WO2022145034A1 - Batterie rechargeable au nickel-hydrogène - Google Patents

Batterie rechargeable au nickel-hydrogène Download PDF

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Publication number
WO2022145034A1
WO2022145034A1 PCT/JP2020/049285 JP2020049285W WO2022145034A1 WO 2022145034 A1 WO2022145034 A1 WO 2022145034A1 JP 2020049285 W JP2020049285 W JP 2020049285W WO 2022145034 A1 WO2022145034 A1 WO 2022145034A1
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WO
WIPO (PCT)
Prior art keywords
nickel
separator
negative electrode
positive electrode
metal hydride
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Application number
PCT/JP2020/049285
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English (en)
Japanese (ja)
Inventor
クーシャン ヤン
泰平 大内
浩 福永
伸二 椎▲崎▼
Original Assignee
カワサキモータース株式会社
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Application filed by カワサキモータース株式会社 filed Critical カワサキモータース株式会社
Priority to PCT/JP2020/049285 priority Critical patent/WO2022145034A1/fr
Publication of WO2022145034A1 publication Critical patent/WO2022145034A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel 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
    • 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

Definitions

  • the present invention relates to a nickel-metal hydride secondary battery, and more particularly to a nickel-metal hydride secondary battery provided with a separator that contributes to weight reduction of the battery.
  • Nickel-metal hydride secondary batteries have excellent charge / discharge characteristics and overcharge / discharge characteristics, and can be used repeatedly with a long life, so they are widely used in electronic devices that are significantly smaller and lighter (see, for example, Patent Document 1).
  • a separator for a nickel-metal hydride secondary battery a polyolefin-based non-woven fabric having a large fiber diameter, such as polyethylene or polypropylene, which is produced by graft polymerization and has a high grain weight has been conventionally used.
  • the separator itself is heavy and absorbs a large amount of electrolytic solution between the fibers, so that the amount of electrolytic solution required as a battery also increases. As a result, the miniaturization and weight reduction originally required for nickel-metal hydride secondary batteries could not be sufficiently achieved.
  • An object of the present invention is to provide a nickel-metal hydride secondary battery provided with a separator that contributes to miniaturization and weight reduction of the battery in order to solve the above problems.
  • the nickel-metal hydride secondary battery according to the present invention is A negative electrode having a negative electrode active material whose main component is a hydrogen storage alloy, and a negative electrode A positive electrode having a positive electrode active material containing nickel hydroxide as a main component, A separator that is interposed between the negative electrode and the positive electrode and contains an anion exchange membrane that allows hydroxide ions to permeate. To prepare for.
  • the thickness and weight of the separator can be dramatically reduced while maintaining the charge / discharge performance of the battery equal to or higher than that when the conventional separator is used. Therefore, the nickel-metal hydride secondary battery can be made smaller and lighter.
  • the ion resistivity of the anion exchange membrane may be 1000 ⁇ ⁇ cm or less, further 500 ⁇ ⁇ cm or less, and further 300 ⁇ ⁇ cm or less. May be.
  • the nickel-hydrogen secondary battery according to the embodiment of the present invention may include an electrolytic solution consisting of an alkaline aqueous solution containing potassium, sodium, calcium, lithium, or an hydroxide of any combination thereof.
  • the nickel-hydrogen secondary battery according to the present embodiment includes a negative electrode having a negative electrode active material containing a hydrogen storage alloy as a main component, a positive electrode having a positive electrode active material containing nickel hydroxide as a main component, and the negative electrode and the positive electrode.
  • a separator including an anion exchange film which is interposed between the above and allows the hydroxide ion to permeate is provided.
  • this nickel-metal hydride secondary battery includes an electrolytic solution that enables ion conduction between the positive electrode and the negative electrode.
  • the "negative electrode” refers to a pole on the side containing a substance that electrochemically receives electrons during charging
  • the "positive electrode” means that electrons are electrochemically emitted during charging. Refers to the pole on the side containing the substance.
  • the positive electrode active material is, for example, a hydroxide of a transition metal.
  • the positive electrode active material may be, for example, a nickel hydroxide or a nickel-containing composite hydroxide containing nickel and other transition metals. More specifically, the positive electrode active material is represented by, for example, Ni (1-xy) Co x Zn y (OH) 2 (where 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.1). It may be a compound to be used.
  • the negative electrode active material is, for example, a hydrogen storage alloy capable of storing hydrogen electrochemically generated in an electrolytic solution during charging and easily releasing the stored hydrogen during discharging.
  • a hydrogen storage alloy may have a structure represented as an ABx type.
