WO2015118691A1 - アルカリ二次電池 - Google Patents

アルカリ二次電池 Download PDF

Info

Publication number
WO2015118691A1
WO2015118691A1 PCT/JP2014/053088 JP2014053088W WO2015118691A1 WO 2015118691 A1 WO2015118691 A1 WO 2015118691A1 JP 2014053088 W JP2014053088 W JP 2014053088W WO 2015118691 A1 WO2015118691 A1 WO 2015118691A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
carbon
secondary battery
alkaline secondary
conductive agent
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/JP2014/053088
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
堤　香津雄
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.)
Exergy Power Systems Inc
Original Assignee
Exergy Power Systems Inc
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 Exergy Power Systems Inc filed Critical Exergy Power Systems Inc
Priority to JP2014535442A priority Critical patent/JP5648772B1/ja
Priority to PCT/JP2014/053088 priority patent/WO2015118691A1/ja
Priority to JP2015519677A priority patent/JP5927372B2/ja
Priority to KR1020167024872A priority patent/KR101763169B1/ko
Priority to ES15745785T priority patent/ES2805538T3/es
Priority to CN201580007665.8A priority patent/CN106133993B/zh
Priority to PT157457854T priority patent/PT3107144T/pt
Priority to PCT/JP2015/050010 priority patent/WO2015118892A1/ja
Priority to HUE15745785A priority patent/HUE050294T2/hu
Priority to DK15745785.4T priority patent/DK3107144T3/da
Priority to RU2016134026A priority patent/RU2671836C2/ru
Priority to EP15745785.4A priority patent/EP3107144B1/en
Priority to US15/117,315 priority patent/US10381647B2/en
Priority to PL15745785T priority patent/PL3107144T3/pl
Priority to BR112016018185-9A priority patent/BR112016018185B1/pt
Publication of WO2015118691A1 publication Critical patent/WO2015118691A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • 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
    • H01M10/24—Alkaline accumulators
    • 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
    • H01M10/34—Gastight accumulators
    • 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
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • 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
    • H01M4/383—Hydrogen absorbing 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an invention related to a secondary battery, and more particularly to an alkaline secondary battery using carbon as a conductive agent.
  • Nickel metal hydride batteries have excellent output characteristics and can realize stable charge and discharge. For this reason, it is widely used in household electric devices, mobile phones, mobile devices such as notebook computers, and charge / discharge power tools. Nickel metal hydride batteries are expected to be used as emergency power sources for facilities such as factories or hospitals where reliability is important. In addition, in combination with natural energy power generation facilities where the amount of power generation is fluctuated by wind power or sunlight, it plays a role in mitigating power fluctuations and is used for power peak cutting, etc. It is expected to be used in a wide range of fields, such as for the purpose of ensuring safety.
  • Patent Document 1 describes an example in which a nickel metal hydride secondary battery is used for system interconnection.
  • Patent Document 2 discloses an alkaline secondary battery in which manganese dioxide is used for the positive electrode instead of nickel hydroxide.
  • M represents a metal element (hydrogen storage alloy).
  • Patent Document 3 discloses an active material obtained by adding a higher cobalt oxide as a conductive agent to nickel hydroxide. In this active material, a conductive network is formed by high-order cobalt oxide between the nickel hydroxide particles, so that the charge / discharge reaction easily proceeds in the entire nickel hydroxide particles, and a high capacity can be achieved. .
  • Patent Documents 4 and 5 disclose an inexpensive active material in which a graphitized carbon material is added as a conductive agent instead of an expensive higher-order cobalt oxide.
  • JP 2008-171515 A International Publication No. 2012/173091 JP-A-11-97008 Japanese Patent No. 3433039 Japanese Patent No. 4641329
  • Nickel hydroxide used as the positive electrode active material for alkaline secondary batteries has low conductivity.
  • an active material in which higher cobalt oxide is added as a conductive agent to nickel hydroxide is employed.
  • the alkaline secondary battery using this active material has a problem that high overvoltage is high and high output is difficult to obtain.
  • amorphous carbon such as acetylene black which is inexpensive and has a small specific gravity is known. With such a conductive agent, sufficient conductivity can be obtained, but since the corrosion resistance is not good, repeated charge / discharge causes oxidative degradation, and the conductivity gradually decreases.
  • carbon When a carbon material is used as the conductive agent for the positive electrode, carbon combines with oxygen in the battery and is oxidized to generate carboxyl groups (COOH) and carbonates, so that the electrode loses conductivity. This is due to the property that carbon is strong against reduction but weak against oxidation. In particular, oxidation proceeds during charging.
  • COOH carboxyl groups
  • cobalt compound contained in the electrode is eluted into the electrolytic solution to form cobalt complex ions.
  • the cobalt complex ions are oxidized during charging to become cobalt oxyhydroxide ( ⁇ -CoOOH), which is reprecipitated in the vicinity of the positive electrode.
  • This cobalt oxyhydroxide is reduced at the time of overdischarge, and the conductive matrix collapses so that it cannot be charged. Therefore, the cycle life of the battery is short. This is due to the property that cobalt is vulnerable to reduction.
  • Oxygen generated at the positive electrode during charging oxidizes lanthanum, manganese, etc. in the hydrogen storage alloy of the negative electrode, reducing the hydrogen storage capacity.
  • the hydrogen storage alloy repeatedly expands and contracts due to the storage and release of hydrogen, and the crystal lattice spacing increases.
  • the surface area is increased by pulverization of the hydrogen storage alloy, and the oxidation of the hydrogen storage alloy is promoted. By repeating charging and discharging, the hydrogen storage capacity of the hydrogen storage alloy decreases, and the battery life decreases.
  • the present invention has been made in view of the above circumstances, and by developing an alkaline secondary battery in which the conductive agent does not undergo oxidative degradation even when charging and discharging are repeated, and the hydrogen storage alloy does not undergo oxidative degradation. It aims at providing the alkaline secondary battery excellent in the characteristic.
  • An alkaline secondary battery of the present invention is an alkaline secondary battery comprising a negative electrode containing a hydrogen storage alloy and a positive electrode containing a positive electrode active material and a conductive agent, and the alkaline secondary battery includes a hydrogen Gas is enclosed, the conductive agent contains carbon, and the electrode surfaces of the negative electrode and the positive electrode are in contact with the hydrogen gas. According to this configuration, the conductive agent contained in the positive electrode does not undergo oxidative degradation, and the hydrogen storage alloy contained in the negative electrode does not undergo oxidative degradation.
  • the conductive agent contains soft carbon partially graphitized.
  • the conductive agent includes soft carbon obtained by firing a soft carbon precursor at 1500 to 2800 ° C.
  • the conductive agent contains particulate soft carbon having a graphitization degree (G value) of 0.3 or more and 0.8 or less analyzed by Raman spectroscopy.
  • the soft carbon is a granulated particle.
  • the soft carbon of the conductive agent may be formed by granulation.
  • the positive electrode includes the positive electrode active material coated with the soft carbon.
  • the positive electrode active material coated with the soft carbon is combined.
  • the total of the positive electrode active material and the soft carbon is 100 wt. %, The amount of the soft carbon is 2 to 5 wt. %.
  • the pressure of the hydrogen gas is 0.2 Mpa to 278 MPa.
  • 8 to 400 g of hydrogen gas per 22.4 L is held on the positive electrode and / or the negative electrode.
  • the positive electrode does not contain a cobalt compound as the conductive agent.
  • the electrode surfaces of the positive electrode and the negative electrode are in contact with hydrogen gas sealed in the alkaline battery. Oxygen generated in the positive electrode is combined with hydrogen gas sealed in the battery, so that the positive electrode conductive agent and the negative electrode hydrogen storage alloy are not oxidized. The conductive agent and the hydrogen storage alloy are not deteriorated by oxidation, and an alkaline secondary battery excellent in cycle life characteristics can be realized.
  • the above carbon material is resistant to oxidation, and the conductivity is hardly lowered. Even if the alkaline secondary battery of the present invention is overcharged, the cycle life is unlikely to be impaired.
  • the conductive agent was eluted by overcharging. However, since the alkaline secondary battery of the present invention uses a carbon-based conductive agent for the positive electrode, the conductive agent remains even if overdischarged. It does not dissolve in the electrolyte, and the cycle life of the battery is not easily lost.
  • the positive electrode material is not particularly limited as long as it can be used for a positive electrode of an alkaline secondary battery, and may be a nickel hydroxide positive electrode material or a silver oxide positive electrode material. For example, it may be nickel hydroxide or manganese dioxide.
