EP4305687A1 - Negative elektrode mit einem elektrochemisch aktiven zinkmaterial - Google Patents

Negative elektrode mit einem elektrochemisch aktiven zinkmaterial

Info

Publication number
EP4305687A1
EP4305687A1 EP22711537.5A EP22711537A EP4305687A1 EP 4305687 A1 EP4305687 A1 EP 4305687A1 EP 22711537 A EP22711537 A EP 22711537A EP 4305687 A1 EP4305687 A1 EP 4305687A1
Authority
EP
European Patent Office
Prior art keywords
mass
coating
electrode according
zinc
mercury
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.)
Pending
Application number
EP22711537.5A
Other languages
English (en)
French (fr)
Inventor
Mélanie VILLALOBOS
Anaïs BERTHELLEMY
Tanalou BOURA
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.)
SAFT Societe des Accumulateurs Fixes et de Traction SA
Original Assignee
SAFT Societe des Accumulateurs Fixes et de Traction SA
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 SAFT Societe des Accumulateurs Fixes et de Traction SA filed Critical SAFT Societe des Accumulateurs Fixes et de Traction SA
Publication of EP4305687A1 publication Critical patent/EP4305687A1/de
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M10/32—Silver 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

Definitions

  • Negative electrode comprising an electrochemically active zinc material
  • the technical field of the present invention is that of plasticized negative electrodes comprising an electrochemically active zinc material, which can be used in an electrochemical element with an alkaline electrolyte.
  • the technical field is also that of methods for preparing such electrodes.
  • the document CN 111304959 describes the manufacture of an electrochemical cell with an alkaline electro lyte without mercury.
  • This element includes a separator made of a paper support covered with a coating.
  • This coating is obtained by drying a paste which itself is prepared by mixing polyacrylamide, polyvinyl alcohol, zinc chloride, an acid catalyst in solution, a modified starch solution, an emulsifier and a zinc corrosion inhibitor. The paste obtained is therefore not deposited on a current collector but on a paper support, an electrical insulator.
  • Document EP 1683218 describes the preparation of a paste comprising a zinc alloy, carboxymethylcellulose, surfactants and potash.
  • the manufactured element is of cylindrical format and this paste is simply poured into the cylindrical space of the container of the electrochemical element. This paste is not deposited on a current collector.
  • the anode in the center of the cell is a metal rod inserted into the batter to make electrical contact.
  • the small surface area of the anode current collector does not allow high power to be obtained.
  • it is a primary electrochemical element, therefore not rechargeable.
  • the paste is prepared using potash and not water.
  • a secondary electrochemical element with an alkaline electrolyte capable of providing high power, for example greater than 1000 W/kg in the case of the AgO/Zn couple, and whose anode comprises at most 0.5% by mass of mercury or mercury compound.
  • the subject of the invention is a paste electrode comprising a current collector support, which is coated on at least one of its faces with a coating of a composition comprising:
  • the mass of zinc alloy represents from 5 to 95% of the mass of the coating.
  • the mass of zinc alloy represents from 10 to 50%, preferably from 15 to 30% of the mass of the coating.
  • the active material further comprises zinc oxide ZnO.
  • the mass of zinc oxide represents from 90 to 50%, preferably from 70 to 85% of the mass of the coating.
  • the zinc oxide has a BET specific surface area of at least 3 m 2 /g.
  • the coating contains at most 0.5% by mass of mercury or mercury compound.
  • the coating is free of mercury or mer curiel compound.
  • the coating results from the drying of a paste having a dynamic viscosity ranging from 30 Pa.s to 200 Pa.s for a temperature of 20° C. and at atmospheric pressure.
  • the zinc is alloyed with at least one element chosen from the group consisting of lead, bismuth, indium, aluminum, gallium, tin and a mixture of several of these elements.
  • the binder is a cellulosic compound or a rubber of the styrene-butadiene type or a mixture of a cellulosic compound and a rubber of the styrene-butadiene type.
  • the coating further comprises at least one surfactant.
  • the coating comprises:
  • the current collector support is a strip of copper or nickel-plated steel.
  • the invention also relates to an electrochemical element comprising an alkaline electrolyte, at least one cathode and at least one anode which is the paste electrode as defined above.
  • the cathode comprises at least one active material chosen from the group consisting of silver, nickel, manganese dioxide and atmospheric oxygen.
  • the alkaline electrolyte comprises zinc oxide or tin or a mixture of both.
  • the container is of prismatic format.
  • a paste electrode is an electrode in which the active material is applied in the form of a paste to a current-conducting collector.
  • the paste electrode typically comprises a current-conducting reader neck on which is deposited a paste, which paste comprises a zinc alloy and at least one binder.
  • the present invention therefore excludes negative electrodes which are not impastoed or sintered, for example those consisting of a rolled-out zinc or zinc deposited by electrolysis on a metal support.
  • the active material necessarily comprises zinc alloyed with one or more chemical elements.
  • These chemical elements can be selected from the group consisting of lead, bismuth, indium, aluminum, gallium and tin or a mixture of several of these elements.
  • the overall content of alloyed elements generally ranges from 100 to 1000 ppm.
  • the alloyed element can be lead present in an amount ranging from 400 to 600 ppm.
  • Associated alloy elements may be bismuth and indium, each present in a content ranging from 300 to 500 ppm, preferably from 350 to 450 ppm.
  • Associated alloy elements can also be bismuth, indium and aluminum present in contents ranging from 50 to 150 ppm for bismuth, from 150 to 250 for indium and from 50 to 150 ppm for aluminium.
  • the zinc alloy is generally used in the form of a powder.
  • the mass of zinc alloy can represent from 5 to 95% of the mass of the coating. In general, it represents from 10 to 50%, preferably from 15 to 30% of the mass of the coating.
  • the term “coating” here designates the mixture of compounds resulting from the drying of the paste, therefore after elimination of the water which is necessary for the formulation of the paste and for obtaining an adequate viscosity.
  • the zinc alloy can advantageously be mixed with zinc oxide ZnO.
  • the zinc oxide makes it possible to improve the performance of the element in discharge.
  • the zinc oxide preferably has a BET specific surface of at least 3 m 2 /g or at least 5 m 2 /g or at least 10 m 2 /g. A high specific surface improves the chargeability of the element.
  • the mass of zinc oxide can represent from 90 to 50% of the mass of the coating. In general, it represents 70 to 85% of the mass of the coating.
  • the mass ratio between zinc oxide and zinc alloy generally ranges from 2 to
  • the nature of the binder is not limited.
  • the binder is preferably a binder which is dispersible in an aqueous medium or which can form an aqueous solution. It can be a cellulosic compound or an elastomer or a thermoplastic compound.
