a positive electrode active material.
  • Patent Document 1 discloses a metal negative electrode outer cylinder, a powder filler made of an oxidant filled in the negative electrode outer cylinder, and a rod-like positive electrode made of carbon inserted into the powder filler.
  • a battery including a current collector and a water absorbing member injected into the negative electrode outer cylinder for absorbing water and supplying it to the powder filler is disclosed.
  • the battery described in Patent Document 1 uses an oxidizing substance having a strong oxidizing power such as manganese dioxide as a positive electrode active material, and water is merely used as a solvent for an electrolytic solution, and water is directly used as a positive electrode active material. It is not used as.
  • water is widely present in nature and can be easily obtained, and the reduction potential is ⁇ 0.83 V vs.
  • SHE has a high reduction potential and a large theoretical capacity of 1488 mAhg ⁇ 1 . For this reason, it is expected that a high-capacity battery can be constructed by using water as the positive electrode active material.
  • an object of the present invention is to provide a battery that uses a water reduction reaction, that is, uses water as a positive electrode active material.
  • the present inventors use a polyvalent carboxylate as an electrolyte contained in an electrolytic solution and manganese dioxide as a positive electrode-containing catalyst, the overvoltage of the water reduction reaction can be suppressed, and water is used as a positive electrode active material. As a result, the present invention has been completed. Specifically, the present invention provides the following.
  • a battery in which the positive electrode active material is water using an aqueous solution of a polyvalent carboxylate as an electrolyte and manganese dioxide as a positive electrode-containing catalyst.
  • a polyvalent carboxylate is used as the electrolyte contained in the electrolytic solution, and manganese dioxide is used as the positive electrode-containing catalyst. Since these electrolytes and the positive electrode-containing catalyst catalyze a positive electrode reaction (2H 2 O + 2e ⁇ ⁇ 2OH ⁇ + H 2 ) using water as a positive electrode active material and suppress overvoltage, a battery using water as a positive electrode active material Can be provided (see FIGS. 1 and 2).
  • the invention described in (2) defines the crystal structure of the positive electrode-containing catalyst used in the invention described in (1).
  • tetragonal manganese dioxide is used as the positive electrode-containing catalyst, the capacity of the battery can be increased as compared with the case where manganese dioxide such as electrolytic manganese dioxide is used (see FIGS. 1 and 3).
  • the invention described in (3) defines the pH of the electrolytic solution in the invention described in (1) and (2).
  • the cause of termination of the electrochemical reaction in the positive electrode of the battery of the present invention includes inhibition of the electrochemical reaction due to the formation of a film on the positive electrode surface.
  • the electrolyte contained in the battery is strongly alkaline (around pH 14), a passive film composed of magnesium citrate or magnesium oxide is formed on the surface of the positive electrode, and the electrochemical reaction at the positive electrode is inhibited.
  • the initial electrolyte has a low pH within a range in which self-discharge at the negative electrode can be suppressed.
  • the invention described in (4) defines the polyvalent carboxylate used in the invention described in (1) to (3).
  • Citrate and succinate ions have a relatively low molecular weight and high solubility in water among the polyvalent carboxylate ions chelating to metal ions, so even when chelated to polyvalent metal ions, they dissolve in water. Sex can be kept high. For this reason, film formation on the positive electrode surface can be suppressed.
  • the invention described in (5) defines the concentration of the polyvalent carboxylate in the electrolytic solution of the invention described in (1) to (4).
  • concentration of the polyvalent carboxylate is less than 0.2 mol / L, the catalytic effect on the reduction reaction of water decreases, the resistance of the electrolytic solution decreases due to the decrease in ionic strength, and the effect of suppressing the formation of the coating film decreases. For this reason, the capacity
  • the polyvalent carboxylate concentration exceeds 0.9 mol / L, film formation occurs on the positive electrode surface even at a lower pH, and the capacity of the battery decreases (see FIG. 4).
  • the invention described in (6) defines the negative electrode material in the invention described in (1) to (5).
  • magnesium has an oxidation potential (-2.37 V vs. SHE) lower than the reduction potential of water, and has a large theoretical capacity (2290 mAhg ⁇ 1 ).
  • the solubility of magnesium hydroxide in water is low, there is a problem that a film is formed on the negative electrode surface and the electrochemical reaction is inhibited.
  • the polyvalent carboxylate ion that catalyzes the reduction reaction of water can chelate magnesium hydroxide having a low solubility to improve the solubility. For this reason, it can suppress that the negative electrode surface is coat
  • a liquid retaining part that can hold water disposed between the positive electrode and the negative electrode, and a hole that can introduce water into the liquid retaining part from the outside, and the liquid retaining part is a polyvalent carboxylic acid in a dry state The battery according to any one of (1) to (6), which contains a salt.
  • the invention described in (7) is a person who specified a specific embodiment of the invention described in (1). If water that is a positive electrode active material is not included in the inside of the battery until just before use but is supplied from the outside just before use, the weight of the battery can be reduced. Further, since the electrolytic solution is also an aqueous solution, an electrochemical reaction does not occur if stored in a dry state, and the battery can be stored for a long period of time.
  • the battery of the present invention uses a polyvalent carboxylate as the electrolyte contained in the electrolytic solution and manganese dioxide as the positive electrode-containing catalyst. Since these electrolytes and the positive electrode-containing catalyst catalyze a positive electrode reaction (2H 2 O + 2e ⁇ ⁇ 2OH ⁇ + H 2 ) using water as a positive electrode active material and suppress overvoltage, a battery using water as a positive electrode active material Can be provided.
  • the polyvalent carboxylate ions have low solubility. To improve the solubility of magnesium hydroxide. For this reason, magnesium oxide does not coat the surface of the negative electrode, and the battery can maintain the electromotive force for a long time.