  • the positive electrode active material can easily achieve a high capacity, a material having a large bulk density, for example, a spherical material is preferable.
  • a positive electrode for an alkaline secondary battery can be obtained by depositing and forming a positive electrode material of the following examples on a current collector.
  • the conductive agent contained in the positive electrode is preferably blended in the range of 1 to 25% by weight when the total of the positive electrode active material, the binder, and the conductive agent is 100% by weight. More preferably, it is set to 3 to 15% by weight.
  • the conductive agent is for imparting conductivity to the active material and increasing its utilization rate.
  • the conductive agent used in this example is preferably a carbon material that does not elute into the electrolyte during discharge and is not easily reduced by hydrogen.
  • Such carbon materials include graphite and / or amorphous carbon.
  • Amorphous carbon is a concept including carbon black, soft carbon, hard carbon, activated carbon, carbon nanotube (CNT), vapor grown carbon fiber (VGCF), and the like.
  • Carbon black includes furnace black, acetylene black (AB), and ketjen black (KB).
  • Soft carbon is also referred to as highly crystalline carbon
  • hard carbon is also referred to as low crystalline carbon.
  • These conductive agents contain a particulate carbon material as an essential component.
  • the soft carbon means “carbon that becomes a graphite crystal by performing a treatment required for graphitization”.
  • soft carbon is a carbon that easily develops a graphite structure-a structure in which hexagonal network planes composed of carbon atoms are regularly layered-when heated in an inert atmosphere. It is also called graphitizable carbon.
  • graphite is carbon obtained by graphitizing the soft carbon and is also referred to as graphite.
  • hard carbon means carbon that cannot be converted into graphite crystals even if the treatment required for graphitization (for example, high temperature treatment) is performed.
  • hard carbon is carbon having an irregular structure in which the development of the above-described graphite structure is suppressed, and is also referred to as non-graphitizable carbon.
  • soft carbons partially graphitized carbon is preferred. Of these, those in which the surface portion of the soft carbon is graphitized are preferable. Soft carbon with advanced graphitization tends to deteriorate. If there is little graphitization, conductivity will not improve.
  • the ratio of graphitization is 100 wt. %, 10 to 90 wt. %, Preferably 20 to 60 wt. % Is more preferable.
  • the soft carbon preferably has a specific graphitization degree of graphitization degree (G value) analyzed by Raman spectroscopy of 0.3 to 0.8, preferably 0.4 to 0.7.
  • Such soft carbon can be produced, for example, by heat-treating a soft carbon precursor in a non-oxidizing gas atmosphere.
  • the heat treatment temperature here is preferably set to 1000 ° C. or higher and 2800 ° C. or lower and fired.
  • a granulated carbon material As the granulation method, the mechanical milling process described later can be used, but may be a rolling granulation method, a fluidized bed granulation method, a stirring granulation method, a compression granulation method, or the like, and is not limited to these. It is not something.
  • the soft carbon precursor examples include coal-based heavy oil such as tar and pitch or petroleum-based heavy oil.
  • the firing temperature of the soft carbon precursor is 1500-2800 ° C., preferably 2000-2600 ° C. When the firing temperature of the soft carbon precursor is less than 500 ° C., the soft carbon precursor is difficult to be carbonized and it is difficult to obtain soft carbon. Soft carbon is generated when the temperature is in the range of 500 ° C. or more and less than 1500 ° C., but output characteristics are lacking because of low conductivity as a conductive agent. On the other hand, when the firing temperature rises, soft carbon gradually graphitizes from around 2800 ° C. Graphite tends to oxidize and deteriorate when repeated charging and discharging, and therefore battery life tends to be shortened when overcharged or rapidly charged.
  • Non-oxidizing gas atmosphere means a gas atmosphere with a very small amount of oxygen, for example, in a vacuum or in an inert gas atmosphere (for example, nitrogen, helium, neon, argon, hydrogen, carbon dioxide, or those Of mixed gas).
  • the particulate carbon material raw material used here has an average particle diameter of 20 nm or more and 100 nm or less.
  • the average particle diameter is less than 20 nm, it is likely to be damaged during the heat treatment, and the target particulate carbon material may be difficult to obtain.
  • the resulting particulate carbon material may not easily reduce the resistance value of the electrode even when the same weight as that of the other particulate carbon material is added to the active material.
  • the conductive agent used in the present embodiment may further include a fibrous carbon material or a flaky carbon material having a high aspect ratio as an auxiliary component in addition to the above-described particulate carbon material.
  • the conductive agent includes a carbon material having a high aspect ratio, the ratio is preferably limited to 20% by weight or less.
  • the positive electrode using the carbon material of Example 1 can realize an alkaline secondary battery excellent in cycle life characteristics.
  • the carbon material of Example 2 is manufactured by forming a soft carbon coating film on the surface of the conductive material by performing a heat treatment on the conductive material.
  • a metal, a compound, a carbon material, and the like that are easily eluted into the electrolytic solution can be selected.
  • graphite, furnace black, acetylene black (AB), ketjen black (KB), soft carbon, hard carbon, activated carbon, carbon nanotube (CNT), vapor grown carbon fiber (VGCF), copper, nickel, iron, gold Platinum, conductive ceramics, conductive polymer, etc. are used.
  • materials having higher conductivity than soft carbon are preferable, and examples thereof include graphite, furnace black, AB, KB, CNT, VGCF, copper, nickel, iron, gold, and platinum.
  • the heat treatment for example, a treatment in which the conductive material is coated with a soft carbon precursor and then held at a temperature of 1500 to 2800 ° C. in a non-oxidizing gas atmosphere for 0.1 to 10 hours is employed.
  • the heat treatment temperature is less than 1500 ° C.
  • the conductivity improvement effect of soft carbon may be small.
  • the apparatus becomes large and not only the cost is increased, but the film is graphitized and easily oxidized.
  • the heat treatment time is less than 0.1 hour, it may be difficult to obtain a uniform soft carbon coating.
  • the heat source must be driven for a long time, which may increase the cost.
  • the heat treatment atmosphere may be a non-oxidizing gas atmosphere, that is, in a vacuum, nitrogen, helium, neon, argon, hydrogen, carbon dioxide, or a mixed gas thereof.
  • the coating method an existing method such as sputtering, fluidized bed, spray method, rotary kiln method, or dipping method can be used.
  • the mechanical strength of soft carbon is lower than that of the coated object
  • a complex of objects can also be formed.
  • the gravitational acceleration of the mechanical milling process is preferably 5 to 100G, and more preferably 10 to 50G.
  • the acceleration of gravity is less than 10 G, it is difficult to coat the particle surface of the object to be coated with soft carbon, resulting in poor oxidation resistance.
  • the coated object may be pulverized in addition to the soft carbon, and the coated object may be exposed on the composite particle surface.
  • the mechanical milling atmosphere is preferably a non-oxidizing gas atmosphere rather than an air atmosphere.
  • a non-oxidizing gas atmosphere By performing in a non-oxidizing gas atmosphere, the self-lubricating property of the carbon material can be suppressed, so that the pulverization of the carbon material, especially the soft carbon, is improved, and the particle surface of the object to be coated is coated with the carbon material. It is easy to obtain a composite material.
  • the non-oxidizing gas atmosphere is more preferably a reducing atmosphere in which hydrogen gas or the like is enclosed.
  • the mechanical milling process is a method capable of applying external forces such as impact, tension, friction, compression, and shear to the raw material powder (at least the positive electrode material and soft carbon), and includes a rolling mill, a vibration mill, Examples include a method using a planetary mill, a rocking mill, a horizontal mill, an attritor mill, a jet mill, a crusher, a homogenizer, a fluidizer, a paint shaker, a mixer and the like.
  • the raw material powder can be pulverized / mixed or subjected to solid phase reaction by mechanical energy generated by putting both the raw material powder and balls in a container and rotating and revolving.
  • Soft carbon has lower mechanical strength than the object to be coated, and materials having high conductivity include, for example, graphite, hard carbon, activated carbon, carbon nanotube (CNT), vapor grown carbon fiber (VGCF), copper, Nickel, iron, gold, platinum, etc. can be used.
  • the soft carbon-coated conductive agent thus produced is an effect of improving the conductivity of the positive electrode because the soft carbon coating film is a thin film having oxidation resistance and the coating exhibits high conductivity.