  • A is a hydride-forming element
  • B is a non-hydride-forming element
  • x is a real number of 1 to 5.
  • the hydride forming element (A) includes, but is not limited to, for example, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, yttrium, titanium, zirconium or combinations thereof, or other metals such as mischmetal.
  • Non-hydride forming elements include, but are not limited to, for example, aluminum, nickel, cobalt, copper, manganese, or metals that are combinations thereof.
  • hydrogen storage alloys AB 5 type systems such as LaNi 5 and MmNi 5 (Mm is Mish metal), AB 3 type systems such as rare earth-magnesium-nickel system, and rare earths having a superlattice structure-magnesium.
  • a 2 B 7 type systems such as nickel type and AB 2 type systems such as (Zr, Ti) Ni 2
  • the present invention is not limited thereto.
  • One or both of the negative electrode active material and the positive electrode active material may be in the form of powder or granules.
  • the particles can be held by the binder and formed in layers on the current collector in the formation of the negative electrode or the positive electrode.
  • the binder any binder known in the art can be used as long as it is suitable for use in forming a negative electrode, a positive electrode, or both, and is suitable for proton conduction.
  • binders used to form negative electrodes include, but are not limited to, polymer binder materials.
  • the binder material include an elastomer material, and more specifically, for example, styrene-butadiene (SB), styrene-butadiene-styrene block copolymer (SBS), and styrene-isoprene-styrene block.
  • SB styrene-butadiene
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-isoprene-styrene block.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), teflonated acetylene black (TAB-2), styrene-butadiene binder material, or carboxymethyl cellulose (CMC). , Not limited to these.
  • PTFE polytetrafluoroethylene
  • PVA polyvinyl alcohol
  • TAB-2 teflonated acetylene black
  • CMC carboxymethyl cellulose
  • One or both of the positive electrode and the negative electrode may further contain one or more kinds of additives contained in the active material.
  • the additive is, for example, a conductive material.
  • This conductive material is preferably conductive carbon.
  • Examples of conductive carbon include graphite or graphitized carbon such as graphitized coke.
  • Still other examples of conductive carbon include amorphous or amorphous non-graphitized carbons such as petroleum coke and carbon black.
  • the conductive material is contained in the positive electrode or the negative electrode, for example, in the range of 0.1% by weight to 20% by weight.
  • the negative electrode and the positive electrode can be formed by any method known in the art.
  • the active material of the negative electrode or the active material of the positive electrode is mixed with a binder in a suitable solvent and optionally a conductive material to form a slurry, and the slurry is coated on the current collector and dried.
  • a layer of active material can be formed on the surface of the current collector.
  • the current collector may be in the form of a mesh, foil, or other suitable form.
  • the current collector can be formed of an aluminum-based metal such as an aluminum alloy, nickel or a nickel alloy, steel such as stainless steel, copper or a material such as a copper alloy.
  • the current collector may be, for example, in the form of a sheet, and may be a foil, a solid substrate, a porous substrate, a grid, a foam, or a form known in the art.
  • the current collector may be any suitable electron conductive and selectively impermeable or substantially impermeable material, such as copper, stainless steel, titanium, or carbon paper / film, non-permeable.
  • the nickel-metal hydride secondary battery according to the present embodiment includes a separator interposed between the negative electrode and the positive electrode.
  • a separator that is permeable to hydroxide ions is used so as to ensure electrical insulation between the negative electrode and the positive electrode and not to limit the ion transfer to an acceptable or unacceptable level. That is, in this embodiment, an anion exchange membrane is used as the separator.
  • an anion exchange membrane is used as the separator.
  • FIG. 1 in the conventional separator made of polyethylene / polypropylene-based non-woven fabric, not only hydroxide ions but also water molecules ( H2O ) can permeate during the reaction at the positive and negative negatives, but anion exchange. The membrane selectively permeates only hydroxide ions.
  • the anion exchange membrane used as the material of the separator may have an ion resistivity of 1000 ⁇ ⁇ cm or less, further may be 500 ⁇ ⁇ cm or less, and more specifically, an ion resistivity of 300 ⁇ ⁇ cm or less. May be.
  • the anion exchange membrane may be a hydroxide ion permeable polymer material.
  • Anion exchange materials that form such anion exchange membranes are generally based on a polymer material that is bonded to or contains one or more cationic groups that allow anion conduction.
  • the anion exchange membrane forming the separator in the present embodiment may also be made of such a material.
  • the anion exchange membrane may be one in which an anion exchange material is bonded or embedded in polyolefin.
  • Typical examples of the above-mentioned cationic group include a quaternary ammonium group or an imidazolium group.
  • Other examples of the above cationic groups include guanidinium-based, DABCO-based, benzimidazolium-based, pyrrolidinium-based, sulfonium-based, phosphonium-based, and ruthenium-based cationic groups.