  • FIG. 1 is a diagram illustrating a relationship between a polyvalent carboxylic acid concentration and a capacity obtained by an example of the present invention. 1 is an X-ray diffraction pattern of tetragonal manganese dioxide.
  • the battery of the present invention includes a positive electrode, a negative electrode, and a liquid retaining part held between the positive electrode and the negative electrode.
  • the positive electrode is composed of manganese dioxide, which is a positive electrode-containing catalyst, a conductive agent, and a binder.
  • each material is mixed at a predetermined ratio (for example, 7 parts by mass of manganese dioxide, 2 parts by mass of a conductive agent, and 1 part by mass of a binder), applied to a current collector, and bonded. What is necessary is just to dry at the temperature which the solvent of an adhesive evaporates.
  • Manganese dioxide acts as a positive electrode-containing catalyst, but the amount of reaction field correlates with the amount of manganese dioxide, so it is preferable that the content of manganese dioxide is large.
  • the crystal structure of manganese dioxide is preferably a tetragonal type (see FIG. 5).
  • the conductive agent Since the conductive agent does not participate in the electrochemical reaction, it is preferable that the content is as small as possible as long as the content is sufficient to perform the function.
  • the conductive agent include carbon black such as ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black, scaly graphite, and graphite.
  • the binder Since the binder does not participate in the electrochemical reaction, the smaller the content, the better, as long as the content is sufficient to perform the function.
  • the binder is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin. Specifically, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene -Perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride
  • the positive electrode current collector for example, one made of a material such as graphite, copper, nickel, aluminum, iron, and titanium is suitable, but it is not limited to these as long as it is a conductor.
  • the negative electrode is not particularly limited as long as it does not cause a rapid chemical reaction with water and is made of a material whose oxidation potential is lower than the reduction potential of water ( ⁇ 0.83 V vs. SHE).
  • examples of such materials include magnesium, thorium, beryllium, aluminum, titanium, zirconium, manganese, and alloys thereof.
  • magnesium or a magnesium alloy is preferable from the viewpoints of battery voltage and capacity exhibiting favorable numerical values and availability as a resource.
  • the liquid holding part has hydrophilicity, has a liquid holding function for holding the electrolytic solution, and functions as a separator for preventing a short circuit between the electrodes.
  • a material constituting the liquid retaining portion a polypropylene nonwoven fabric, a polyphenylene sulfide nonwoven fabric, glass fiber, filter paper, a porous film of an olefin resin, etc. can be used, but it has insulating properties and a fluid retaining function. As long as it is not limited to these.
  • the battery of the present invention may be stored in a state where the liquid retaining part is dried, and the liquid retaining part may be water-containing during use. In that case, an aqueous solution of polyvalent carboxylate is held in the liquid retaining part by containing the polyvalent carboxylate in the liquid retaining part and supplying water.
  • the electrolytic solution held in the liquid holding part is an aqueous solution of polyvalent carboxylate. Since polyvalent carboxylate ions contained in the electrolyte catalyze the reduction reaction of water together with manganese dioxide, a battery using water as a positive electrode active material can be provided. Furthermore, even when magnesium or a magnesium alloy is used as the negative electrode active material, polyvalent carboxylic acid ions are chelated to the eluted magnesium ions, so that the solubility of the magnesium salt is improved, and the film formation on the positive electrode and negative electrode surfaces is suppressed. be able to. Moreover, it can prevent that electrolyte solution changes easily to alkaline by the buffer effect
  • the pH of the electrolytic solution is preferably 7 or more and 14 or less.
  • Factors for terminating the electrochemical reaction at the positive electrode of the battery include inhibition of the electrochemical reaction due to the formation of a film on the surface of the positive electrode, in addition to the disappearance of water as the positive electrode active material.
  • the electrolyte contained in the battery is strongly alkaline (around pH 14)
  • a passive film composed of magnesium citrate or magnesium oxide is formed on the surface of the positive electrode, and the electrochemical reaction at the positive electrode is inhibited.
  • the initial electrolyte has a low pH within a range in which self-discharge at the negative electrode can be suppressed.
  • polyvalent carboxylate for example, citrate or succinate can be used.
  • citrate or succinate can be used.
  • the concentration of the polyvalent carboxylate contained in the electrolytic solution is preferably 0.2 mol / L or more and 0.9 mol / L or less.
  • concentration of the polyvalent carboxylate is less than 0.2 mol / L, the catalytic effect on the reduction reaction of water decreases, the resistance of the electrolytic solution decreases due to the decrease in ionic strength, and the effect of suppressing the formation of the coating film decreases. For this reason, the capacity
  • Example 1 [Production of positive electrode] 2 parts by mass of acetylene black and 1 part by mass of polyvinylidene fluoride were mixed with 7 parts by mass of manganese dioxide powder having a tetragonal crystal structure. This mixture was applied to carbon paper and fired at 110 ° C. for 1 hour to obtain a positive electrode.
  • the measurement cell was produced from the produced positive electrode and the electrolytic solution, and the negative electrode and the reference electrode.
  • a magnesium alloy (AZ31) was used for the negative electrode and a magnesium alloy was used for the reference electrode, and the voltage and capacity of the positive electrode were measured.
  • Example 1, 2, and 3 are drawings showing discharge polarities in Example 1, Comparative Example 2, and Comparative Example 3, respectively.
  • FIG. 1 and FIG. 2 it can be seen that when the electrolytic solution containing trisodium citrate is used, the capacity is remarkably larger than when the electrolytic solution containing sodium chloride is used. . It can also be seen that when tetragonal manganese dioxide is used for the positive electrode, the capacity is significantly greater than when electrolytic manganese dioxide is used. As described above, according to the present invention, a battery having sufficient performance can be provided even when water is used as the positive electrode active material.