  • the cellulosic compound can be chosen from methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC) and hydroxyethylcellulose (HEC) and a mixture of several compounds among these. this.
  • it is hydroxypropyl methylcellulose (HPMC) because it provides better resistance of zinc to corrosion.
  • the elastomer can be chosen from a copolymer of styrene/ethylene/butylene/styrene (SEBS), a copolymer of butadiene, such as a copolymer of styrene/butadiene (SBR), optionally carboxylated, a terpolymer of styrene/ butadiene/vinylpyridine (SBVR).
  • SEBS styrene/ethylene/butylene/styrene
  • SBR copolymer of styrene/butadiene
  • SBVR terpolymer of styrene/ butadiene/vinylpyridine
  • the thermoplastic polymer can be a styrene-acrylate copolymer or an ethylene-vinyl acetate (EVA) copolymer.
  • EVA ethylene-vinyl acetate
  • the binder can also be polyvinyl alcohol, optionally
  • hydroxypropyl methylcellulose is blended with a styrene/butadiene copolymer and polyvinyl alcohol.
  • the binder can represent from 1 to 5% of the mass of the coating, preferably from 1 to 3%.
  • the coating does not contain a fluorinated polymer as a binder.
  • the coating may comprise one or more additives intended to reduce the corrosion of the zinc, other than mercury or derivatives of mercury.
  • the additives may be intended to improve the dispersion of the constituents of the dough.
  • the dispersing agent can be a polycarboxylic acid. Each additive is generally used at the rate of less than 1% by weight of the deposited coating.
  • the coating may also contain one or more electronically conductive compounds.
  • a typical coating comprises:
  • the pasted electrode can be prepared by following the following procedure: A paste is made by mixing water with one or more binders and with a zinc alloy powder, optionally mixed beforehand with a powder of zinc oxide ZnO. We knead the dough. The dough can then be rested. The viscosity of the dough can be adjusted during mixing and after resting the dough by adding water. The viscosity of the paste can range from 30 Pa.s to 200 Pa.s for a temperature of 20° C. and at atmospheric pressure. The paste manufacturing step does not involve the addition of an alkaline solution, such as a KOH, NaOH or LiOH solution. The paste is then deposited on one or both faces of the current collector.
  • a paste is made by mixing water with one or more binders and with a zinc alloy powder, optionally mixed beforehand with a powder of zinc oxide ZnO. We knead the dough. The dough can then be rested. The viscosity of the dough can be adjusted during mixing and after resting the dough by adding water. The visco
  • the support serving as a current collector can be two-dimensional such as a solid or perforated metal strip or an expanded metal or a grid. It can be three-dimensional such as felt or foam, metal or carbon.
  • the thickness of the two-dimensional current collector is generally less than or equal to 100 ⁇ m.
  • the current collector can be copper or nickel-plated steel.
  • the paste has a mercury or mercury compound content lower than or equal to 0.5%, or lower or equal to 0.2%, or lower or equal to 0.1%, or lower or equal to equal to 0.01%. Preferably, it does not contain any.
  • the electrode obtained is dried in order to eliminate the water contained in the paste.
  • the electrode is then rolled if necessary in order to adjust its thickness to the desired value. This gives the impastoed electrode.
  • the positive electrode may comprise at least one active material chosen from the group consisting of silver, nickel, manganese dioxide and atmospheric oxygen. Silver and nickel are the preferred positive active materials. In the case of a silver electrode, it comes in the form of a silver powder deposited on a support which is a deployed silver.
  • An electrochemical beam is prepared by superimposing at least one cathode, at least one anode, separated by a separator.
  • the separator can be based on untreated polyolefin fibers or treated with acrylic acid, or sulfonated, or based on polyamide fibers, or a cellophane which consists of cellulose hydrates.
  • a membrane is generally inserted between an anode and a separator. This membrane has pores of smaller diameter than those of the separator. These pores are small enough to prevent the passage of zincate ions from the anode.
  • the membrane is generally made of polyolefin or cellulose.
  • the electrochemical bundle is introduced into the container of the element.
  • the container can be cylindrical or prismatic.
  • the electrodes are spiral.
  • the electrodes are planar and the format of the element is prismatic. This format makes it possible to obtain an element with high power.
  • the container is filled with an alkaline electrolyte, such as a solution of NaOH, KOH or LiOH or a mixture of several of these bases.
  • Zinc oxide or a component containing tin can be added to the electrolyte. A reduction in the corrosion of the zinc anode has been observed, therefore a limitation of the loss of capacity when these compounds are present in the electrolyte.
  • the elements comprising the paste electrode according to the invention can generally perform at least twenty cycles without observing a loss of capacity greater than 20% of their initial capacity.
  • compositions A) to D) of the various anodes are described in Table 1.
  • Composition A) contains 1 to 2% of mercury compound and serves as a reference.
  • Compositions C) and D) are according to the invention. They either contain little mercury compound (composition D), or are free of mercury compound (composition C).
  • Three different zinc alloy compositions C)1, C)2 and C)3 were tested.
  • the anode of the four elements contains 2% by mass of binder. Table 1 compares the corrosion rate and mercury-related toxicity of electrochemical elements made with anodes of composition A to D.
  • composition of the zinc alloy used in the four anodes containing little or no mercury is detailed in Table 2 below.
  • the cathodes are identical in these four elements A) to D). It is an electrode comprising a layer of silver on which a silver powder is deposited.
  • the quantity of silver in the cathode is calculated to correspond to a capacity equal to 1.3 times the capacity of the anode. The capacity of the element is therefore limited by the cathode.
  • the capacitance discharged during cycling by the elements comprising the mercury-free electrodes C)1, C)2 and C)3 was compared with that discharged by the element comprising an electrode D) containing little mercury.
  • the discharged capacitor values are given in Table 3 at different times of cycling.
  • Table 3 shows that the capacity of the elements containing the anodes of composition C) 1 , C) 2, C) 3 without mercury is not lower than that of the element whose anode contains little mercury.
  • a measurement of the voltage of the cell containing the mercury-free electrode C)1 was carried out when the cell is used for charging and discharging.
  • the voltage values are comparable to those obtained for the element containing the electrode D) with little mercury.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP22711537.5A 2021-03-12 2022-03-09 Negative elektrode mit einem elektrochemisch aktiven zinkmaterial Pending EP4305687A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2102475A FR3120744B1 (fr) 2021-03-12 2021-03-12 Electrode négative comprenant une matière électrochimiquement active en zinc
PCT/EP2022/055994 WO2022189485A1 (fr) 2021-03-12 2022-03-09 Electrode négative comprenant une matière électrochimiquement active en zinc