  • the thickness of the soft carbon coating film is not particularly limited because it includes bubbles and fluctuates during coating or heat treatment, but is preferably in the range of 10 nm to 1000 nm, for example. If the thickness of the soft carbon coating film is less than 10 nm, the improvement in oxidation resistance is insufficient, the conductivity of the conductive agent is likely to be uneven, and current concentration during charge / discharge is likely to occur, resulting in a high rate. It may be difficult to improve the charge / discharge characteristics. On the other hand, when the thickness of the carbon coating film exceeds 1000 nm, the electrode capacity density may be reduced.
  • the coverage of the carbon coating film needs to be 0.1 to 30% by mass with respect to 100% by mass of the conductive coating. If the coverage is less than 0.1% by mass, the improvement in oxidation resistance is insufficient, the conductivity of the conductive agent is likely to be uneven, current concentration tends to occur during charge / discharge, and high rate charge / discharge It may be difficult to improve the characteristics. On the other hand, when the coverage exceeds 10% by mass, there is a problem in that the electrode capacity density is reduced.
  • the minimum with a preferable coverage is 0.2 mass%, and a more preferable minimum is 0.5 mass%.
  • the upper limit with preferable coverage is 10 mass%, and a more preferable upper limit is 5 mass%.
  • the soft carbon has a graphitization degree (G value) analyzed by Raman spectroscopy of 0.3 or more and 0.8 or less, preferably 0.4 or more and 0.7 or less, exhibiting a specific degree of graphitization. preferable.
  • G value graphitization degree
  • a metal that is easily eluted and a carbon material that is easily oxidized can be used as the positive electrode material. This makes it possible to complement each other between a metal that is easy to conduct electricity but is easily dissolved in an electrolytic solution, and a carbon material that has a higher electrical resistance than metal.
  • the positive electrode material shown in Example 3 is manufactured by combining the conductive agent of Example 1 or Example 2. That is, a positive electrode material is produced by combining a powder obtained by coating a positive electrode active material with a carbon material. However, since the positive electrode active material decomposes at 230 ° C. or higher, a soft carbon coating film cannot be formed on the surface of the positive electrode active material by performing a heat treatment on the positive electrode active material. Therefore, in this example, it is important to produce a positive electrode material by forming a soft carbon coating film on the surface of the positive electrode active material without performing heat treatment.
  • the positive electrode active material and soft carbon are subjected to mechanical milling to form a soft carbon / positive electrode active material composite in which the particle surface of the positive electrode active material is coated with soft carbon.
  • the gravitational acceleration of the mechanical milling process is preferably 1 to 50G, and more preferably 5 to 30G.
  • the gravitational acceleration is less than 1 G, it is difficult to coat the particle surface of the positive electrode active material with soft carbon, resulting in poor life characteristics.
  • the positive electrode active material is likely to be crushed, and the positive electrode active material may be exposed on the surface of the composite particles, resulting in poor output characteristics.
  • the positive electrode active material is, for example, nickel hydroxide or manganese dioxide.
  • the mechanical milling process is a method capable of imparting external forces such as impact, tension, friction, compression, and shear to the raw material powder (at least the positive electrode active material and soft carbon), and the method described in Example 2 Is available.
  • the positive electrode includes at least a positive electrode active material and a conductive agent.
  • soft carbon which is a conductive agent, has lower mechanical strength than the positive electrode active material, and therefore soft carbon is more easily pulverized than the positive electrode active material. Therefore, the soft carbon powder in the form of fine particles is pressed against the surface of the positive electrode active material powder by a ball or the like, and the positive carbon active material can be covered with soft carbon.
  • the soft carbon coated on the surface of the powder of the positive electrode material containing the positive electrode active material one produced by the same method as that used in Example 1 is used.
  • the soft carbon preferably has a specific graphitization degree of graphitization degree (G value) analyzed by Raman spectroscopy of 0.3 to 0.8, preferably 0.4 to 0.7.
  • the binder examples include polyacrylic acid soda, methyl cellulose, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), ethylene-vinyl alcohol, ethylene vinyl acetate copolymer (EVA), polyethylene ( PE), polypropylene (PP), fluororesin, and styrene-ethylene-butylene-styrene copolymer (SEBS).
  • the weight ratio of the binder mixed in the positive electrode is preferably set to 20% by weight or less, and preferably 10% by weight or less. More preferably, it is set to 5% by weight or less. When the proportion of the binder exceeds 20% by weight, it is difficult to increase the capacity.
  • the positive electrode for an alkaline secondary battery of this embodiment may contain other components than the above-described essential components as long as the purpose of the present invention is not impaired.
  • the positive electrode for an alkaline secondary battery according to this embodiment is obtained, for example, by sufficiently and uniformly mixing a positive electrode material and a conductive agent, adding a binder thereto, and kneading it into a paste.
  • the current collector for the positive electrode is not particularly limited as long as it is a material having electronic conductivity and capable of energizing the held negative electrode material.
  • conductive materials such as C, Fe, Ti, Cr, Ni, Mo, Ta, W, Pt, and Au, and alloys containing two or more of these conductive materials (for example, stainless steel) can be used.
  • Ni is preferable as the current collector from the viewpoint of high electrical conductivity and good stability in the electrolytic solution and good oxidation resistance. Note that iron coated with nickel may be used.
  • the positive electrode current collector is preferably one in which the surface of the current collector is coated with carbon.
  • the oxidation resistance of the current collector can be improved by forming a carbon layer on the current collector surface in advance.
  • the carbon layer to be formed may be any carbon layer that has good adhesion between the active material layer and the current collector and has conductivity.
  • the carbon layer can be formed by coating, spraying, or dipping a binder mixed with a carbon-based conductive agent in a thickness of 0.1 ⁇ m to 50 ⁇ m on the current collector.
  • the conductive agent for the carbon layer is preferably soft carbon powder. If it is a metal-based conductive agent, it is oxidized during overcharge or rapid charge, and the conductive network of the electrode is easily destroyed, so that the input / output characteristics are deteriorated.
  • the carbon-based conductive agent the carbon materials described in Example 1 and Example 2 can be used. One kind of these may be used, or two or more kinds may be used in combination.
  • the soft carbon coated on the surface of the current collector one produced by the same method as that used in Example 1 is used.
  • the soft carbon preferably has a specific graphitization degree of graphitization degree (G value) analyzed by Raman spectroscopy of 0.3 to 0.8, preferably 0.4 to 0.7.
  • the type of binder for the carbon layer formed on the current collector is not limited as long as it can bind the carbon-based conductive agent.
  • a carbon layer is formed using a material that dissolves in water, such as PVA, CMC, and sodium alginate, the carbon layer dissolves when the electrode slurry is applied or filled, and the effect is often not exhibited significantly. . Therefore, when using such an aqueous binder, the carbon layer may be crosslinked in advance.
  • the crosslinking material include a zirconia compound, a boron compound, a titanium compound, and the like, and may be added in an amount of 0.1 to 20% by mass with respect to the amount of the binder when forming the slurry for the carbon layer.
  • the carbon layer thus produced has low polarization and good high rate charge / discharge characteristics even when overcharged or rapidly charged.
  • the shape of the current collector there are a linear shape, a rod shape, a plate shape, a foil shape, a net shape, a woven fabric, a non-woven fabric, an expanded, a porous body, an embossed body, or a foamed body.
  • An embossed body or a foamed body is preferable because of good characteristics.
  • it may be a two-dimensional substrate such as a punching metal, an expanded metal, and a wire mesh.
  • it may be a three-dimensional substrate such as a foamed nickel substrate, a reticulated sintered fiber substrate, or a nickel-plated substrate that is a nonwoven fabric plated with metal.
  • a conductive network can be imparted to the positive electrode material by using the above-described current collector. As a result, it is easy to achieve high capacity.
  • the positive electrode material powder, the binder, and the conductive powder are mixed and kneaded into a paste. This paste is applied or filled into a current collector and dried. Then, a positive electrode is produced by rolling a collector with a roller press or the like.
  • the hydrogen storage alloy contained in the negative electrode material is not particularly limited as long as it can store and release hydrogen.
  • AB5 type which is a rare earth alloy
  • AB2 type which is a Laves phase alloy
  • AB type which is a titanium-zirconium alloy
  • A2B type which is a magnesium alloy.