Landscapes

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

Abstract

L'invention concerne une batterie qui utilise une réaction de réduction de l'eau, c'est-à-dire une batterie qui utilise l'eau comme matériau actif de l'électrode positive. Plus précisément, l'invention concerne une batterie dans laquelle une solution aqueuse d'un sel d'acide carboxylique polyvalent est utilisée comme solution électrolytique, le dioxyde de manganèse est utilisé comme catalyseur contenu dans l'électrode positive et l'eau est utilisée comme matériau actif de l'électrode positive. Etant donné que l'électrolyte et le catalyseur contenu dans l'électrode positive catalysent une réaction d'électrode positive utilisant l'eau comme matériau actif d'électrode positive (2H2O + 2e- -> 2OH- + H2) et évitent les surtensions, il est possible de fournir une batterie qui utilise l'eau comme matériau actif de l'électrode positive.
PCT/JP2011/053353 2010-02-19 2011-02-17 Batterie WO2011102409A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010034336A JP2011171132A (ja) 2010-02-19 2010-02-19 電池
JP2010-034336 2010-02-19

Publications (1)

Publication Number Publication Date
WO2011102409A1 true WO2011102409A1 (fr) 2011-08-25

Family

ID=44482995

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/053353 WO2011102409A1 (fr) 2010-02-19 2011-02-17 Batterie

Country Status (2)

Country Link
JP (1) JP2011171132A (fr)
WO (1) WO2011102409A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5451923B1 (ja) * 2013-04-10 2014-03-26 三嶋電子株式会社 水電池
JP5681307B1 (ja) * 2014-02-26 2015-03-04 博幸 塩谷 マグネシウム電池及びこれを含む発電装置
WO2019044042A1 (fr) * 2017-08-28 2019-03-07 杉山　修 Batterie ayant une solution électrolytique contenant de l'eau minérale alcaline ionisée, matériau actif d'électrolyte et procédé de production d'une solution électrolytique de batterie

