WO2019069760A1 - Structure d'électrode négative pour batterie secondaire au zinc - Google Patents

Structure d'électrode négative pour batterie secondaire au zinc Download PDF

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WO2019069760A1
WO2019069760A1 PCT/JP2018/035647 JP2018035647W WO2019069760A1 WO 2019069760 A1 WO2019069760 A1 WO 2019069760A1 JP 2018035647 W JP2018035647 W JP 2018035647W WO 2019069760 A1 WO2019069760 A1 WO 2019069760A1
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Prior art keywords
negative electrode
ldh
active material
zinc
material layer
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PCT/JP2018/035647
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English (en)
Japanese (ja)
Inventor
淳宣 松矢
裕一 権田
鬼頭　賢信
毅 八木
直仁 山田
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日本碍子株式会社
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Priority to JP2019546647A priority Critical patent/JP6993422B2/ja
Publication of WO2019069760A1 publication Critical patent/WO2019069760A1/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
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • 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
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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 a negative electrode structure for a zinc secondary battery.
  • the short circuit resulting from such zinc dendrite repeatedly leads to shortening of the charge and discharge life.
  • Patent Document 1 discloses that an LDH separator is provided between a positive electrode and a negative electrode in a nickel zinc secondary battery.
  • Patent Document 2 International Publication No. 2016/076047 discloses a separator structure including an LDH separator fitted or joined to a resin outer frame, and the LDH separator is gas impermeable and It is disclosed that it has high compactness so as to have water impermeability. This document also discloses that the LDH separator can be complexed with a porous substrate.
  • Patent Document 3 discloses various methods for forming an LDH dense film on the surface of a porous substrate to obtain a composite material (LDH separator).
  • a starting material capable of giving an origin of crystal growth of LDH is uniformly attached to the porous substrate, and the porous substrate is subjected to a hydrothermal treatment in a raw material aqueous solution to form an LDH dense film on the surface of the porous substrate. And the process of forming it.
  • a zinc secondary battery such as a nickel zinc battery is configured using the LDH separator as described above, a short circuit or the like due to zinc dendrite can be prevented. And, in order to maximize this effect, it is desirable that the positive electrode and the negative electrode be reliably separated by the LDH separator. In particular, it is extremely advantageous if the stacked battery can be easily assembled by combining a plurality of positive electrodes and a plurality of negative electrodes in order to obtain a high voltage and a large current while securing such a configuration.
  • the separation of the positive electrode and the negative electrode by the LDH separator in the conventional zinc secondary battery is cleverly and carefully sealed and joined using a resin frame, an adhesive and the like so as to ensure liquid tightness between the LDH separator and the battery container. It was easy to make the battery configuration and the manufacturing process complicated. Such complication of the battery configuration and the manufacturing process can be particularly remarkable in the case of constructing a laminated battery. This is because it is necessary to perform sealing and bonding for securing liquid tightness to each of the plurality of unit cells constituting the laminated battery.
  • the inventors of the present invention eliminate the need for complicated sealing and bonding between the LDH separator and the battery container by covering or encasing the whole of the negative electrode active material layer with a liquid holding member or an LDH separator with a liquid holding member. It has been found that it is possible to provide a negative electrode structure capable of producing a zinc secondary battery (in particular, a laminated battery thereof) capable of preventing the extension of zinc dendrite extremely easily and with high productivity.
  • the object of the present invention is to simplify the zinc secondary battery (especially its laminated battery) which can prevent the zinc dendrite extension without requiring complicated sealing and bonding between the LDH separator and the battery container, and the productivity is extremely simple and high.
  • An object of the present invention is to provide a negative electrode structure which can be manufactured by
  • a negative electrode structure for a zinc secondary battery comprising: An anode active material layer comprising at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy and a zinc compound, A composite layer that contains a liquid holding member and layered double hydroxide (LDH), or a liquid holding member, layered double hydroxide (LDH) and a porous base material, and covers or wraps the whole of the negative electrode active material layer; The liquid retaining member and / or the porous substrate such that at least a part of the composite layer in the thickness direction functions as an LDH separator exhibiting hydroxide ion conductivity and gas impermeability.
  • a negative electrode structure is provided that is blocking at least a portion of the pores of the
  • Positive electrode The negative electrode structure; An electrolytic solution, A zinc secondary battery is provided, wherein the positive electrode and the negative electrode active material layer are separated from each other through the LDH separator.
  • FIG. 2 is a schematic cross-sectional view showing the electrochemical measurement system used in Example 1.
  • FIG. 6 is a conceptual diagram showing an example of a He permeability measurement system used in Example 1. It is a schematic cross section of the sample holder used for the measurement system shown by FIG. 6A, and its periphery structure. It is a SEM image which shows the cross-section microstructure of the LDH separator produced in Example 1.
  • FIG. It is a schematic cross section which shows an example of the sealing end of the negative electrode structure of this invention. It is a schematic cross section which shows another example of the sealing end of the negative electrode structure of this invention. It is a schematic cross section which shows another example of the sealing end of the negative electrode structure of this invention. It is a schematic cross section which shows an example of the sealing end of the negative electrode structure to which improvement by this invention is not given.
  • FIG. 1 It is a schematic cross section which shows an example of the internal structure of the zinc secondary battery of this invention. It is a figure for demonstrating the mechanism of the shape change of the negative electrode plate in a zinc secondary battery, While the perspective view of a negative electrode plate is shown by the upper stage, sectional drawing of a negative electrode plate is shown with a LDH separator in the lower stage. It is a conceptual diagram for demonstrating the phenomenon considered to occur in the electrode end part in the zinc secondary battery which does not have an LDH separator, a positive electrode reaction suppression structure, and a negative electrode reaction suppression structure. It is a conceptual diagram for demonstrating the phenomenon considered to occur in an electrode edge part in the zinc secondary battery of this invention.
  • a top view is shown in the upper part, and its A-A 'line sectional view is shown in the lower part.
  • a top view is shown in the upper part, and a B-B 'line sectional view is shown in the lower part.
  • the negative electrode structure of the present invention is used in a zinc secondary battery.
  • An example of the negative electrode structure of the present invention is shown in FIGS. 1A and 1B.
  • the negative electrode structure 10 shown in FIG. 1 includes a negative electrode active material layer 12 and a composite layer 14 which covers or wraps the whole of the negative electrode active material layer 12.
  • the negative electrode active material layer 12 contains at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy, and a zinc compound.
  • the composite layer 14 includes a liquid retaining member 14a, layered double hydroxide (LDH), and optionally a porous substrate. In FIGS. 1A and 1B, the LDH and the porous member are drawn as an LDH separator 14b composed of them.
  • LDH layered double hydroxide
  • an LDH separator 14c composed of a liquid holding member and an LDH may be adopted as the composite layer 14 ′.
  • a porous substrate can be dispensed with. That is, the porous substrate is an optional component.
  • LDH separator is a separator containing LDH and is defined as selectively passing hydroxide ions utilizing exclusively hydroxide ion conductivity of LDH.
  • the composite layer 14 (or 14 ') in the thickness direction exhibits hydroxide ion conductivity and gas impermeability (therefore, as an LDH separator exhibiting hydroxide ion conductivity)
  • the LDH blocks the pores of at least a portion of the liquid retaining member and / or the porous substrate, and as a result, the configuration as the LDH separator is secured.
  • the separation of the positive electrode and the negative electrode by the LDH separator is accomplished carefully and carefully using a resin frame, an adhesive, etc. so as to ensure liquid tightness between the LDH separator and the battery container.
  • the battery configuration and the manufacturing process are likely to be complicated. Such complication of the battery configuration and the manufacturing process can be particularly remarkable in the case of constructing a laminated battery.
  • the entire negative electrode active material layer 12 is covered or wrapped with the composite layer 14 (or 14') including the LDH separator 14b (or 14c).
  • the negative electrode structure 10 (or 10 ') itself has a function capable of preventing a short circuit or the like due to zinc dendrite. Moreover, since the composite layer 14 (or 14 ') includes the liquid holding member 14a alone (or the liquid holding member is provided internally to the LDH separator 14c), the electrolyte solution in the negative electrode structure 10 (or 10')
  • the negative electrode chamber of the zinc secondary battery can be simply configured in such a manner that the zinc dendrite extension can be prevented. Therefore, when the negative electrode structure 10 (or 10 ') of the present invention is adopted for producing a zinc secondary battery, separation of the positive electrode and the negative electrode by the LDH separator can be realized simply by laminating the positive electrode plate and the negative electrode structure. it can.