  • a ternary alloy containing MmNiCoMnAl misch metal which is an AB5 type rare earth-nickel alloy.
  • a LaMgNi system called a superlattice hydrogen storage alloy is preferable. These alloys may be used alone or in combination of two or more.
  • the conductive agent for negative electrode should just be a powder which has electroconductivity.
  • the conductive agent may be a carbon material powder such as graphite powder, acetylene black, and ketjen black, or may be a metal powder such as nickel or copper.
  • the weight ratio of the conductive agent mixed in the negative electrode may be mixed in the range of 0.1 to 10% by weight. preferable.
  • Hydrogen storage alloy powder, binder, and conductive powder are mixed and kneaded into a paste. This paste is applied or filled into a current collector and dried. Then, a negative electrode is produced by rolling a collector with a roller press or the like.
  • binder for negative electrode>
  • the binder include polyacrylic acid soda, methyl cellulose, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), ethylene-vinyl alcohol, ethylene vinyl acetate copolymer (EVA), polyethylene (PE ), Polypropylene (PP), styrene butadiene rubber (SBR), fluororesin, styrene-ethylene-butylene-styrene copolymer (SEBS), nylon, xanthan gum.
  • CMC carboxymethyl cellulose
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • EVA ethylene-vinyl alcohol
  • EVA ethylene vinyl acetate copolymer
  • PE polyethylene
  • PP Polypropylene
  • SBR styrene butadiene rubber
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • nylon
  • the weight ratio of the binder mixed in the negative electrode is preferably set to 20% by weight or less. It is more preferably set to 10% by weight or less, and further preferably set to 5% by weight or less. When the proportion of the binder exceeds 20% by weight, it is difficult to increase the capacity.
  • the negative electrode for an alkaline secondary battery of this embodiment may contain other components than the above-mentioned essential components as long as the purpose of the present invention is not impaired.
  • the negative electrode for an alkaline secondary battery according to the present embodiment can be usually prepared by mixing the above-described components at a required ratio. For example, it can be obtained by sufficiently and uniformly mixing the electrode material and the conductive agent, adding a binder thereto, and kneading it into a paste.
  • the current collector for the negative electrode is not particularly limited as long as it is a material that has electronic conductivity and can conduct electricity to the held negative electrode material.
  • conductive materials such as C, Fe, Ti, Cr, Ni, Cu, Mo, Ta, W, Pt, and Au, and alloys containing two or more of these conductive materials (for example, stainless steel) are used. obtain. From the viewpoint of high electrical conductivity and good stability in the electrolyte and reduction resistance, Ni or the like is preferable as the current collector.
  • Ni or the like is preferable as the current collector. Note that iron coated with nickel or carbon may be used.
  • the shape of the current collector there are a linear shape, a rod shape, a plate shape, a foil shape, a net shape, a woven fabric, a non-woven fabric, an expanded, a porous body, an embossed body, or a foamed body.
  • An embossed body or a foamed body is preferable because of good characteristics.
  • it may be a two-dimensional substrate such as a punching metal, an expanded metal, and a wire mesh.
  • it may be a three-dimensional substrate such as a foamed nickel substrate, a reticulated sintered fiber substrate, or a nickel-plated substrate that is a nonwoven fabric plated with metal.
  • a conductive network can be imparted to the negative electrode material by using the above-described current collector. For this reason, it is easy to achieve high capacity.
  • a paste is prepared by mixing the negative electrode material powder, the binder, and the conductive powder. This paste is applied or filled into a current collector and dried. Then, a negative electrode is produced by rolling a collector with a roller press or the like.
  • the electrolyte is not particularly limited as long as it is used in a battery using hydrogen as an active material.
  • a salt such as potassium hydroxide (KOH), lithium hydroxide (LiOH), or sodium hydroxide (NaOH) in water. What was melt
  • dissolved is suitable.
  • the electrolytic solution is preferably an aqueous potassium hydroxide solution.
  • the electrolyte may be a non-aqueous solvent, a solid electrolyte, a gel electrolyte, an ionic liquid, or the like in addition to the above-described aqueous solvent.
  • a separator As a separator, a well-known thing used for the battery which uses hydrogen as an active material can be used. Examples of the shape of the separator include a microporous film, a woven fabric, a nonwoven fabric, and a green compact. Among these, a nonwoven fabric is preferable from the viewpoint of output characteristics and production cost.
  • the material of the separator is not particularly limited, but is preferably a separator having alkali resistance, oxidation resistance, and reduction resistance. Examples thereof include materials such as polytetrafluoroethylene (PTFE), polyimide (PI), polyamide, polyamideimide, aramid, polyethylene, and polypropylene. Moreover, the separator which coat
  • a wound battery 1 shown in FIG. 1 includes a positive electrode 3, a negative electrode 4, a separator 5, and an electrolytic solution disposed in a battery case 2 as main components.
  • the battery case 2 is a substantially cylindrical container having an opening 2a in the upper part, and the bottom part thereof serves as a negative electrode terminal.
  • the strip-like positive electrode 3 and the negative electrode 4 are accommodated in the battery case 2 in a state of being wound in a spiral while sandwiching the separator 5 therebetween. Further, the opening 2 a of the battery case is sealed in a liquid-tight manner by the sealing plate 7 in a state where the electrolytic solution is injected into the battery case 2.
  • the cap 6 provided on the upper surface of the sealing plate 7 serves as a positive electrode terminal.
  • the positive electrode terminal is connected to the positive electrode 3 by a lead wire (not shown).
  • the separator is arranged in the order of separator-negative electrode-separator-positive electrode and wound around one end in the longitudinal direction of the separator to produce a wound block.
  • a nickel tab is welded to each of the negative electrode side and the positive electrode side of the wound block, and the wound block is immersed in the electrolytic solution.
  • the winding block is impregnated with the electrolytic solution by releasing to atmospheric pressure.
  • this wound block is housed inside a battery case having a pressure-resistant container property, a hydrogen gas tank of 4 MPa is connected, hydrogen gas is sealed inside the battery, and sealed.
  • the laminated battery 11 shown in FIG. 2 includes an exterior body 15, a current collector rod 17, and an electrode body 13 housed inside the exterior body as main components.
  • the exterior body 15 includes a bottomed cylindrical can 12 and a disk-shaped lid member 16 attached to the opening 12c of the cylindrical can.
  • the lid member 16 is closely fitted in the opening 12c of the cylindrical can after the electrode body 13 is accommodated.
  • An electrode body 13 composed of a positive electrode 13a, a negative electrode 13b, and a separator 13c interposed between the positive electrode 13a and the negative electrode 13b is laminated in the axial direction of the cylindrical can 12 (X direction in FIG. 2), and the outer package 15 Is housed inside.
  • the outer edge portion 13ab of the positive electrode is in contact with the inner surface 12a of the cylindrical can, and the positive electrode 13a and the cylindrical can 12 are electrically connected.
  • a current collecting rod 17 passes through the center of the electrode body 13.
  • the peripheral edge portion 13ba of the hole of the negative electrode is in contact with the shaft portion 17a, and the negative electrode 13b and the current collecting rod 17 are electrically connected.
  • the lid member 16 is provided with a supply port 19 for supplying an electrolytic solution and hydrogen gas, and a hydrogen gas tank 20 can be connected to the supply port 19.
  • the negative electrode and the positive electrode are overlapped with each other through a separator impregnated with an electrolytic solution in advance and accommodated in an exterior body, and sealed to assemble a battery.
  • a vacuum is drawn at 80 ° C. for 1 hour to eliminate air inside the battery.
  • a hydrogen gas tank of 4 MPa is connected and hydrogen gas is sealed inside the battery.
  • a vacuum is drawn again at 80 ° C. for 1 hour, and hydrogen gas is supplied into the battery from a 4 MPa hydrogen gas tank.
  • the hydrogen gas supplied to the battery is not held in a special space such as a hydrogen storage chamber, but is held in a gap inside the battery. Examples of such a gap include a gap between the positive electrode and the outer package serving as the current collector, a gap between the negative electrode and the current collector rod serving as the current collector, a gap between the electrodes, and a gap between the electrode and the separator. . Furthermore, hydrogen gas is also retained in the voids existing inside the electrode. In particular, oxygen generated in the positive electrode is immediately combined with hydrogen gas held in the gap of the positive electrode to become water, so that the conductive agent contained in the positive electrode is not oxidized.
  • hydrogen gas is replenished to the space
  • the pressure of the hydrogen gas sealed in the battery is in the range of 0.1 to 278 MPa.
