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WO2011125150A1 - Batterie au magnésium - Google Patents

Batterie au magnésium Download PDF

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Publication number
WO2011125150A1
WO2011125150A1 PCT/JP2010/056034 JP2010056034W WO2011125150A1 WO 2011125150 A1 WO2011125150 A1 WO 2011125150A1 JP 2010056034 W JP2010056034 W JP 2010056034W WO 2011125150 A1 WO2011125150 A1 WO 2011125150A1
Authority
WO
WIPO (PCT)
Prior art keywords
magnesium
negative electrode
magnesium battery
cathode
battery
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2010/056034
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English (en)
Japanese (ja)
Inventor
鈴木　進
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AQUMO
Original Assignee
AQUMO
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 AQUMO filed Critical AQUMO
Priority to PCT/JP2010/056034 priority Critical patent/WO2011125150A1/fr
Publication of WO2011125150A1 publication Critical patent/WO2011125150A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • 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 magnesium battery including a negative electrode made of magnesium.
  • a battery using magnesium or an alloy thereof as a negative electrode active material is known (for example, see Patent Document 1 and Non-Patent Document 1).
  • a manganese dioxide dry battery described in Patent Document 1 uses magnesium or an alloy thereof as a negative electrode active material, manganese dioxide as a positive electrode active material, and magnesium perchlorate as a main electrolyte.
  • the air magnesium battery described in Non-Patent Document 1 uses oxygen in the air as a positive electrode active material, magnesium as a negative electrode active material, and saline as an electrolyte.
  • the magnesium battery as described above has a problem that the redox potential is high and hydrogen is generated on the negative electrode, so that the theoretical negative electrode capacity cannot be obtained stably.
  • a magnesium oxide film is formed on the negative electrode surface due to low solubility of magnesium hydroxide, and the battery reaction does not continue. .
  • the method of adding an organic compound etc. in a neutral region and suppressing self-discharge is also considered, the capacity
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a magnesium battery capable of continuously increasing the negative electrode capacity of the magnesium battery.
  • a magnesium battery according to the present invention includes a negative electrode made of magnesium and a liquid holding part capable of holding an aqueous electrolyte solution that elutes magnesium ions from the negative electrode.
  • the liquid part is characterized by holding an aqueous solution of a polyvalent carboxylate as an aqueous electrolyte.
  • the magnesium battery of the present invention uses an aqueous solution of a polyvalent carboxylate as an electrolyte.
  • a polyvalent carboxylate ion and the magnesium ion eluted from the negative electrode are complexed, and the solubility of the magnesium ion is increased.
  • the negative electrode capacity of the magnesium battery can be continuously increased by suppressing the deposition of magnesium oxide on the negative electrode and enabling the continuous electrolysis of magnesium.
  • the magnesium battery according to the present invention is characterized in that the liquid retaining part holds a polyvalent carboxylate in a dry state. Thereby, a magnesium battery can be stored for a long time in a dry state. And, when water is infiltrated into the liquid retaining part at the time of use, an aqueous solution of polyvalent carboxylate salt is generated and an electromotive force is generated.
  • the magnesium battery according to the present invention is characterized in that the liquid retaining part holds an aqueous solution of a polyvalent carboxylate salt as an aqueous electrolyte.
  • the magnesium battery according to the present invention is characterized in that the concentration of polyvalent carboxylate ions contained in the aqueous electrolyte is 0.2 mol / L or more and 0.9 mol / L or less.
  • the concentration of the polyvalent carboxylate ion is 0.2 mol / L or more, the polyvalent carboxylate ion and the magnesium ion are easily complexed.
  • the concentration of the polyvalent carboxylate ion is 0.9 mol / L or less, the solubility of the complex can be maintained high. As a result, the negative electrode capacity of the magnesium battery can be continuously increased.
  • the magnesium battery according to the present invention is characterized in that the pH of the aqueous electrolyte is 7 or more and 11 or less.
  • pH since pH is 7 or more, hydrogen does not generate
  • pH since pH is 11 or less, the production
  • the magnesium battery according to the present invention is characterized in that the aqueous electrolyte contains an aluminum hydroxide complex in which a trivalent or higher carboxylic acid ion is coordinated.
  • the hydrogenation voltage increases, so that self-discharge is suppressed even in the acidic region, and the original capacity of magnesium can be obtained.
  • the electromotive force of the battery can be maintained even when the pH varies due to the positive electrode reaction.
  • polyvalent carboxylate ions and magnesium ions eluted from the negative electrode are complexed to increase the solubility of magnesium hydroxide, thereby suppressing magnesium oxide precipitation and enabling continuous electrolysis of magnesium. To do. As a result, the negative electrode capacity of the magnesium battery can be continuously increased.
  • FIG. 1 is a cross-sectional view of the magnesium battery 100.
  • the magnesium battery 100 includes a negative electrode 110, a separator 120, an oxygen adsorber 130, and a positive electrode current collector 140.
  • the negative electrode 110 is made of magnesium and is provided at one end of the magnesium battery 100.
  • the separator 120 holds an aqueous solution, this magnesium is eluted into the aqueous solution (Mg ⁇ Mg +2 + 2e ⁇ ) to generate magnesium ions.