Publications (1)

Publication Number Publication Date
EP4305687A1 true EP4305687A1 (de) 2024-01-17

Family

ID=76283863

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22711537.5A Pending EP4305687A1 (de) 2021-03-12 2022-03-09 Negative elektrode mit einem elektrochemisch aktiven zinkmaterial

Country Status (4)

Country Link
US (1) US20240162429A1 (de)
EP (1) EP4305687A1 (de)
FR (1) FR3120744B1 (de)
WO (1) WO2022189485A1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436539B1 (en) 1998-08-10 2002-08-20 Electric Fuel Ltd. Corrosion-resistant zinc alloy powder and method of manufacturing
US6652676B1 (en) 1999-10-18 2003-11-25 Big River Zinc Corporation Zinc alloy containing a bismuth-indium intermetallic compound for use in alkaline batteries
US7947393B2 (en) 2003-11-14 2011-05-24 Eveready Battery Company, Inc. Alkaline electrochemical cell
US8048566B2 (en) * 2008-02-07 2011-11-01 Powergenix Systems, Inc. Nickel hydroxide electrode for rechargeable batteries
WO2013150519A1 (en) * 2012-04-04 2013-10-10 Phinergy Ltd. Zinc electrode for use in rechargeable batteries
CN111304959B (zh) 2020-02-26 2021-11-19 常州大学 一种防漏型无汞电池用浆层纸的制备方法

Also Published As

Publication number Publication date
FR3120744B1 (fr) 2023-05-12
US20240162429A1 (en) 2024-05-16
WO2022189485A1 (fr) 2022-09-15
FR3120744A1 (fr) 2022-09-16

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