  • the pressure is 278 MPa or more, the outer package serving as a pressure vessel becomes large. Moreover, when it becomes a negative pressure, it becomes inconvenient to handle.
  • a preferable hydrogen gas pressure is 0.2 MPa to 100 MPa. It may be 0.4 MPa to 20 MPa. If it is this range, it can apply easily also to a small battery.
  • the amount of hydrogen gas held inside the electrode depends on the hydrogen gas pressure, and is preferably 8 g to 400 g per 22.4 L.
  • the hydrogen gas is not generated inside the battery by electrolysis of the electrolytic solution, but is previously sealed inside the battery from the outside of the battery.
  • Positive electrode is nickel hydroxide and various carbon materials, polyolefin binder (Mitsui Chemicals: Chemipearl 0.5 wt.%), Acrylic acid thickener (Sumitomo Seika: SS gel 0.15 wt.%), Non-ionic interface It was prepared by filling a foamed nickel substrate (Sumitomo Electric: Celmet # 8) with a slurry made of an activator (Sigma-Aldrich: Triton X 0.15 wt.%).
  • the positive electrode composition includes nickel hydroxide (99.2-X wt.%), Carbon material (X wt.%), Polyolefin binder (0.5 wt.%), Acrylic thickener (0.15 wt.%), Non- An ionic surfactant (0.15 wt.%) was used, and carbon material X was added with 0, 2, 3 wt.%, Respectively.
  • carbon material acetylene black (AB) and soft carbon (SC) fired at 2300 ° C. were used.
  • the negative electrode used as the counter electrode is manufactured by coating a punched metal base material with an AB5 type hydrogen storage alloy.
  • the separator is a sulfonated 130 ⁇ m thick polypropylene nonwoven fabric (manufactured by Japan Vilene).
  • the electrolyte is water.
  • a potassium oxide aqueous solution (6 mol / L) containing 30 g / L of lithium hydroxide was used.
  • the negative electrode capacity and the positive electrode capacity ratio (N / P) were adjusted to 2.5, and a wound battery having a nominal capacity of 1000 mAh was manufactured using a pressure vessel as a battery case.
  • These batteries were charged with 0.4 MPa of hydrogen gas, charged and discharged at 0.1 CA, 0.2 CA, and 0.5 CA once each for chemical conversion treatment, and then evaluated for life characteristics by a 1 CA constant current charge / discharge test.
  • FIG. 3 is a graph comparing the cycle life characteristics of a battery in which hydrogen gas is sealed in a battery and a battery in which air is sealed and the discharge amount of the battery is measured and a conductive agent is used as a parameter.
  • curve (1) is a test result in a hydrogen atmosphere using a carbon material of AB 2 wt% as the conductive agent.
  • Curves (2) and (3) are test results in an air atmosphere using carbon materials of 2 wt% and 3 wt% AB, respectively, as the conductive agent.
  • a curve (4) is a test result in an air atmosphere when no conductive agent is used.
  • Curve (5) is a test result in a hydrogen atmosphere using soft carbon (SC) fired at 2300 ° C. as the conductive agent.
  • SC soft carbon
  • the battery in which hydrogen gas is sealed shows that the life characteristics are dramatically improved as compared with the battery in which air is sealed. This is because the conductive agent contained in the positive electrode was inhibited from being oxidized by the action of hydrogen sealed in the battery, and as a result, it is presumed that the life characteristics of the battery were dramatically improved.
  • the reaction shown in Formula 5 occurs. In Formula 5, the oxidation of the hydrogen storage alloy (M) does not proceed. That is, if hydrogen gas is sealed inside the battery, it can be seen that there is almost no decrease in discharge capacity even after 200 cycles.
  • Negative electrode H 2 + 2OH ⁇ ⁇ 2H 2 O + 2e ⁇
  • a battery in which hydrogen gas is encapsulated using AB as the positive electrode conductive agent (curve (1)) begins to gradually deteriorate after 300 cycles, while a battery in which hydrogen gas is encapsulated using soft carbon (curve ( 5)), no tendency to deteriorate after 500 cycles. From this, it can be seen that the carbon of the conductive agent for the positive electrode is preferably soft carbon rather than acetylene black.
  • FIG. 4 shows a charge / discharge curve of a battery in which hydrogen gas is sealed using AB as a conductive agent.
  • FIG. 5 shows a charge / discharge curve of a battery in which hydrogen gas is sealed using SC as a conductive agent. Comparing both, it can be seen that the charge / discharge characteristics of FIG. 4 have a larger variation than that of FIG.
  • Example 2 (Examination of conductive agent) Various carbon materials shown in Table 1 were used as the conductive agent for the positive electrode.
  • a conductive agent having a coating was obtained by forming a soft carbon coating film on the surface of the conductive agent and baking it.
  • the total of the covering object and the covering (soft carbon precursor) is 100 wt. %
  • the covering object is 90 wt. %
  • the coating is 10 wt. %.
  • the positive electrode composition is nickel hydroxide (97.2 wt.%), Carbon material (2 wt.%), Polyolefin binder (0.5 wt.%), Acrylic acid thickener (0.15 wt.%). %), A positive electrode made of a nonionic surfactant (0.15 wt.%) was produced.
  • the negative electrode used as the counter electrode is manufactured by coating a punched metal base material with an AB5 type hydrogen storage alloy.
  • the separator is a sulfonated 130 ⁇ m thick polypropylene nonwoven fabric (manufactured by Japan Vilene).
  • the electrolyte is water.
  • a solution containing 30 g / L of lithium hydroxide in an aqueous potassium oxide solution (6 mol / L) was used.
  • the negative electrode capacity and the positive electrode capacity ratio (N / P) were adjusted to 2.5, and a wound battery having a nominal capacity of 1000 mAh was manufactured using a pressure vessel as a battery case.
  • These batteries were charged with 0.4MPa hydrogen gas, charged and discharged at 0.1CA, 0.2CA, and 0.5CA once each and then subjected to chemical conversion treatment. Then, the battery capacity for each cycle was determined by a 1CA constant current charge / discharge test. Compared. Other conditions not described are the same as in the battery of Example 1.
  • Table 2 shows battery life characteristics using various carbon materials as the positive electrode conductive agent. It can be seen from Table 2 that all batteries encapsulating hydrogen gas have satisfactory battery capacity.
  • Example 3> (Positive electrode material coated with a conductive agent) As the positive electrode material, nickel hydroxide powder and soft carbon powder fired at 2300 ° C were prepared to 97: 3 wt.%, And ball milling (400rpm, 3h) was performed in a hydrogen gas atmosphere (0.3MPa). Nickel was coated with soft carbon.
  • the positive electrode composition is soft carbon / nickel hydroxide composite (97.29wt.%), Carbon material (2 wt.%), Polyolefin binder (0.5 wt.%), Acrylic A positive electrode was prepared using an acid thickener (0.15 wt.%) And a nonionic surfactant (0.15 wt.%).
  • the negative electrode used as the counter electrode is manufactured by coating a punched metal base material with an AB5 type hydrogen storage alloy.
  • the separator is a sulfonated 130 ⁇ m thick polypropylene nonwoven fabric (manufactured by Japan Vilene).
  • the electrolyte is water.
  • a solution containing 30 g / L of lithium hydroxide in an aqueous potassium oxide solution (6 mol / L) was used. Subsequently, the negative electrode capacity and the positive electrode capacity ratio (N / P) were adjusted to be 2, and a wound battery having a nominal capacity of 1000 mAh was manufactured using a pressure vessel as a battery case. These batteries were charged with 0.2 MPa of hydrogen gas, charged and discharged at 0.1 CA, 0.2 CA, and 0.5 CA once each, followed by chemical conversion treatment, and then the high rates of 1 CA, 2 CA, 5 CA, and 7.5 CA were high. A rate discharge test was performed to evaluate the output characteristics of the battery. Other conditions not described are the same as in the battery of Example 1.
  • FIG. 6 shows a high-rate discharge curve comparing a battery using a soft carbon / nickel hydroxide composite as a positive electrode material and a battery using nickel hydroxide which has not been subjected to a composite treatment as a positive electrode material. From FIG. 6, the battery using the positive electrode material in which the soft carbon is coated and composited with nickel hydroxide (shown by the solid line) is compared with the battery (shown by the broken line) in which the nickel hydroxide and the soft carbon are simply blended. It can be seen that the output characteristics are improved.
  • ⁇ Negative electrode test results> AB5 type hydrogen storage alloy was applied to a punching metal base material to prepare a 150 mAh negative electrode, and a half cell using silver as a reference electrode was prepared. This battery was fully charged and fully discharged in a hydrogen gas atmosphere of 100 MPa, and the cycle life characteristics of the battery were evaluated. The result is shown in FIG. An example of the charge / discharge cycle characteristics of the negative electrode in an air atmosphere is shown in FIG. Although the specifications of the negative electrode are different from those used in the test of FIG. 7, it can be seen that the discharge capacity decreases with the charge / discharge cycle. This is probably because the hydrogen storage alloy was oxidized and deteriorated. On the other hand, the result of FIG. 7 is a test under a hydrogen atmosphere, and the hydrogen storage alloy is not oxidized and shows good cycle life characteristics.
  • the alkaline secondary battery in which hydrogen gas is sealed inside the battery described above has a long life and a high capacity, it can be suitably used as a secondary battery not only for industrial use but also for consumer use.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
PCT/JP2014/053088 2014-02-10 2014-02-10 アルカリ二次電池 Ceased WO2015118691A1 (ja)