  • the negative electrode active material layer 12 contains at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy, and a zinc compound. That is, zinc may be contained in any form of zinc metal, zinc compound and zinc alloy as long as it has electrochemical activity suitable for the negative electrode. Preferred examples of the negative electrode material include zinc oxide, zinc metal, calcium zincate and the like, and a mixture of zinc metal and zinc oxide is more preferable.
  • the negative electrode active material layer 12 may be formed in a gel form, or may be mixed with an electrolytic solution to form a negative electrode mixture. For example, a gelled negative electrode can be easily obtained by adding an electrolytic solution and a thickener to the negative electrode active material. Examples of the thickener include polyvinyl alcohol, polyacrylate, CMC, alginic acid and the like, and polyacrylic acid is preferable because it is excellent in chemical resistance to strong alkali.
  • a mercury-free and lead-free zinc alloy known as a zinc-free zinc alloy.
  • a zinc alloy containing 0.01 to 0.1% by mass of indium, 0.005 to 0.02% by mass of bismuth, and 0.0035 to 0.015% by mass of aluminum has the effect of suppressing the generation of hydrogen gas So preferred.
  • Indium and bismuth are particularly advantageous in improving the discharge performance.
  • the use of the zinc alloy for the negative electrode can improve the safety by suppressing the generation of hydrogen gas by reducing the self-dissolution rate in the alkaline electrolyte.
  • the shape of the negative electrode material is not particularly limited, but is preferably in the form of powder, whereby the surface area is increased and it becomes possible to cope with high current discharge.
  • the average particle diameter of the preferred negative electrode material is in the range of 3 to 100 ⁇ m in the short diameter, and within this range, the surface area is large, so that it is suitable for large current discharges. It is easy to mix uniformly with the agent, and the handling at the time of battery assembly is also good.
  • the negative electrode structure 10 preferably further includes a current collector 13 in contact with the negative electrode active material layer 12.
  • the current collector 13 preferably has a current collector extension 13 a extending from one side of the negative electrode active material layer 12, and the tip of the current collector extension 13 a is not covered with the composite layer 14. It is preferable to make an exposed part.
  • the current collector 13 (particularly, the current collector extension 13a) can be desirably connected to the negative electrode terminal (not shown) through the exposed portion.
  • the LDH separator 14b covers the end of the negative electrode active material layer 12 on the current collector extension 13a side with a predetermined margin M so as to sufficiently hide the end. Or it is preferable to wrap. By so doing, extension of zinc dendrite from the end of the negative electrode active material layer 12 on the current collector extension 13a side or in the vicinity thereof can be prevented more effectively.
  • the negative electrode current collector 13 include copper foil, copper expanded metal and copper punching metal, and more preferably copper expanded metal.
  • a negative electrode comprising a negative electrode / negative electrode current collector by applying a mixture comprising zinc oxide powder and / or zinc powder, and optionally a binder (for example, polytetrafluoroethylene particles) on copper expanded metal.
  • the plate can be made preferably. At that time, it is also preferable to press-process the dried negative electrode plate (that is, the negative electrode / negative electrode current collector) to prevent the electrode active material from falling off and improve the electrode density.
  • the composite layer 14 is a layer that covers or wraps the whole of the negative electrode active material layer 12, and includes a liquid retaining member, layered double hydroxide (LDH), and optionally a porous substrate.
  • the number of composite layers 14 (or 14 ') or LDH separators contained therein is typically 1 (one on both sides facing each other or one folded) on one side, but may be 2 or more.
  • the whole of the negative electrode active material layer 12 may be covered or encased with several layers of the composite layer 14 (or 14 ') or several layers of the LDH separator 14b (or 14c).
  • the composite layer 14 (or 14 ') in the thickness direction exhibits hydroxide ion conductivity and gas impermeability (therefore, as an LDH separator exhibiting hydroxide ion conductivity)
  • the LDH blocks the pores of at least a portion of the liquid retaining member and / or the porous substrate, and as a result, the configuration as the LDH separator is secured.
  • the composite layer 14 includes the liquid retaining member 14a, the LDH and the porous substrate, and the LDH and the porous substrate constitute the LDH separator 14b. And, as the LDH separator 14 b exhibits hydroxide ion conductivity and gas impermeability (so that it functions as an LDH separator exhibiting hydroxide ion conductivity), the LDH is at least one of the porous substrates. Blocking the hole in the department.
  • the liquid retaining member 14a constitute the side adjacent to the negative electrode active material layer 12 of the composite layer 14 and the LDH separator 14b constitute the side away from the negative electrode active material layer 12 of the composite layer 14 .
  • the electrolytic solution can be uniformly present between the negative electrode active material layer 12 and the LDH separator 14b, and the exchange of hydroxide ions between the negative electrode active material layer 12 and the LDH separator 14b can be realized. It can be done efficiently.
  • the liquid holding member 14a is not particularly limited as long as it can hold the electrolytic solution, but is preferably a sheet-like member.
  • Preferred examples of the liquid retaining member include nonwoven fabric, water absorbing resin, liquid retaining resin, porous sheet, and various spacers, and particularly preferably nonwoven fabric in that the negative electrode structure 10 with good performance can be produced at low cost. is there.
  • the liquid holding member 14a preferably has a thickness of 0.01 to 0.20 mm, more preferably 0.02 to 0.20 mm, still more preferably 0.02 to 0.15 mm, particularly preferably It is 0.02 to 0.10 mm, most preferably 0.02 to 0.06 mm. When the thickness is within the above range, a sufficient amount of electrolytic solution can be held in the liquid holding member 14a while suppressing the entire size of the negative electrode structure 10 in a compact manner without waste.
  • the liquid retaining member 14a is depicted as being smaller in size than the LDH separator 14b in FIGS. 1A and 1B, the liquid retaining member 14a may be the same size as the LDH separator 14b (or the folded LDH separator 14b), The outer edge of the liquid holding member 14a can reach the outer edge of the LDH separator 14b. That is, the outer peripheral portion of the liquid holding member 14 a may be sandwiched between the LDH separators 14 b constituting the outer peripheral portion. By doing this, the outer edge sealing of the composite layer 14 described later can be effectively performed by heat welding or ultrasonic welding.
  • the heat welding or ultrasonic welding may be indirectly performed by interposing the heat welding property liquid retaining member 14a between the LDH separators 14b.
  • the heat welding property of the liquid retaining member 14a itself can be utilized, sealing can be performed more effectively.
  • the end of the liquid retaining member 14a to be sealed can be used as if it were a hot melt adhesive.
  • a nonwoven fabric in particular, a nonwoven fabric made of a thermoplastic resin (for example, polyethylene, polypropylene) can be mentioned.
  • the LDH separator 14 b is composed of an LDH and a porous substrate. Specifically, at least a part of the composite layer 14 in the thickness direction exhibits hydroxide ion conductivity and gas impermeability (so that it functions as an LDH separator exhibiting hydroxide ion conductivity), The LDH blocks at least a part of the pores of the porous substrate, and as a result, the configuration as the LDH separator is secured. Preferably, LDH is incorporated throughout the thickness of the porous substrate.
  • the thickness of the LDH separator 14b is preferably 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • the LDH separator 14b is a separator containing layered double hydroxide (LDH), and when it is incorporated into a zinc secondary battery, it separates the positive electrode plate and the negative electrode plate so that they can conduct hydroxide ions. . That is, the LDH separator 14b functions as a hydroxide ion conductive separator.
  • the preferred LDH separator 14b is gas impermeable and / or water impermeable. In other words, it is preferable that the LDH separator 14b be dense enough to be gas impermeable and / or water impermeable.
  • having gas impermeability refers to one side of the object to be measured being contacted with helium gas at a differential pressure of 0.5 atm, as described in Patent Documents 2 and 3. This also means that no bubbles due to helium gas are observed from the other side. Further, in the present specification, “having water impermeability” means that water in contact with one side of the object to be measured does not permeate to the other side as described in Patent Documents 2 and 3. .
  • the fact that the LDH separator 14b has gas impermeability and / or water impermeability means that the LDH separator 14b has such a high degree of compactness as to be impervious to gas or water, and water permeability or gas It means that it is not a porous film or other porous material having permeability.
  • the LDH separator 14 b can selectively pass only hydroxide ions due to its hydroxide ion conductivity, and can exhibit a function as a battery separator. Therefore, the configuration is extremely effective for physically preventing penetration of the separator due to zinc dendrite generated during charging to prevent short circuit between positive and negative electrodes. Since the LDH separator 14b has hydroxide ion conductivity, it enables efficient movement of hydroxide ions required between the positive electrode plate and the negative electrode plate to realize charge / discharge reactions in the positive electrode plate and the negative electrode plate. Can.
  • the LDH separator 14b preferably has a He permeability of 10 cm / min ⁇ atm or less, more preferably 5.0 cm / min ⁇ atm or less, and still more preferably 1.0 cm / min ⁇ atm or less per unit area. .