  • a modified benzimidazolium-based polymer material for example, poly [2,2'-(2,2'', 4,4'', 6,6''- Hexamethyl-p-terphenyl-3,3''-diyl) -5,5'-bibenzoimidazole] (HMT-PBI) or its methylated product, HMT-PMBI.
  • HMT-PBI poly [2,2'-(2,2'', 4,4'', 6,6''- Hexamethyl-p-terphenyl-3,3''-diyl) -5,5'-bibenzoimidazole]
  • HMT-PMBI methylated product
  • anion exchange membrane poly [2,2'-(m-mesitylene) -5,5'-bis (N, N'-dimethylbenzoimidazolium)] (Mes-PDMBI, 2-X- ) And poly [2,2'-(m-phenylene) -5,5'-bis (N, N'-dimethylbenzoimidazolium)] (PDMBI, 3-X-).
  • IONOMR poly [2,2'-(m-mesitylene) -5,5'-bis (N, N'-dimethylbenzoimidazolium)]
  • the electrolytic solution used in the nickel-hydrogen secondary battery according to the present embodiment is an alkaline aqueous solution containing potassium, sodium, calcium, lithium, or an hydroxide of any combination thereof.
  • the above negative electrode, positive electrode, separator, and electrolytic solution are housed in the exterior body.
  • the exterior may be, for example, a metal or polymer can, or a laminated film such as heat sealable aluminum foil such as an aluminum coated polypropylene film.
  • the electrochemical battery provided in the present specification may be any known form, for example, a button battery, a pouch battery, a cylindrical battery, a square battery, or the like.
  • the current collector and / or the substrate may be provided with one or more tabs for allowing the transfer of electrons from the current collector to the outside of the battery and for connecting the current collector to a device such as a circuit.
  • the tabs can be made of any suitable conductive material (eg nickel, aluminum, or other metal) and are connected to the current collector, eg, by welding.
  • the positive electrode active material As the positive electrode active material, a powder of sintered Ni (OH) 2 particles (China: manufactured by Shandong Xinxu) was used. A positive electrode was prepared by mixing this powder with a dry TAB-2 (Japan: manufactured by Hosen Co., Ltd.) binder at a weight ratio of 1: 3 and then press-molding it on a nickel mesh substrate as a current collector. ..
  • an AB5 type hydrogen storage alloy (Michigan, USA: manufactured by Eutectix ) prepared by a standard method was used.
  • a 30% by weight KOH aqueous solution was used as the electrolytic solution.
  • AF-1-ENN5-50-X Example 1
  • AF-1-ENN8-50-X Example 2
  • AF-1 manufactured by Ionomr Vancouver, Canada
  • -ENN5-25-X Example 3
  • AF-1-ENN8-25-X Example 4
  • a separator according to the comparative example a polypropylene / polyethylene-based non-woven fabric (Germany: Scimat 700/79 manufactured by Freudenberg Co., Ltd.) was used.
  • an electrochemical cell for conducting a comparative test of electrochemical properties was prepared.
  • the structure of the test cell T used for this charge / discharge test is shown in FIG. After immersing the separator 1 as a test sample in the electrolytic solution, a sheet-shaped positive electrode 3 and a negative electrode 5 are laminated via the separator 1, sandwiched between two plexiglas plates 7 from both sides, and two of these.
  • the test cell T was produced by tightening the plexiglas sheet 7 of the above with stainless steel bolts 9 and nuts 11.
  • Test results The thickness and the weight of the separator according to each of the above Examples and Comparative Examples after immersion in the electrolytic solution were measured.
  • the charge rate and the discharge rate shown below are values per weight (g) of the positive electrode active material.
  • charging conditions charging rate 50mA / g, charging time 8 hours.
  • the discharge conditions after discharging for 3 hours at a discharge rate of 50 mA / g, the discharge time is 30 seconds in the order of discharge rate 100 mA / g ⁇ 50 mA / g ⁇ 12 mA / g.
  • the discharge is a discharge for adjusting the charge state (SOC) of the test cell to the level in the intermediate region.
  • the slope (dV / dI) of the change in voltage value with respect to the change in current value is obtained by linear approximation from the measurement results (current value and voltage value) of the subsequent three-step constant current discharge, and this slope is obtained.
  • This slope is obtained.
  • the voltage profiles of the three-stage constant current discharge of each cell of Example 1, Example 2, and Comparative Example are shown in FIGS. 3, 4, and 5, respectively.
  • the thickness and weight of the anion exchange membrane separators according to the examples are significantly reduced as compared with the comparative example separators. Specifically, in Examples 1 and 2, the thickness is reduced to 1/3 or less and the weight is reduced to 1/2 or less, and in Examples 3 and 4, the thickness is about 1/6 and the weight is about 1. It is reduced to 4/4.
  • the separator of the example is an order of magnitude larger than the separator of the comparative example in terms of resistivity, the DC resistance of the separator as a whole is the same as that of the comparative example.
  • the discharge performance of the cell which can be seen from the discharge capacity and the high current discharge efficiency, was equal to or higher than that of the comparative example.
  • the thickness and weight of the separator can be significantly increased while ensuring the same or better discharge performance as when the conventional separator is used. Can be reduced to. This makes it possible to reduce the size and weight of the nickel-metal hydride secondary battery.