Priority Applications (15)

Application Number Priority Date Filing Date Title
JP2014535442A JP5648772B1 (ja) 2014-02-10 2014-02-10 アルカリ二次電池
PCT/JP2014/053088 WO2015118691A1 (ja) 2014-02-10 2014-02-10 アルカリ二次電池
JP2015519677A JP5927372B2 (ja) 2014-02-10 2015-01-05 アルカリ二次電池およびアルカリ二次電池の製造方法
KR1020167024872A KR101763169B1 (ko) 2014-02-10 2015-01-05 알칼리 2차전지
ES15745785T ES2805538T3 (es) 2014-02-10 2015-01-05 Pila secundaria alcalina
CN201580007665.8A CN106133993B (zh) 2014-02-10 2015-01-05 碱性二次电池
PT157457854T PT3107144T (pt) 2014-02-10 2015-01-05 Bateria secundária alcalina
PCT/JP2015/050010 WO2015118892A1 (ja) 2014-02-10 2015-01-05 アルカリ二次電池
HUE15745785A HUE050294T2 (hu) 2014-02-10 2015-01-05 Alkáli szekunder elem
DK15745785.4T DK3107144T3 (da) 2014-02-10 2015-01-05 Alkalisk sekundært batteri
RU2016134026A RU2671836C2 (ru) 2014-02-10 2015-01-05 Щелочной аккумуляторный элемент
EP15745785.4A EP3107144B1 (en) 2014-02-10 2015-01-05 Alkaline secondary battery
US15/117,315 US10381647B2 (en) 2014-02-10 2015-01-05 Alkaline secondary cell
PL15745785T PL3107144T3 (pl) 2014-02-10 2015-01-05 Akumulator alkaliczny
BR112016018185-9A BR112016018185B1 (pt) 2014-02-10 2015-01-05 Célula secundária alcalina