  • a separator having a He permeability of 10 cm / min ⁇ atm or less can extremely effectively suppress the permeation of Zn (typically, the permeation of zinc ions or zincate ions) in the electrolytic solution.
  • the separator of the present embodiment is considered to be capable of effectively suppressing the growth of zinc dendrite when used in a zinc secondary battery because Zn permeation is significantly suppressed.
  • the He permeability is through the steps of supplying He gas to one side of the separator and allowing the separator to permeate He gas, and calculating the He permeability to evaluate the compactness of the hydroxide ion conductive separator. It is measured.
  • the He permeability is expressed by the formula of F / (P ⁇ S) using the permeation amount F of He gas per unit time, the differential pressure P applied to the separator at the time of He gas permeation, and the membrane area S at which He gas permeates. calculate.
  • He gas has the smallest structural unit among a wide variety of atoms or molecules that can constitute the gas, and the reactivity is extremely low. That is, He forms He gas with He atoms alone without forming molecules. In this respect, since hydrogen gas is composed of H 2 molecules, a single He atom is smaller as a gas constituent unit. First of all, H 2 gas is dangerous because of flammable gas.
  • the indicator of He gas permeability defined by the above-mentioned equation, objective evaluation regarding compactness can be simply performed regardless of various sample sizes and differences in measurement conditions. Thus, it can be evaluated simply, safely and effectively whether the separator has a sufficiently high compactness suitable for a zinc secondary battery separator.
  • the measurement of the He permeability can be preferably performed according to the procedure shown in Evaluation 7 of Example 1 described later.
  • the LDH is composed of a plurality of hydroxide base layers and an intermediate layer interposed between the plurality of hydroxide base layers.
  • the hydroxide base layer is mainly composed of metal elements (typically metal ions) and OH groups.
  • the interlayer of LDH is composed of anions and H 2 O.
  • the anion is a monovalent or higher anion, preferably a monovalent or divalent ion.
  • anions in the LDH is OH - containing and / or CO 3 2- and.
  • LDH has excellent ion conductivity due to its inherent properties.
  • LDH is, 2 O (wherein M 2+ 1-x M 3+ x (OH) 2 A n- x / n ⁇ mH, M 2+ is a divalent cation, M 3+ is a trivalent A n ⁇ is a cation, n is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more. It is known as being represented.
  • M 2+ may be any divalent cation, but preferred examples include Mg 2+ , Ca 2+ and Zn 2+ , more preferably Mg 2+ .
  • M 3 + may be any trivalent cation, but preferred examples include Al 3 + or Cr 3 + , and more preferably Al 3 + .
  • An - can be any anion but preferred examples include OH - and CO 3 2- .
  • M 2+ comprises Mg 2+
  • M 3+ comprises Al 3+
  • a n-is OH - and / or CO preferably contains 3 2-.
  • n is an integer of 1 or more, preferably 1 or 2.
  • x is 0.1 to 0.4, preferably 0.2 to 0.35.
  • m is an arbitrary number meaning the number of moles of water, and is a real number of 0 or more, typically more than 0 or 1 or more.
  • the above-mentioned basic composition formula is only a formula of "basic composition” typically illustrated typically regarding LDH, and can substitute a component ion suitably.
  • part or all of M 3+ may be replaced by a tetravalent or higher valence cation, in which case the coefficient x / n of the anion A n ⁇ in the above general formula May be changed as appropriate.
  • the hydroxide base layer of LDH may be composed of Ni, Ti, OH groups, and optionally unavoidable impurities.
  • the interlayer of LDH is composed of anions and H 2 O as described above.
  • the alternate layered structure itself of the hydroxide basic layer and the intermediate layer is basically the same as the generally known alternate layered structure of LDH, but the LDH of this embodiment is mainly composed of Ni, the hydroxide basic layer of the LDH.
  • Ni in LDH can take the form of nickel ion.
  • the nickel ion in LDH is typically considered to be Ni 2+ but is not particularly limited as it may have other valences such as Ni 3+ .
  • Ti in LDH can take the form of titanium ions.
  • the titanium ion in LDH is typically considered to be Ti 4+ , but is not particularly limited as other valences such as Ti 3+ may also be present.
  • Unavoidable impurities are optional elements that can be inevitably mixed in the manufacturing method, and may be mixed into LDH derived from, for example, a raw material or a base material.
  • the hydroxide base layer is mainly composed of Ni 2+ , Ti 4+ and OH groups
  • the corresponding LDH has the general formula: Ni 2+ 1 ⁇ x Ti 4+ x (OH) 2
  • An ⁇ 2x / n ⁇ mH 2 O (wherein, A n ⁇ is an n-valent anion, n is an integer of 1 or more, preferably 1 or 2, and 0 ⁇ x ⁇ 1 preferably 0.01 ⁇ x ⁇ 0.5, m is 0 or more, and is typically a real number greater than 0 or 1 or more.
  • the hydroxide base layer of LDH may contain Ni, Al, Ti and OH groups.
  • the middle layer is composed of anions and H 2 O as described above.
  • the alternate layered structure itself of the hydroxide basic layer and the intermediate layer is basically the same as the generally known alternate layered structure of LDH, but in the LDH of this embodiment, the hydroxide basic layer of LDH is made of Ni, Al Excellent alkali resistance can be exhibited by using predetermined elements or ions containing Ti, and OH groups. The reason is not necessarily clear, but the LDH of this embodiment is considered to be because Al, which was conventionally considered to be easily eluted in an alkaline solution, becomes difficult to be eluted in an alkaline solution due to any interaction with Ni and Ti.
  • the LDH of this embodiment can also exhibit high ion conductivity suitable for use as a separator for an alkaline secondary battery.
  • Ni in LDH can take the form of nickel ion.
  • the nickel ion in LDH is typically considered to be Ni 2+ but is not particularly limited as it may have other valences such as Ni 3+ .
  • Al in LDH can take the form of aluminum ion.
  • the aluminum ion in LDH is typically considered to be Al 3+ , but is not particularly limited as it may have other valences.
  • Ti in LDH can take the form of titanium ions.
  • the titanium ion in LDH is typically considered to be Ti 4+ , but is not particularly limited as other valences such as Ti 3+ may also be present.
  • the hydroxide base layer may contain other elements or ions as long as it contains Ni, Al, Ti and OH groups. However, it is preferable that the hydroxide base layer contains Ni, Al, Ti and OH groups as main components. That is, the hydroxide base layer preferably consists mainly of Ni, Al, Ti and OH groups. Thus, the hydroxide base layer is typically composed of Ni, Al, Ti, OH groups and optionally unavoidable impurities. Unavoidable impurities are optional elements that can be inevitably mixed in the manufacturing method, and may be mixed into LDH derived from, for example, a raw material or a base material.
  • the hydroxide base layer is mainly composed of Ni 2+ , Al 3+ , Ti 4+ and OH groups
  • the corresponding LDH has the general formula: Ni 2+ 1 ⁇ x ⁇ y Al 3+ x Ti 4 + y (OH) 2 A n- (x + 2 y) / n m H 2 O
  • n is an n-valent anion
  • n is an integer of 1 or more, preferably 1 or 2, 0 ⁇ x ⁇ 1, preferably 0.01 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1, preferably 0.01 ⁇ y ⁇ 0.5, 0 ⁇ x + y ⁇ 1,
  • m is 0 or more, typically 0 It can be represented by a basic composition of “more than one or more real numbers”.
  • the porous substrate has water permeability and gas permeability so that when it is incorporated into a zinc secondary battery, the electrolyte can reach the LDH, but the porous substrate is It is also possible to hold hydroxide ions more stably by the LDH separator 14b.
  • the porous base material can impart strength, the LDH separator 14b can be thinned to reduce resistance.
  • the porous substrate is preferably composed of a polymeric material.
  • the porous polymer substrate has 1) flexibility (therefore, it is difficult to be broken even if it is thin), 2) it is easy to increase the porosity, 3) it is easy to increase the conductivity (the thickness is increased while the porosity is increased) To be thin) and 4) easy to manufacture and handle.
  • the LDH separator 14b including the porous base material made of a polymer material can be easily bent or sealed and joined as described later
  • at least one side of the outer edge of the composite layer 14 (or 14 ') can be easily formed in a closed state (in the case of bending, there is also an advantage that the sealing step of one outer edge can be reduced) .
  • polystyrene polystyrene, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide, hydrophilized fluorocarbon resin (tetrafluorinated resin: such as PTFE), cellulose, nylon, polyethylene and any combination thereof Can be mentioned.
  • All the various preferable materials mentioned above have alkali resistance as resistance with respect to the electrolyte solution of a battery.