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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)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

Selon la présente invention, un séparateur qui comprend une membrane échangeuse d'anions qui est perméable aux ions hydroxyde est utilisée comme séparateur d'une batterie rechargeable au nickel-hydrogène qui est pourvue d'une électrode négative comprenant un matériau actif d'électrode négative qui est principalement composé d'un alliage de stockage d'hydrogène et d'une électrode positive comprenant un matériau actif d'électrode positive qui est principalement composé d'hydroxyde de nickel, ledit séparateur étant interposé entre l'électrode négative et l'électrode positive. Il est préférable que la résistivité ionique de la membrane échangeuse d'anions soit de 1,000 Ω·cm ou moins.
PCT/JP2020/049285 2020-12-29 2020-12-29 Batterie rechargeable au nickel-hydrogène WO2022145034A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/JP2020/049285 WO2022145034A1 (fr) 2020-12-29 2020-12-29 Batterie rechargeable au nickel-hydrogène

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Application Number Priority Date Filing Date Title
PCT/JP2020/049285 WO2022145034A1 (fr) 2020-12-29 2020-12-29 Batterie rechargeable au nickel-hydrogène

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11288734A (ja) * 1998-04-01 1999-10-19 Toshiba Battery Co Ltd アルカリ二次電池
JP2017033717A (ja) * 2015-07-30 2017-02-09 株式会社Ｇｓユアサ 蓄電池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11288734A (ja) * 1998-04-01 1999-10-19 Toshiba Battery Co Ltd アルカリ二次電池
JP2017033717A (ja) * 2015-07-30 2017-02-09 株式会社Ｇｓユアサ 蓄電池

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