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/053088 WO2015118691A1 (ja) 2014-02-10 2014-02-10 アルカリ二次電池

Publications (1)

Publication Number Publication Date
WO2015118691A1 true WO2015118691A1 (ja) 2015-08-13

Family

ID=52344803

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2014/053088 Ceased WO2015118691A1 (ja) 2014-02-10 2014-02-10 アルカリ二次電池
PCT/JP2015/050010 Ceased WO2015118892A1 (ja) 2014-02-10 2015-01-05 アルカリ二次電池

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/050010 Ceased WO2015118892A1 (ja) 2014-02-10 2015-01-05 アルカリ二次電池

Country Status (13)

Country Link
US (1) US10381647B2 (enExample)
EP (1) EP3107144B1 (enExample)
JP (2) JP5648772B1 (enExample)
KR (1) KR101763169B1 (enExample)
CN (1) CN106133993B (enExample)
BR (1) BR112016018185B1 (enExample)
DK (1) DK3107144T3 (enExample)
ES (1) ES2805538T3 (enExample)
HU (1) HUE050294T2 (enExample)
PL (1) PL3107144T3 (enExample)
PT (1) PT3107144T (enExample)
RU (1) RU2671836C2 (enExample)
WO (2) WO2015118691A1 (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018147626A (ja) * 2017-03-02 2018-09-20 トヨタ自動車株式会社 アルカリ二次電池
JP2019125472A (ja) * 2018-01-16 2019-07-25 トヨタ自動車株式会社 アルカリ二次電池
EP3457467A4 (en) * 2016-05-12 2019-11-20 Eliiy Power Co., Ltd. POSITIVE ELECTRODE FOR A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE AND SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE
JP6931950B1 (ja) * 2020-03-27 2021-09-08 株式会社堤水素研究所 固体電解質電池

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5648772B1 (ja) 2014-02-10 2015-01-07 エクセルギー・パワー・システムズ株式会社 アルカリ二次電池
US10587012B2 (en) * 2015-03-26 2020-03-10 Basf Corporation Electrolyte compositions comprising ionic liquids and metal hydride batteries comprising same
JP6286632B2 (ja) * 2016-02-26 2018-03-14 エクセルギー・パワー・システムズ株式会社 バイポーラ電池
CN109155402B (zh) * 2016-05-12 2023-04-28 艾利电力能源有限公司 非水电解质二次电池用正极和非水电解质二次电池
JP6606041B2 (ja) * 2016-09-16 2019-11-13 トヨタ自動車株式会社 高圧型水素化物二次電池
US11335918B2 (en) 2016-10-21 2022-05-17 Form Energy, Inc. Corrugated fuel electrode
JP6473869B2 (ja) * 2017-06-02 2019-02-27 エクセルギー・パワー・システムズ株式会社 蓄電デバイス
JP6867260B2 (ja) * 2017-09-08 2021-04-28 国立大学法人広島大学 蓄電装置
WO2019133702A1 (en) 2017-12-29 2019-07-04 Staq Energy, Inc. Long life sealed alkaline secondary batteries
CA3105128A1 (en) 2018-07-27 2020-01-30 Form Energy, Inc. Negative electrodes for electrochemical cells
US12294086B2 (en) 2019-07-26 2025-05-06 Form Energy, Inc. Low cost metal electrodes
JP7488639B2 (ja) * 2019-10-15 2024-05-22 本田技研工業株式会社 リチウムイオン二次電池用電極、およびリチウムイオン二次電池
JP7153279B2 (ja) * 2020-09-24 2022-10-14 株式会社堤水素研究所 固体電解質アルカリ電池
CN114122393B (zh) * 2021-11-11 2025-04-11 上海市翔丰华科技股份有限公司 锂离子电池用高功率密度负极材料的制备方法
CN114883668A (zh) * 2022-03-23 2022-08-09 东莞超霸电池有限公司 镍氢电池
CN116613320B (zh) * 2023-06-30 2024-09-03 湖北万润新能源科技股份有限公司 软碳硬碳共包覆磷酸钒钠正极材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6139461A (ja) * 1984-07-31 1986-02-25 Toshiba Corp 密閉型アルカリ蓄電池の製造方法
JPH01204371A (ja) * 1988-02-08 1989-08-16 Matsushita Electric Ind Co Ltd アルカリ二次電池の製造法
JPH02250260A (ja) * 1989-03-23 1990-10-08 Matsushita Electric Ind Co Ltd 水素吸蔵電極及びその製造法
JPH11233106A (ja) * 1998-02-16 1999-08-27 Canon Inc アルカリ二次電池およびその製造方法
JP2010010097A (ja) * 2008-06-30 2010-01-14 Panasonic Corp ニッケル水素蓄電池の製造方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127703A (en) * 1976-02-05 1978-11-28 Eic Corporation Nickel-hydrogen secondary battery
JPH06124703A (ja) 1991-10-31 1994-05-06 Akihisa Ozawa アルカリ二次電池の製造方法
RU2020656C1 (ru) 1992-03-10 1994-09-30 Давид Ефимович Богатин Способ формировки металл-гидридного аккумулятора
RU2071621C1 (ru) 1994-11-29 1997-01-10 Акционерное общество "Элит" Способ изготовления электрода электрического аккумулятора
JP3223858B2 (ja) 1996-12-24 2001-10-29 松下電器産業株式会社 アルカリ蓄電池とその正極活物質およびその製造方法
JP3191752B2 (ja) 1996-12-26 2001-07-23 松下電器産業株式会社 ニッケル−水素二次電池およびその電極の製造方法
JP3433039B2 (ja) * 1997-02-06 2003-08-04 三洋電機株式会社 アルカリ蓄電池
CN1085419C (zh) * 1998-12-15 2002-05-22 冶金工业部钢铁研究总院 碱性二次镍氢电池及其制造方法
CN1127163C (zh) 1999-04-05 2003-11-05 深圳市比亚迪股份有限公司 高温镍氢电池及其制造方法
JP3893230B2 (ja) 1999-05-19 2007-03-14 日本バイリーン株式会社 スルホン化処理方法及び電池用セパレータの製造方法
JP2002203530A (ja) 2000-12-27 2002-07-19 Daiwabo Co Ltd 電池セパレータ及びこれを用いたアルカリ蓄電池
JP4230691B2 (ja) * 2001-11-12 2009-02-25 日本製箔株式会社 二次電池用集電体
RU2229185C1 (ru) 2002-11-14 2004-05-20 ООО "Химэлектро" Способ изготовления электрода щелочного аккумулятора
JP4641329B2 (ja) * 2004-08-10 2011-03-02 川崎重工業株式会社 アルカリ二次電池用正極組成物、アルカリ二次電池の正極用導電材およびアルカリ二次電池
JP4812447B2 (ja) 2006-01-31 2011-11-09 三洋電機株式会社 ニッケル水素蓄電池
JP2008171515A (ja) 2007-01-15 2008-07-24 Polymatech Co Ltd 緩衝部材
JP2008235173A (ja) 2007-03-23 2008-10-02 Sanyo Electric Co Ltd ニッケル水素二次電池
RU2344519C1 (ru) * 2007-06-04 2009-01-20 ОАО "Аккумуляторная компания "Ригель" Герметичный никель-цинковый аккумулятор
KR100798429B1 (ko) * 2007-08-09 2008-01-28 공주대학교 산학협력단 고비표면적의 다공성 전극의 제조 방법
JP2012199203A (ja) 2011-03-23 2012-10-18 Mitsubishi Paper Mills Ltd 電池用セパレータ
JP2012204177A (ja) * 2011-03-25 2012-10-22 Kawasaki Heavy Ind Ltd コバルトフリーのアルカリ二次電池
WO2012173091A1 (ja) * 2011-06-15 2012-12-20 国立大学法人 東京大学 リバーシブル燃料電池、リバーシブル燃料電池システム、リバーシブル燃料電池モジュール、および、リバーシブル燃料電池バンク
JP2014035858A (ja) 2012-08-08 2014-02-24 Toyota Motor Corp 二次電池
JP5648772B1 (ja) 2014-02-10 2015-01-07 エクセルギー・パワー・システムズ株式会社 アルカリ二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6139461A (ja) * 1984-07-31 1986-02-25 Toshiba Corp 密閉型アルカリ蓄電池の製造方法
JPH01204371A (ja) * 1988-02-08 1989-08-16 Matsushita Electric Ind Co Ltd アルカリ二次電池の製造法
JPH02250260A (ja) * 1989-03-23 1990-10-08 Matsushita Electric Ind Co Ltd 水素吸蔵電極及びその製造法
JPH11233106A (ja) * 1998-02-16 1999-08-27 Canon Inc アルカリ二次電池およびその製造方法
JP2010010097A (ja) * 2008-06-30 2010-01-14 Panasonic Corp ニッケル水素蓄電池の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3457467A4 (en) * 2016-05-12 2019-11-20 Eliiy Power Co., Ltd. POSITIVE ELECTRODE FOR A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE AND SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE
US11276849B2 (en) 2016-05-12 2022-03-15 ELIIY Power Co., Ltd Positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP2018147626A (ja) * 2017-03-02 2018-09-20 トヨタ自動車株式会社 アルカリ二次電池
JP2019125472A (ja) * 2018-01-16 2019-07-25 トヨタ自動車株式会社 アルカリ二次電池
JP6931950B1 (ja) * 2020-03-27 2021-09-08 株式会社堤水素研究所 固体電解質電池
WO2021192251A1 (ja) * 2020-03-27 2021-09-30 株式会社堤水素研究所 固体電解質電池