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56159058A (en) * 1980-05-08 1981-12-08 Matsushita Electric Ind Co Ltd Alkali manganese battery and its manufacture
JPS57189459A (en) * 1981-05-16 1982-11-20 Sumakichi Shiratori Charging dry cell
JPH02226657A (ja) * 1989-02-27 1990-09-10 Ryuichi Yamamoto マンガン電池
JPH071566U (ja) * 1992-05-11 1995-01-10 久也 広瀬 クエン酸電解液で満たされているマンガン一次乾電池
JP2002110223A (ja) * 2000-09-28 2002-04-12 Sanyo Electric Co Ltd アルカリ蓄電池
WO2007116872A1 (fr) * 2006-04-03 2007-10-18 Tsc Co., Ltd. Alliage pour production d'énergie hydroélectrique, générateur d'énergie hydroélectrique utilisant l'alliage et procédé de production d'énergie hydroélectrique
JP3154488U (ja) * 2009-07-08 2009-10-22 日本協能電子株式会社 水電池
JP2010182435A (ja) * 2009-02-03 2010-08-19 Suzuki Senkei マグネシウム電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56159058A (en) * 1980-05-08 1981-12-08 Matsushita Electric Ind Co Ltd Alkali manganese battery and its manufacture
JPS57189459A (en) * 1981-05-16 1982-11-20 Sumakichi Shiratori Charging dry cell
JPH02226657A (ja) * 1989-02-27 1990-09-10 Ryuichi Yamamoto マンガン電池
JPH071566U (ja) * 1992-05-11 1995-01-10 久也 広瀬 クエン酸電解液で満たされているマンガン一次乾電池
JP2002110223A (ja) * 2000-09-28 2002-04-12 Sanyo Electric Co Ltd アルカリ蓄電池
WO2007116872A1 (fr) * 2006-04-03 2007-10-18 Tsc Co., Ltd. Alliage pour production d'énergie hydroélectrique, générateur d'énergie hydroélectrique utilisant l'alliage et procédé de production d'énergie hydroélectrique
JP2010182435A (ja) * 2009-02-03 2010-08-19 Suzuki Senkei マグネシウム電池
JP3154488U (ja) * 2009-07-08 2009-10-22 日本協能電子株式会社 水電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5451923B1 (ja) * 2013-04-10 2014-03-26 三嶋電子株式会社 水電池
WO2014168155A1 (fr) * 2013-04-10 2014-10-16 三嶋電子株式会社 Batterie à eau
JP5681307B1 (ja) * 2014-02-26 2015-03-04 博幸 塩谷 マグネシウム電池及びこれを含む発電装置
WO2019044042A1 (fr) * 2017-08-28 2019-03-07 杉山　修 Batterie ayant une solution électrolytique contenant de l'eau minérale alcaline ionisée, matériau actif d'électrolyte et procédé de production d'une solution électrolytique de batterie

Also Published As

Publication number Publication date
JP2011171132A (ja) 2011-09-01

Similar Documents

Publication Publication Date Title
JP5218406B2 (ja) 水系リチウム二次電池
JP5192613B2 (ja) マグネシウム金属空気電池
WO2013163695A1 (fr) Matériaux d'électrode de batterie
JP5358533B2 (ja) マグネシウム電池
JP4788560B2 (ja) 蓄電デバイス
JP2008153097A (ja) アルカリ蓄電池
JP2010182435A (ja) マグネシウム電池
JP2012049060A (ja) 非水電解質二次電池用正極及びその正極を用いた非水電解質二次電池
JP6695287B2 (ja) 水系ナトリウムイオン二次電池
JP2017124951A (ja) 遮水性ナトリウムイオン伝導膜およびナトリウム電池
JP4600136B2 (ja) 水系電解液リチウム二次電池
CN103931049B (zh) 用于锂‑空气电池的水性电解液
JP2013254647A (ja) リチウムイオン−リチウム空気複合二次電池、リチウムイオン−リチウム空気複合二次電池を用いた充放電方法、およびリチウムイオン−リチウム空気複合二次電池用正極材料
JP2008262859A (ja) 非水電解液及びリチウムイオン二次電池
CN106207261A (zh) 电解液及电池
WO2011102409A1 (fr) Batterie
JP5256649B2 (ja) 水系リチウム二次電池
JP2006040748A (ja) 電気化学デバイス
JP2010146908A (ja) アルカリ金属硫黄二次電池
JP2008269824A (ja) 電気化学セル
JP5557385B2 (ja) プロトンを挿入種とする蓄電デバイス
JP4862356B2 (ja) 負極活物質及び水系リチウム二次電池
JP2009146756A (ja) 水系リチウムイオン二次電池
JP2007207461A (ja) 非水電解質二次電池
CN103956460B (zh) 一种用于提高磷酸铁锂电池循环使用寿命的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11744695

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11744695

Country of ref document: EP

Kind code of ref document: A1