  • Particularly preferable polymer materials are polyolefins such as polypropylene and polyethylene in that they are excellent in hot water resistance, acid resistance and alkali resistance and are low in cost, and most preferably polypropylene.
  • the LDH layer is incorporated throughout the thickness direction of the porous substrate (for example, most or almost all pores inside the porous substrate are filled with LDH) Is particularly preferred.
  • the preferable thickness of the porous polymer substrate in this case is 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • a microporous film commercially available as a separator for lithium batteries can be preferably used, or commercially available cellophane can also be used.
  • the porous substrate preferably has an average pore size of at most 100 ⁇ m or less, more preferably at most 50 ⁇ m or less, eg typically 0.001 to 1.5 ⁇ m, more typically 0.001 ⁇ 1.25 ⁇ m, more typically 0.001 to 1.0 ⁇ m, particularly typically 0.001 to 0.75 ⁇ m, and most typically 0.001 to 0.5 ⁇ m.
  • the measurement of the average pore diameter can be performed by measuring the longest distance of pores based on the electron microscope image of the surface of the porous substrate.
  • the magnification of the electron microscope image used for this measurement is 20000 times or more, and all the pore diameters obtained are arranged in order of size, and the upper 15 points and lower 15 points in order of closeness from the average value
  • An average pore diameter can be obtained by calculating an average value for two fields of view.
  • a length measurement function of software of SEM, image analysis software (for example, Photoshop, manufactured by Adobe), or the like can be used.
  • the porous substrate preferably has a porosity of 10 to 60%, more preferably 15 to 55%, still more preferably 20 to 50%. By setting the content within these ranges, it is possible to form a dense LDH separator so as to exhibit gas impermeability while securing desired permeability and strength as a support on the porous substrate.
  • the porosity of the porous substrate can be preferably measured by the Archimedes method. However, when the porous substrate is made of a polymer material and LDH is incorporated throughout the thickness direction of the porous substrate, the porosity of the porous substrate is preferably 30 to 60%, and more preferably Is 40 to 60%.
  • the method for producing the LDH separator 14b is not particularly limited, and the LDH-containing functional layer and the composite material (that is, the LDH separator) can be produced by appropriately changing various conditions of known methods (see, for example, patent documents 1 to 3). can do.
  • a porous substrate is prepared, and (2) a titanium oxide sol or a mixed sol of alumina and titania is applied to the porous substrate and heat treated to form a titanium oxide layer or an alumina-titania layer.
  • the porous base material is immersed in a raw material aqueous solution containing nickel ions (Ni 2+ ) and urea, and (4) the porous base material is hydrothermally treated in the raw material aqueous solution to make the LDH-containing functional layer a porous base material
  • the LDH-containing functional layer and the composite material i.e., LDH separator
  • LDH separator can be manufactured by forming on the top and / or the porous substrate.
  • the porous substrate is made to function as a starting point of LDH crystal growth.
  • the highly densified LDH-containing functional layer can be uniformly formed uniformly on the surface. Further, due to the presence of urea in the step (3), the pH value is raised by the generation of ammonia in the solution by utilizing the hydrolysis of urea, and the coexisting metal ions form a hydroxide. LDH can be obtained by In addition, since the hydrolysis involves the generation of carbon dioxide, it is possible to obtain a carbonate ion LDH as the anion.
  • the alumina in the above (2) when producing a composite material (i.e., LDH separator) in which the porous substrate is composed of a polymer material and the functional layer is incorporated throughout the thickness direction of the porous substrate, the alumina in the above (2)
  • the application of the mixed sol of titania and titania to the substrate is preferably carried out in such a manner that the mixed sol penetrates the whole or most of the interior of the substrate. In this way, most or almost all pores inside the porous substrate can be finally filled with LDH.
  • preferred coating techniques include dip coating, filtration coating and the like, with dip coating being particularly preferred.
  • the adhesion amount of the mixed sol can be adjusted by adjusting the number of times of application such as dip coating.
  • the base on which the mixed sol is applied by dip coating or the like may be dried, and then the steps (3) and (4) may be performed.
  • the composite layer 14 ′ may be composed of a liquid retaining member and an LDH, and the LDH and the liquid retaining member may be an LDH separator 14c.
  • the LDH separator 14c exhibits hydroxide ion conductivity and gas impermeability (so that it functions as an LDH separator exhibiting hydroxide ion conductivity), at least a part of the liquid holding member Blocking the hole of In this case, the composite layer 14 'is constituted by the LDH separator 14c alone.
  • the LDH separator 14c corresponds to a configuration in which a liquid retaining member is used instead of the porous substrate in the above-described LDH separator 14b.
  • the thickness of the LDH separator 14c is preferably 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 5 to 30 ⁇ m. Except for this thickness, the various preferred embodiments of the LDH described in connection with the LDH separator 14b apply to the LDH separator 14c as it is. Therefore, the production of the LDH separator 14c can also be performed in the same manner as the LDH separator 14b except that a liquid holding member (for example, non-woven fabric) is used instead of the porous substrate.
  • a liquid holding member for example, non-woven fabric
  • the composite layer 14 typically has a quadrilateral (typically square) shape.
  • at least two sides of the outer edge of the composite layer 14 (or 14 ') are preferably closed.
  • the negative electrode active material layer 12 can be reliably isolated from the positive electrode, and extension of zinc dendrite can be prevented more effectively.
  • the negative electrode structure 10 (or 10 ') has the current collector extension 13a, in order to enable extension of the current collector extension 13a, at least two sides that can be closed are current collectors. It is desirable that the side is not in contact with the body extension 13a.
  • one side or two sides of the outer edge of the composite layer 14 may be open.
  • the negative electrode structure 10 is a main component of the sealed zinc secondary battery by being accommodated together with the positive electrode in the sealed container with the electrolyte also contained therein.
  • the negative electrode structure 10 (or 10 ') itself can be a simple configuration of the upper open type. Also, by opening one side of the outer edge of the composite layer 14 (or 14 '), the current collector extension 13a can be extended therefrom.
  • the open outer edge 1 side for extending the current collector extension 13a may be an upper end 1 side providing an upper open portion, or may be another outer edge 1 side.
  • At least two sides of the outer edge of the composite layer 14 (or 14 ') are closed by sealing the pair of composite layers 14 (or 14') or folding the composite layer 14 (or 14 ').
  • Preferred examples of sealing techniques include adhesives, heat welding, ultrasonic welding, adhesive tapes, sealing tapes, and combinations thereof.
  • the composite layer 14 (or 14) Preferably, one side of the outer edge is closed by forming '' in a long shape and bending it.
  • heat welding and ultrasonic welding may be performed using a commercially available heat sealer or the like, in the case of sealing of the composite layer 14, the outer peripheral portion of the liquid retaining member 14a is sandwiched between the LDH separators 14b constituting the outer peripheral portion. It is preferable to perform heat welding and ultrasonic welding in that the sealing can be performed more effectively.
  • a commercial item may be used for an adhesive agent, an adhesive tape, and a sealing tape, in order to prevent deterioration in an alkaline electrolyte solution, what contains the resin which has alkali resistance is preferable.
  • examples of preferable adhesives include epoxy resin adhesives, natural resin adhesives, modified olefin resin adhesives, and modified silicone resin adhesives, among which epoxy resin adhesives are resistant It is more preferable in that it is particularly excellent in alkalinity.
  • an epoxy adhesive Hysol registered trademark (manufactured by Henkel) may be mentioned.
  • the LDH separator 14b or 14c and the end of the negative electrode active material layer 12 are in direct or indirect contact with each other, whereby the LDH separator 14b or 14c and the negative electrode active material There may be no excess space between the end of the layer 12 and the electrolyte reservoir. That is, when a large amount of extra electrolyte is present between the LDH separator 14 b or 14 c and the end of the negative electrode active material layer 12, metal Zn is concentrated at the end of the negative electrode active material layer 12 (ZnO layer) at the time of charge reaction.
  • the metal Zn diffuses as Zn (OH) 4 2 ⁇ and precipitates as ZnO at the central portion of the negative electrode, which may cause the shape change of the negative electrode plate. Therefore, by eliminating the excess space that allows electrolyte solution accumulation, it is possible to effectively prevent the shape change of the negative electrode plate (particularly, the negative electrode active material layer 12) due to the repetition of charge and discharge.
  • a liquid retaining member 14a may be present between the LDH separator 14b and the end of the negative electrode active material layer 12 so as not to provide an excess space for allowing electrolyte solution accumulation.
  • the excess space for allowing the electrolytic solution reservoir may be eliminated.