Also Published As

Publication number Publication date
ES2805538T3 (es) 2021-02-12
DK3107144T3 (da) 2020-07-20
KR20160121556A (ko) 2016-10-19
EP3107144B1 (en) 2020-06-17
US10381647B2 (en) 2019-08-13
CN106133993A (zh) 2016-11-16
JP5927372B2 (ja) 2016-06-01
CN106133993B (zh) 2020-11-03
JPWO2015118892A1 (ja) 2017-03-23
RU2671836C2 (ru) 2018-11-07
EP3107144A1 (en) 2016-12-21
BR112016018185B1 (pt) 2022-05-31
HUE050294T2 (hu) 2020-11-30
EP3107144A4 (en) 2017-07-26
KR101763169B1 (ko) 2017-07-31
WO2015118892A1 (ja) 2015-08-13
PL3107144T3 (pl) 2020-11-02
RU2016134026A (ru) 2018-03-15
RU2016134026A3 (enExample) 2018-03-15
US20160351907A1 (en) 2016-12-01
PT3107144T (pt) 2020-07-20
BR112016018185A2 (enExample) 2017-08-08
JPWO2015118691A1 (ja) 2017-03-23
JP5648772B1 (ja) 2015-01-07

Similar Documents

Publication Publication Date Title
JP5648772B1 (ja) アルカリ二次電池
JP5749264B2 (ja) 炭素繊維亜鉛電極
JP4992128B2 (ja) リチウム二次電池用負極活物質粒子および負極の製造方法
JP2010277989A (ja) 非水電解液電池用負極及び非水電解液電池
JPWO2003021698A1 (ja) ニッケル電極材料及びその製造方法、並びに、ニッケル電極及びアルカリ蓄電池
JP2018116784A (ja) 固体電池用の正極材料、固体電池および固体電池の製造方法
US9802254B2 (en) Zinc electrodes for batteries
WO2010037025A1 (en) Rechargeable znmn flat plate electrode cell
JP2012227106A (ja) ニッケル水素蓄電池
JP5557385B2 (ja) プロトンを挿入種とする蓄電デバイス
JP4752996B2 (ja) リチウム二次電池用負極活物質粒子の製造方法
JP4789032B2 (ja) リチウム二次電池用負極活物質粒子および負極の製造方法
JP2015130249A (ja) アルカリ蓄電池用正極およびそれを用いたアルカリ蓄電池
CN101809787B (zh) 储氢合金粉末与其表面处理方法、碱蓄电池用负极以及碱蓄电池
JP2012188728A (ja) 複合水素吸蔵合金及びニッケル水素蓄電池
JP6885189B2 (ja) ニッケル金属水素化物電池の活性化方法
JP2011018493A (ja) ニッケル水素二次電池
JP5119689B2 (ja) アルカリ蓄電池用負極材料およびアルカリ蓄電池
JP2008108740A (ja) 電池用電極材および二次電池
JP5769028B2 (ja) ニッケル水素蓄電池
JP2019200982A (ja) ニッケル金属水素化物電池用正極の製造方法
WO2023195233A1 (ja) 亜鉛電池用負極及び亜鉛電池
JP2008159355A (ja) コイン型リチウム電池
JP2020198205A (ja) ニッケル金属水素化物電池
Chen et al. Metal hydride electrodes for rechargeable batteries

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2014535442

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 14881659

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: 14881659

Country of ref document: EP

Kind code of ref document: A1