  • the separator 120 and the oxygen adsorbent 130 constitute a liquid holding part, and can hold the aqueous electrolyte solution.
  • the separator 120 is disposed between the negative electrode 110 and the oxygen adsorber 130.
  • the separator 120 prevents a short circuit, has hydrophilicity, and has a liquid retaining function for holding an aqueous electrolyte solution.
  • the separator 120 polypropylene fiber, glass fiber, filter paper, or the like can be used.
  • the material of the separator 120 is not particularly limited as long as it has an insulating property and a liquid retaining function.
  • the polyvalent carboxylate is held in the separator 120 or the oxygen adsorbent 130 in advance. This includes the case where a polyvalent carboxylate is held between the separator 120 and the oxygen adsorbent 130.
  • the electrolyte is an aqueous solution of a polyvalent carboxylate.
  • the electrolytic solution contains polyvalent carboxylate ions
  • the polyvalent carboxylate ions are complexed with magnesium ions eluted from the negative electrode 110, and the solubility of magnesium hydroxide is increased.
  • the buffering action of citric acid prevents the electrolyte from changing to alkaline. As a result, the deposition of magnesium oxide is suppressed and the continuous electrolysis of magnesium is enabled.
  • the polyvalent carboxylate ion for example, citrate ion or oxalate ion can be used.
  • the concentration of polyvalent carboxylate ions contained in the electrolytic solution is preferably 0.2 mol / L or more and 0.9 mol / L or less. Since the polyvalent carboxylate ion concentration is 0.2 mol / L or more, complexation is facilitated. On the other hand, since the concentration of the polyvalent carboxylate ion is 0.9 mol / L or less, the solubility of the complex can be maintained high.
  • the pH of the electrolytic solution is 7 or more and 11 or less. Since the pH is 7 or more, hydrogen is not generated, and loss of negative electrode capacity due to self-discharge can be prevented. Moreover, since pH is 11 or less, the production
  • the oxygen adsorber 130 is in close contact with the separator 120 and has a porous property.
  • the oxygen adsorber 130 adsorbs oxygen as a positive electrode.
  • the oxygen adsorber 130 may have an oxygen adsorbing material such as activated carbon in the voids of the porous body, or the oxygen adsorber 130 itself may be a carbon fiber of activated carbon. Examples of the porous body that holds the oxygen-adsorbing substance include a nonwoven fabric.
  • the electrolytic solution penetrates into the oxygen adsorbent 130.
  • the oxygen adsorber 130 adsorbs oxygen in the air as a positive electrode and generates hydroxide ions in the electrolytic solution by reduction (O 2 + 2H 2 O + 4e ⁇ ⁇ 4OH ⁇ ).
  • the positive electrode current collector 140 is provided at the other end of the magnesium battery 100.
  • the positive electrode current collector 140 is formed of a conductor and is connected to the oxygen adsorber 130, and supplies electrons to the oxygen adsorber 130.
  • a metal such as copper is suitable for the positive electrode current collector 140, but is not particularly limited as long as it is a conductor.
  • the magnesium battery 100 is preferably laminated in the order of the negative electrode 110, the separator 120, the oxygen adsorber 130, and the positive electrode current collector 140, and are in close contact with each other. The current value can be increased by increasing the mutual contact area. Moreover, the capability can further be improved by laminating
  • the magnesium battery 100 includes the oxygen adsorber 130 and uses oxygen as the positive electrode, but the positive electrode is optional. Although it is common to generate hydroxide ions in the electrolyte, it is not necessarily limited to this.
  • examples of the positive electrode include manganese oxide and nickel hydroxide.
  • the magnesium battery 100 may have these members instead of the oxygen adsorber 130. However, considering the size of the positive electrode capacity per positive electrode active material, oxygen is preferably used as the positive electrode active material.
  • FIGS. 3A to 3C are graphs showing the relationship between the pH of the electrolyte and the negative electrode capacity corresponding to FIGS. 2A to 2C, respectively.
  • the pH of the aqueous solution is in the range of 7 to 11 in any case where the concentration of the aqueous solution is 0.2 mol / L to 0.9 mol / L.
  • a large negative electrode capacity is obtained.
  • the concentration of the aqueous solution is 0.5 mol / L
  • a negative electrode capacity of 1500 mAh / g or more is obtained even when the pH of the aqueous solution is 12, and the capacity is remarkable.
  • the concentration of the aqueous solution was 0.9 mol / L
  • the negative electrode capacity when the pH of the aqueous solution was 12 was as small as 0 mAh / g.
  • the electrolytic solution contains a polyvalent carboxylate ion, but the electrolytic solution further contains an aluminum hydroxide complex in which trivalent or higher carboxylic acid ions are coordinated. It is preferable. Thereby, since the hydrogenation voltage increases in the negative electrode 110 made of magnesium, self-discharge is suppressed even in an acidic region, and the original capacity of magnesium can be obtained. As a result, the electromotive force of the battery can be maintained even when the pH of the electrolyte varies due to the positive electrode reaction.
  • the trivalent or higher carboxylic acid include citric acid.
  • the negative electrode potential is about ⁇ 1.4 V even when the negative electrode capacity exceeds 1500 mAh / g. Maintained.
  • the aluminum hydroxide complex that coordinates citrate ions is not included in the electrolytic solution, the negative electrode potential approaches 0 V with a negative electrode capacity of less than 500 mAh / g.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Primary Cells (AREA)