  • the negative electrode structure of the present invention is preferably applied to a zinc secondary battery. Therefore, according to a preferred embodiment of the present invention, there is provided a zinc secondary battery comprising a positive electrode, a negative electrode structure and an electrolytic solution, wherein the positive electrode and the negative electrode active material layer are separated from each other via the LDH separator. .
  • the zinc secondary battery of the present invention is not particularly limited as long as it is a secondary battery using zinc as a negative electrode and an electrolytic solution (typically, an aqueous alkali metal hydroxide solution). Therefore, a nickel zinc secondary battery, a silver oxide zinc secondary battery, a manganese zinc oxide secondary battery, a zinc air secondary battery, and various other alkaline zinc secondary batteries can be used.
  • the positive electrode contains nickel hydroxide and / or nickel oxyhydroxide, whereby the zinc secondary battery constitutes a nickel zinc secondary battery.
  • the positive electrode may be an air electrode, whereby the zinc secondary battery may form a zinc-air secondary battery.
  • the LDH separator that can be used in the present invention will be more specifically described by the following example.
  • Example 1 Using a polymeric porous substrate, an LDH separator containing Ni, Al and Ti-containing LDH was prepared and evaluated according to the following procedure.
  • the mixed sol was applied by dip coating to the substrate prepared in (1) above. The dip coating was performed by immersing the substrate in 100 ml of the mixed sol, pulling it vertically, and drying it in a dryer at 90 ° C. for 5 minutes.
  • Nickel nitrate hexahydrate Ni (NO 3) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc. and urea ((NH 2) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed into a beaker so as to be 0.015 mol / L, and ion-exchanged water was added there to make the total amount 75 ml.
  • the substrate was removed from the closed vessel, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to obtain LDH incorporated in a porous substrate.
  • an LDH separator was obtained.
  • Evaluation 1 Identification of the LDH Separator
  • the crystal phase of the LDH separator is measured under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10 to 70 ° with an X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation)
  • the XRD profile was obtained.
  • JCPDS card NO. Identification was performed using the diffraction peak of LDH (hydrotalcite-like compound) described in 35-0964.
  • Evaluation 2 Observation of Microstructure The surface microstructure of the LDH separator was observed using a scanning electron microscope (SEM, JSM-6610 LV, manufactured by JEOL) at an acceleration voltage of 10 to 20 kV. In addition, after obtaining a cross-sectional polished surface of the LDH separator with an ion milling apparatus (manufactured by Hitachi High-Technologies Corporation, IM 4000), the microstructure of the cross-sectional polished surface was observed by SEM under the same conditions as the surface microstructure.
  • SEM scanning electron microscope
  • JSM-6610 LV manufactured by JEOL
  • IM 4000 ion milling apparatus
  • Evaluation 3 Elemental Analysis Evaluation (EDS) The cross section polisher (CP) was polished so that the cross-section polished surface of the LDH separator could be observed.
  • a cross-sectional image of the LDH separator was acquired for one field of view at a magnification of 10000 by FE-SEM (ULTRA 55, manufactured by Carl Zeiss). Elemental analysis of the LDH film on the substrate surface and the LDH part inside the substrate (point analysis) of this cross-sectional image was carried out using an EDS analyzer (NORAN System SIX, manufactured by Thermo Fisher Scientific) under conditions of an acceleration voltage of 15 kV. went.
  • NORAN System SIX manufactured by Thermo Fisher Scientific
  • Evaluation 4 Evaluation of alkali resistance Zinc oxide was dissolved in a 6 mol / L aqueous potassium hydroxide solution to obtain a 5 mol / L aqueous potassium hydroxide solution containing zinc oxide at a concentration of 0.4 mol / L. 15 ml of the potassium hydroxide aqueous solution thus obtained was placed in a Teflon (registered trademark) closed container. A 1 cm ⁇ 0.6 cm size LDH separator was placed at the bottom of the closed container and the lid closed. Then, after holding at 70 ° C. for 3 weeks (ie, 504 hours) or 7 weeks (ie, 1176 hours), the LDH separator was removed from the closed vessel. The removed LDH separator was dried overnight at room temperature. The obtained sample was subjected to microstructure observation by SEM and crystal structure observation by XRD.
  • Evaluation 5 Measurement of ionic conductivity The conductivity of the LDH separator in the electrolytic solution was measured as follows using the electrochemical measurement system shown in FIG.
  • the LDH separator sample S was sandwiched by 1 mm thick silicone packing 40 from both sides and incorporated into a PTFE flange type cell 42 with an inner diameter of 6 mm.
  • As the electrode 46 a # 100 mesh nickel wire mesh was incorporated into the cell 42 in a cylindrical shape with a diameter of 6 mm so that the distance between the electrodes was 2.2 mm.
  • As the electrolyte solution 44 6 M KOH aqueous solution was filled in the cell 42.
  • the epoxy adhesive 134 was applied to the depression 132 b of the alumina jig 132, and the LDH separator sample 136 was placed on the depression 132 b and adhered to the alumina jig 132 in an airtight and liquid tight manner. Then, the alumina jig 132 to which the LDH separator sample 136 is bonded is adhered to the upper end of the acrylic container 130 in an airtight and liquid tight manner using the silicone adhesive 138 so as to completely close the opening of the acrylic container 130. The measurement sealed container 140 was obtained.
  • the measurement airtight container 140 was placed in the water tank 142, and the gas supply port 130a of the acrylic container 130 was connected to the pressure gauge 144 and the flow meter 146 so that helium gas could be supplied into the acrylic container 130.
  • the water 143 was put in the water tank 142, and the measurement sealed container 140 was completely submerged.
  • the inside of the sealed container for measurement 140 is sufficiently airtight and liquid-tight, and one side of the LDH separator sample 136 is exposed to the internal space of the sealed container for measurement 140 while the LDH separator sample 136 is exposed.
  • the other side of the water is in contact with the water in the water tank 142.
  • helium gas was introduced into the acrylic container 130 through the gas supply port 130 a into the measurement sealed container 140.
  • the pressure difference between the inside and the outside of the LDH separator sample 136 is 0.5 atm (that is, the pressure applied to the side in contact with the helium gas is 0.5 atm higher than the water pressure applied to the opposite side) Then, it was observed whether bubbles of helium gas were generated from the LDH separator sample 136 in water. As a result, when generation of bubbles due to helium gas was not observed, it was determined that the LDH separator sample 136 had high density so as to exhibit gas impermeability.
  • He Permeation Measurement In order to evaluate the compactness of the LDH separator from the viewpoint of He permeability, a He permeation test was performed as follows. First, the He permeability measurement system 310 shown in FIGS. 6A and 6B was constructed. In the He permeability measurement system 310, the He gas from the gas cylinder filled with the He gas is supplied to the sample holder 316 via the pressure gauge 312 and the flow meter 314 (digital flow meter), and the LDH held by the sample holder 316 It was configured to permeate from one side of the separator 318 to the other side to be discharged.
  • the sample holder 316 has a structure provided with a gas supply port 316a, a sealed space 316b and a gas discharge port 316c, and was assembled as follows.
  • the adhesive 322 was applied along the outer periphery of the LDH separator 318 and attached to a jig 324 (made of ABS resin) having an opening at the center.
  • Packing made of butyl rubber is disposed as sealing members 326a and 326b at the upper and lower ends of the jig 324, and support members 328a and 328b (made of PTFE are provided with openings made of flanges from the outside of the sealing members 326a and 326b) It was pinched by).
  • the sealed space 316b is defined by the LDH separator 318, the jig 324, the sealing member 326a, and the support member 328a.
  • the support members 328a and 328b were tightly tightened with each other by means of fastening means 330 using a screw so that no He gas leaked from portions other than the gas outlet 316c.
  • the gas supply pipe 334 was connected to the gas supply port 316 a of the sample holder 316 thus assembled via the joint 332.
  • He gas was supplied to the He permeability measurement system 310 through the gas supply pipe 334, and permeated to the LDH separator 318 held in the sample holder 316.
  • the gas supply pressure and flow rate were monitored by the pressure gauge 312 and the flow meter 314.
  • the He permeability was calculated.
  • the He permeability is calculated by the amount of He gas permeation F (cm 3 / min) per unit time, the differential pressure P (atm) applied to the LDH separator during He gas permeation, and the membrane area S (cm) through which He gas permeates. It calculated by the formula of F / (PxS) using 2 ).
  • the permeation amount F (cm 3 / min) of He gas was read directly from the flow meter 314. Further, as the differential pressure P, a gauge pressure read from the pressure gauge 312 was used. The He gas was supplied such that the differential pressure P was in the range of 0.05 to 0.90 atm.
  • Evaluation results were as follows. -Evaluation 1: From the obtained XRD profile, it was identified that the crystal phase contained in the LDH separator is LDH (hydrotalcite compound). -Evaluation 2: The SEM image of the cross-sectional microstructure of the LDH separator was as shown in FIG. As can be seen from FIG. 7, it was observed that the LDH was incorporated throughout the thickness direction of the porous substrate, that is, the pores of the porous substrate were uniformly filled with the LDH. Evaluation 3: As a result of EDS elemental analysis, LDH constituent elements C, Al, Ti and Ni were detected from the LDH separator.
  • both sides of the negative electrode active material layer 112 are entirely covered with a pair of LDH separators 114, and the end portions of the pair of LDH separators 114 are sealed, It is conceivable to produce a zinc secondary battery (in particular, a laminated battery thereof) capable of preventing zinc dendrite extension extremely easily and with high productivity without the need for complicated sealing and bonding with the battery container. Since the entire negative electrode active material layer 112 is covered with the LDH separator 114, the negative electrode structure 110 having such a configuration can have a function capable of preventing a short circuit or the like due to zinc dendrite in the negative electrode structure 110 itself. There is an advantage. On the other hand, as shown in FIG.
  • an excess space E is formed between the LDH separator 114 and the negative electrode active material layer 112 in the vicinity of the sealing end 114b of the LDH separator 114. This is due to the distance D between the sealing end 114 b and the end face of the negative electrode active material layer 112 on the excess space E side. If the surplus space E is large, not only the battery case is enlarged and the volumetric energy density is lowered, but also precipitation of a large amount of zinc dendrite in the surplus space E is permitted.
  • the present inventors now cover the whole of the negative electrode active material layer with a pair of LDH separators whose ends are sealed, thereby eliminating the need for complicated sealing and bonding between the LDH separator and the battery case, and zinc
  • the inventors have found that it is possible to provide a negative electrode structure capable of producing a zinc secondary battery (in particular, a laminated battery thereof) capable of preventing dendrite extension extremely easily and with high productivity.
  • the outer edge of the negative electrode active material layer in the vicinity of the sealing end has a tapered cross-sectional shape so that the LDH separator conforms to that shape, thereby significantly reducing the extra space in the negative electrode structure.
  • the present inventors have found that it is possible to realize downsizing of the battery casing and improvement in volumetric energy density, ii) suppression of precipitation of zinc dendrite in the surplus space, and / or reduction of the amount of use of the separator material.
  • an object of the present invention to make a zinc secondary battery (especially its laminated battery) capable of preventing zinc dendrite extension extremely easy and high without the need for complicated sealing and bonding between the LDH separator and the battery container.
  • An object of the present invention is to provide a negative electrode structure which can be manufactured with productivity.
  • Another object of the present invention is to significantly reduce the extra space in the negative electrode structure to i) miniaturize the battery case and thereby improve the volumetric energy density, ii) suppress the precipitation of zinc dendrite in the extra space And / or iii) to reduce the amount of separator material used.
  • a negative electrode structure for a zinc secondary battery comprising: An anode active material layer comprising at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy and a zinc compound, A pair of layered double hydroxide (LDH) separators, which entirely cover both surfaces of the negative electrode active material layer and have an extra portion extending beyond the end of the negative electrode active material layer; Equipped with At least one side of the outer edge of the pair of LDH separators is sealed to form a sealed end, At least one side of the outer edge of the negative electrode active material layer adjacent to the sealing end has a tapered cross-sectional shape in which the thickness decreases toward the outer edge of the negative electrode active material layer, The separation distance of the pair of LDH separators is configured to decrease toward the sealing end in such a manner that the surplus portion of the pair of LDH separators and the vicinity thereof conform to the tapered cross-sectional shape And a negative electrode structure is provided.
  • An anode active material layer comprising at least one selected from the group consisting of
  • a zinc secondary battery comprising a positive electrode, the negative electrode structure, and an electrolytic solution, wherein the positive electrode and the negative electrode active material layer are separated from each other via the LDH separator.
  • the negative electrode structure of the present invention is used in a zinc secondary battery.
  • An example of the negative electrode structure of the present invention is shown in FIG.
  • the negative electrode structure 10 shown in FIG. 8 includes a negative electrode active material layer 12 and a pair of layered double hydroxide (LDH) separators 14.
  • LDH separator is a separator containing LDH and is defined as selectively passing hydroxide ions utilizing exclusively hydroxide ion conductivity of LDH.
  • the negative electrode active material layer 12 contains at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy, and a zinc compound.
  • the pair of LDH separators 14 has an excess portion 14 a that covers the entire surface of the negative electrode active material layer 12 and extends beyond the end of the negative electrode active material layer 12. At least one side of the outer edge of the pair of LDH separators 14 is sealed to form a sealed end 14b, and at least one side of the outer edge of the negative electrode active material layer 12 adjacent to the sealed end 14b is a negative electrode active material layer 12 Have a tapered cross-sectional shape with decreasing thickness towards the outer edge of the Then, the distance between the pair of LDH separators 14 decreases toward the sealing end 14 b in such a manner that the surplus portion 14 a of the pair of LDH separators 14 and the vicinity thereof conform (or follow) the tapered cross-sectional shape.
  • the separation of the positive electrode and the negative electrode by the LDH separator is accomplished carefully and carefully using a resin frame, an adhesive, etc. so as to ensure liquid tightness between the LDH separator and the battery container.
  • the battery configuration and the manufacturing process are likely to be complicated. Such complication of the battery configuration and the manufacturing process can be particularly remarkable in the case of constructing a laminated battery.
  • the negative electrode structure 10 of the present invention since both surfaces of the negative electrode active material layer 12 are entirely covered with the pair of LDH separators 14, the negative electrode structure 10 itself prevents a short circuit or the like due to zinc dendrite.
  • the negative electrode chamber of the zinc secondary battery can be simply configured in the form capable of preventing the extension of zinc dendrite. Therefore, when the negative electrode structure 10 of the present invention is employed for producing a zinc secondary battery, separation of the positive electrode and the negative electrode by the LDH separator can be realized simply by laminating the positive electrode plate and the negative electrode structure. In particular, when producing a laminated battery provided with a plurality of unit cells, it can be said to be extremely advantageous in that a desired configuration can be realized simply by alternately laminating the positive electrode plate and the negative electrode structure. This is because the LDH separator eliminates the need for the elaborate and careful sealing junction conventionally used to separate the positive and negative electrodes.
  • the negative electrode structure 110 is merely covered entirely on both sides of the negative electrode active material layer 112 with the pair of LDH separators 114.
  • an excess space E is formed between the LDH separator 114 and the negative electrode active material layer 112 in the vicinity of the sealing end 114 b of the LDH separator 114. If the surplus space E is large, not only the battery case is enlarged and the volumetric energy density is lowered, but also precipitation of a large amount of zinc dendrite in the surplus space E is permitted.
  • the negative electrode structure 10 of the present invention as shown in FIG.
  • the separation distance between the pair of LDH separators 14 is configured to decrease toward the sealing end 14 b such that the surplus portion 14 a of the pair of LDH separators 14 and the vicinity thereof conform to the tapered cross-sectional shape ing.
  • the surplus space E in negative electrode structure 10 is reduced, a battery case can be miniaturized, and volume energy density can be improved with miniaturization of a battery case. Further, as the surplus space E is smaller, the room for precipitation and growth of the amount of zinc dendrite in the surplus space E is minimized, so that zinc dendrite precipitation in the negative electrode structure 10 can be suppressed. Furthermore, as the surplus space E is smaller, the amount of the LDH separator 14 required to partition the surplus space E can be reduced, so the amount of separator material used can be reduced.
  • the tapered cross-sectional shape and the cross-sectional shape of the pair of LDH separators 14 conforming thereto are obtained by compression of the end of the laminated portion of the LDH separator 14 and the negative electrode active material layer 12 It is preferable that the surplus space E formed by the surplus part of the LDH separator 14 and the end of the negative electrode active material layer 12 be minimized. In this way, it is possible to desirably realize the minimization of the surplus space E by a very simple method of end compression. Also, by thus minimizing the surplus space E, the advantages of the above i), ii) and iii) can be realized more effectively.
  • the compression of the end portion may be performed by a known method such as sandwiching and pressing the end portion with a pair of plates, for example, and is not particularly limited.
  • At least one side, preferably at least two sides, of the outer edge of the LDH separator 14 is preferably sealed. Therefore, three sides of the outer edge of the LDH separator 14 may be sealed.
  • Preferred examples of sealing techniques include adhesives, heat welding, ultrasonic welding, adhesive tapes, sealing tapes, and combinations thereof.
  • FIG. 2 schematically shows a sealing end 14 b ′ sealed with a sealing tape
  • FIG. 3 schematically shows a sealing end 14 b ′ ′ sealed with an adhesive 15.