Abstract

La présente invention concerne une batterie au magnésium pouvant maintenir de manière continue et à un niveau élevé la capacité de la cathode de la batterie au magnésium. La batterie au magnésium comprend une cathode (110) composée de magnésium, et une section de réservoir (120) pouvant contenir une solution d'électrolyte à base d'eau pour éluer des ions magnésium à partir de la cathode (110). La section de réservoir (120) contient une solution aqueuse de carboxylate polyvalent en tant que solution d'électrolyte à base d'eau, permettant ainsi à une force électromotrice de s'exercer de manière continue entre la cathode (110) et l'anode. Ceci permet de former un complexe avec l'ion carboxylique polyvalent et l'ion magnésium élué à partir de la cathode (110), fournissant ainsi une solubilité d'ion magnésium accrue. Il est ainsi possible de prévenir la précipitation d'oxyde de magnésium sur la cathode (110) et de permettre une électrolyse continue de magnésium, ce qui maintient à un niveau élevé la capacité de la cathode de la batterie au magnésium (100).
PCT/JP2010/056034 2010-04-01 2010-04-01 Batterie au magnésium Ceased WO2011125150A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/056034 WO2011125150A1 (fr) 2010-04-01 2010-04-01 Batterie au magnésium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/056034 WO2011125150A1 (fr) 2010-04-01 2010-04-01 Batterie au magnésium

Publications (1)

Publication Number Publication Date
WO2011125150A1 true WO2011125150A1 (fr) 2011-10-13

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ID=44762137

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/056034 Ceased WO2011125150A1 (fr) 2010-04-01 2010-04-01 Batterie au magnésium

Country Status (1)

Country Link
WO (1) WO2011125150A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004537151A (ja) * 2001-08-01 2004-12-09 マグパワー・システムズ・インコーポレイテッド 電池／燃料セルの性能を向上させるための方法および生成物
WO2008015844A1 (fr) * 2006-07-31 2008-02-07 Techno Bank Co., Ltd. Appareil générateur de courant
JP2008533663A (ja) * 2005-03-10 2008-08-21 エバレデイ バツテリ カンパニー インコーポレーテツド 漏れ抵抗性が改善した空気セル

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004537151A (ja) * 2001-08-01 2004-12-09 マグパワー・システムズ・インコーポレイテッド 電池／燃料セルの性能を向上させるための方法および生成物
JP2008533663A (ja) * 2005-03-10 2008-08-21 エバレデイ バツテリ カンパニー インコーポレーテツド 漏れ抵抗性が改善した空気セル
WO2008015844A1 (fr) * 2006-07-31 2008-02-07 Techno Bank Co., Ltd. Appareil générateur de courant

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