  • the LDH separator 14 including the porous base material made of a polymer material has the advantage of being flexible due to its flexibility, the outer edge is formed by forming the LDH separator 14 in a long shape and bending it.
  • heat welding and ultrasonic welding may be performed using a commercially available heat sealer or the like, when the liquid holding member 16 is used, the outer peripheral portion of the liquid holding member 16 is sandwiched between the LDH separators 14 constituting the outer peripheral portion. It is preferable to perform heat welding and ultrasonic welding in that the sealing can be performed more effectively.
  • a commercial item may be used for an adhesive agent, an adhesive tape, and a sealing tape, in order to prevent deterioration in an alkaline electrolyte solution, what contains resin which has alkali resistance is preferable.
  • examples of preferable adhesives include epoxy resin adhesives, natural resin adhesives, modified olefin resin adhesives, and modified silicone resin adhesives, among which epoxy resin adhesives are resistant It is more preferable in that it is particularly excellent in alkalinity.
  • an epoxy adhesive Hysol registered trademark (manufactured by Henkel) may be mentioned.
  • a negative electrode structure for a zinc secondary battery An anode active material layer comprising at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy and a zinc compound, A pair of layered double hydroxide (LDH) separators, which entirely cover both surfaces of the negative electrode active material layer and have an extra portion extending beyond the end of the negative electrode active material layer; Equipped with At least one side of the outer edge of the pair of LDH separators is sealed to form a sealed end, At least one side of the outer edge of the negative electrode active material layer adjacent to the sealing end has a tapered cross-sectional shape in which the thickness decreases toward the outer edge of the negative electrode active material layer, The separation distance of the pair of LDH separators is configured to decrease toward the sealing end in such a manner that the surplus portion of the pair of LDH separators and the vicinity thereof conform to the tapered cross-sectional shape , Negative electrode structure.
  • LDH layered double hydroxide
  • the pores of the porous substrate may be such that the LDH separator includes an LDH and a porous substrate made of a polymer material, and the LDH separator exhibits hydroxide ion conductivity and gas impermeability.
  • the negative electrode structure according to any one of Items A1 to A4, which is [Section A6] The negative electrode structure according to Item A5, wherein the LDH is incorporated throughout the thickness of the porous substrate.
  • the negative electrode active material layer and the LDH separator each have a quadrilateral shape, and at least two sides of the outer edge of the LDH separator are sealed to form a sealed end. body.
  • the negative electrode structure further includes a current collector in contact with the negative electrode active material layer, and the current collector has a current collector extension part extending from one side of the outer edge of the negative electrode active material layer, The tip of the current collector extension portion forms an exposed portion not covered by the LDH separator, provided that the sealed side is a side not in contact with the current collector extension portion
  • the negative electrode structure according to any one of the above.
  • the negative electrode active material layer 17 which was initially square, shrinks non-uniformly toward the center as charge and discharge are repeated, that is, the negative electrode active material layer 17 (ZnO)
  • the phenomenon that the outer part of the layer is eroded unevenly and lost is observed.
  • Such a change in shape of the negative electrode active material layer 17 leads to a decrease in the effective region of the negative electrode facing the positive electrode plate, resulting in an increase in battery resistance and a decrease in battery capacity.
  • the present inventors in a zinc secondary battery provided with an LDH separator, a positive electrode reaction suppression structure for suppressing an electrochemical reaction at an end of the positive electrode active material layer, and / or a positive electrode active material layer of a negative electrode active material layer.
  • an object of the present invention is to prevent the shape change of the negative electrode plate accompanying repetition of charge and discharge in a zinc secondary battery capable of preventing zinc dendrite extension provided with an LDH separator.
  • a positive electrode plate including a positive electrode active material layer and a positive electrode current collector, A negative electrode plate comprising a negative electrode active material layer comprising at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy and a zinc compound, and a negative electrode current collector, A layered double hydroxide (LDH) separator, which separates the positive electrode plate and the negative electrode plate so as to allow hydroxide ion conduction;
  • An electrolytic solution A zinc secondary battery provided with The size of the negative electrode active material layer is larger than the size of the positive electrode active material layer, whereby the negative electrode active material layer has an extra peripheral region along the outer periphery thereof not facing the positive electrode active material layer,
  • the zinc secondary battery has a positive electrode reaction suppression structure that suppresses an electrochemical reaction at an end of the positive electrode active material layer, and / or suppresses an electrochemical reaction in the surplus outer peripheral region of the negative electrode active material layer.
  • a zinc secondary battery having a negative electrode reaction suppression structure, whereby the electrochemical activity at the
  • the zinc secondary battery of the present invention is schematically shown in FIG.
  • the zinc secondary battery shown in FIG. 12 includes a battery element 11, which includes a positive electrode plate 12, a negative electrode plate 16, a layered double hydroxide (LDH) separator 22, and an electrolyte (not shown). ).
  • the positive electrode plate 12 includes a positive electrode active material layer 13 and a positive electrode current collector 14.
  • the negative electrode plate 16 includes a negative electrode active material layer 17 and a negative electrode current collector 18, and the negative electrode active material layer 17 includes at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy, and a zinc compound.
  • the LDH separator 22 separates the positive electrode plate 12 and the negative electrode plate 16 so as to allow hydroxide ion conduction.
  • LDH separator is a separator containing LDH and is defined as selectively passing hydroxide ions utilizing exclusively hydroxide ion conductivity of LDH.
  • the size of the negative electrode active material layer 17 is larger than the size of the positive electrode active material layer 13, so that the negative electrode active material layer 17 has an extra peripheral region along which the positive electrode active material layer 13 does not face.
  • a zinc secondary battery has the positive electrode reaction suppression structure 15 which suppresses the electrochemical reaction in the edge part of the positive electrode active material layer 13, and / or suppresses the electrochemical reaction in the excessive outer periphery area
  • the negative electrode reaction suppression structure 19 is provided.
  • the electrochemical activity at the end of the positive electrode active material layer 13 and / or the surplus outer peripheral region of the negative electrode active material layer 17 is locally reduced.
  • the shape change of the negative electrode plate 16 in particular, the negative electrode active material layer 17
  • the zinc secondary battery of the present invention can be provided with the LDH separator 22 to prevent zinc dendrite extension, thereby preventing a short circuit between positive and negative electrodes.
  • the negative electrode active material layer 17 may be covered with a liquid holding member 20 such as a non-woven fabric, but since the liquid holding member 20 passes the electrolyte solution 21, the space between the liquid holding member 20 and the negative electrode active material layer 17 It can be said that the space formed in the space also allows the presence of the excess electrolyte 21 and becomes a dead space DS. And since there is excess electrolyte solution 21 in this dead space DS, as shown in the cross-sectional view in the lower part of FIG. 13, zincate ion Zn (OH) 4 2 ⁇ which is a component of electrolyte solution 21. It will be present in excess. And, as shown in “charging” (second from left) in FIG.
  • the negative electrode active material layer 17 (ZnO layer), which was initially square, is directed toward the center (in the figure, as shown in “charging” on the right end of FIG. In the direction of the arrow in the photograph, the non-uniform contraction occurs, that is, the outer peripheral portion of the negative electrode active material layer 17 is non-uniformly eroded and lost.
  • the shape change of the negative electrode plate 16 due to the repetition of charge and discharge is concentrated of the metal Zn at the end of the negative electrode active material layer 17 (ZnO layer) due to the extra electrolyte 21 in the dead space DS at the time of charge reaction. It is believed that this is caused by the precipitation of Zn, and the metal Zn diffuses as Zn (OH) 4 2- at the time of discharge reaction and precipitates as ZnO at the central portion of the negative electrode.
  • the gap between the end portions of the positive electrode active material layer 13 and the negative electrode active material layer 17 is also considered. That is, in the zinc secondary battery, in order to suppress an increase in reaction precipitates at the end of the negative electrode active material layer 17 due to current concentration at the end of the positive electrode active material layer 13, the size of the negative electrode active material layer 17 is Although it is desirable to design the cathode active material layer 13 to be slightly larger than the size of the cathode active material layer 13, an extra peripheral region ER in which the anode active material layer 17 does not face the cathode active material layer 13 is formed along the periphery thereof. Become. Then, as shown in FIG.
  • the positive electrode which suppresses the electrochemical reaction at the end of the positive electrode active material layer 13 It can be said effective to provide the reaction suppression structure 15 or to provide the negative electrode reaction suppression structure 19 for suppressing the electrochemical reaction in the surplus outer peripheral region ER of the negative electrode active material layer 17.
  • the positive electrode reaction suppression structure 15 is not particularly limited as long as it can selectively and locally suppress the electrochemical reaction at the end of the positive electrode active material layer 13, and any structure or material may be used.
  • the negative electrode reaction suppression structure 19 is not particularly limited as long as it can selectively and locally suppress the electrochemical reaction in the surplus outer peripheral region ER of the negative electrode active material layer 17, and any structure or material can be used. It is also good. As a result, the electrochemical activity in the end portion of the positive electrode active material layer 13 and / or the surplus outer peripheral region ER of the negative electrode active material layer 17 is locally reduced, so that the negative electrode plate 16 (in particular, the negative electrode active material layer 17
  • the above-mentioned factor causing the shape change of i.e., excessive electrochemical reaction at or near the electrode end
  • the shape change of the negative electrode plate due to repeated charge and discharge can be prevented.
  • the zinc secondary battery 10 has both the positive electrode reaction suppression structure 15 and the negative electrode reaction suppression structure 19, whereby the end of the positive electrode active material layer 13 and the negative electrode active It is more preferable that the electrochemical activity in both of the surplus outer peripheral region ER of the material layer 17 be locally reduced.
  • the zinc secondary battery has the positive electrode reaction suppression structure 15 adjacent to the end of the positive electrode active material layer 13.
  • the positive electrode reaction suppression structure 15 includes an inactive member made of an electrochemically inactive material, and the inactive member covers the end of the positive electrode active material layer 13.
  • the shape of the inactive member is not particularly limited, and may be film-like or bulk-like.
  • the inactive member form a spacer that is adjacent to the end of the positive electrode plate 12 and closes the region facing the extra peripheral region ER of the negative electrode plate 16.
  • the electrochemically inactive material used for the positive electrode reaction suppression structure 15 is preferably a polymer material, and as a preferable example of such a polymer material, an alkaline solution such as polypropylene, polyolefin, polyethylene, epoxy, etc. Among them are resins exhibiting durability.
  • FIG. 16A and 16B An example of the method of providing the positive electrode reaction suppression structure 15 with the liquid retaining member 20 in the positive electrode plate 12 is shown by FIG. 16A and 16B. In this method, as shown in FIG. 16A, a liquid holding member 20 such as a non-woven fabric is placed in a rectangular recess of a tray-like mold 23, and a positive electrode plate 12 of a smaller size is placed on the liquid holding member 20. To place a margin along the three outer sides.
  • the hot melt adhesive is filled in the margin (exposed part of the liquid retaining member 20) along the three outer sides of the positive electrode plate 12 to form a spacer as the positive electrode reaction suppression structure 15.
  • a liquid holding member 20 such as a non-woven fabric is placed to cover the positive electrode reaction suppression structure 15 and the positive electrode plate 12.
  • the pressure plate 25 is placed on the liquid holding member 20 and pressurized to adjust the entire shape of the positive electrode structure into a flat plate having a uniform thickness, and then the mold 23 and the pressure plate 25 are removed.
  • a positive electrode structure provided with the liquid member 20 and the positive electrode reaction suppression structure 15 is obtained.
  • the mold 23 and the pressing plate 25 may be made of a material that can be easily removed from the hot melt adhesive, and is preferably made of Teflon (registered trademark).
  • the adhesive is not limited to the hot melt adhesive, and a wide variety of adhesives can be used.
  • zinc secondary battery 10 may have a negative electrode reaction suppression structure adjacent to surplus outer peripheral region ER of negative electrode active material layer 17.
  • the negative electrode reaction suppression structure includes an inactive member made of an electrochemically inactive material, and the inactive member covers the surplus outer peripheral region ER of the negative electrode active material layer.
  • the shape of the inactive member is not particularly limited, and may be film-like or bulk-like.
  • the electrochemically inactive material used for the negative electrode reaction suppression structure is preferably a polymer material, and preferable examples of such a polymer material include an alkaline solution such as polypropylene, polyolefin, polyethylene, epoxy, etc. And resins that exhibit durability.
  • the battery element 11 of the zinc secondary battery of the present invention includes a positive electrode plate 12, a negative electrode plate 16, an LDH separator 22, and an electrolytic solution (not shown).
  • the positive electrode plate 12 includes a positive electrode active material layer 13.
  • the positive electrode active material layer 13 may be appropriately selected from known positive electrode materials according to the type of zinc secondary battery, and is not particularly limited. For example, in the case of a nickel zinc secondary battery, a positive electrode containing nickel hydroxide and / or nickel oxyhydroxide may be used. Alternatively, in the case of an air zinc secondary battery, the air electrode may be used as the positive electrode.
  • the positive electrode plate 12 further includes a positive electrode current collector (not shown).
  • the positive electrode current collector preferably has a positive electrode current collecting tab 14 a extending from one side of the positive electrode active material layer 13.
  • a preferable example of the positive electrode current collector is a porous substrate made of nickel such as a foamed nickel plate.
  • a positive electrode plate composed of a positive electrode / positive electrode current collector can be preferably produced.
  • the positive electrode plate 12 shown in FIG. 12 contains a positive electrode current collector (for example, foamed nickel), but is not shown. This is because the positive electrode current collector is integrated with the positive electrode active material layer 13 so that the positive electrode current collector can not be drawn separately.
  • the zinc secondary battery 10 preferably further includes a positive electrode current collector plate connected to the tip of the positive electrode current collector tab 14a, and more preferably, a plurality of positive electrode current collector tabs 14a are connected to one positive electrode current collector plate .
  • a positive electrode current collector plate connected to the tip of the positive electrode current collector tab 14a, and more preferably, a plurality of positive electrode current collector tabs 14a are connected to one positive electrode current collector plate .
  • the positive electrode current collector itself may be used as a positive electrode terminal.
  • the negative electrode plate 16 includes a negative electrode active material layer 17.
  • the negative electrode active material layer 17 contains at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy, and a zinc compound. That is, zinc may be contained in any form of zinc metal, zinc compound and zinc alloy as long as it has electrochemical activity suitable for the negative electrode.
  • Preferred examples of the negative electrode material include zinc oxide, zinc metal, calcium zincate and the like, and a mixture of zinc metal and zinc oxide is more preferable.
  • the negative electrode active material layer 17 may be formed in a gel form, or may be mixed with an electrolytic solution to form a negative electrode mixture.
  • a gelled negative electrode can be easily obtained by adding an electrolytic solution and a thickener to the negative electrode active material. Examples of the thickener include polyvinyl alcohol, polyacrylate, CMC, alginic acid and the like, and polyacrylic acid is preferable because it is excellent in chemical resistance to strong alkali.
  • a mercury-free and lead-free zinc alloy known as a zinc-free zinc alloy.
  • a zinc alloy containing 0.01 to 0.1% by mass of indium, 0.005 to 0.02% by mass of bismuth, and 0.0035 to 0.015% by mass of aluminum has the effect of suppressing the generation of hydrogen gas So preferred.
  • Indium and bismuth are particularly advantageous in improving the discharge performance.
  • the use of the zinc alloy for the negative electrode can improve the safety by suppressing the generation of hydrogen gas by reducing the self-dissolution rate in the alkaline electrolyte.
  • the shape of the negative electrode material is not particularly limited, but is preferably in the form of powder, whereby the surface area is increased and it becomes possible to cope with high current discharge.
  • the average particle diameter of the preferred negative electrode material is in the range of 3 to 100 ⁇ m in the short diameter, and within this range, the surface area is large, so that it is suitable for large current discharges. It is easy to mix uniformly with the agent, and the handling at the time of battery assembly is also good.
  • the negative electrode plate 16 further includes a negative electrode current collector 18.
  • the negative electrode current collector 18 preferably has a negative electrode current collection tab 18 a extending from one side of the negative electrode active material layer 17. As shown in FIG. 12, the negative electrode current collection tab 18a extends beyond the end of the LDH separator 22 from one side of the negative electrode active material layer 17 opposite to the positive electrode current collection tab 14a. In this case, the battery element 11 can collect current from opposite sides through the positive electrode current collecting tab 14a and the negative electrode current collecting tab 18a. Alternatively, the negative electrode current collection tab 18a may extend beyond the end of the LDH separator 22 from a different position on one side of the negative electrode active material layer 17 on the same side as the positive electrode current collection tab 14a.
  • the battery element 11 can collect current from the same side via the positive electrode current collecting tab 14a and the negative electrode current collecting tab 18a.
  • the zinc secondary battery 10 preferably further includes a negative electrode current collector plate connected to the tip of the negative electrode current collector tab 18a, and more preferably, a plurality of negative electrode current collector tabs 18a is one negative electrode current collector Connected to the board. In this way, current collection can be performed space-efficiently with a simple configuration, and connection to the negative electrode terminal can be facilitated.
  • the negative electrode current collector itself may be used as a negative electrode terminal.
  • the tip end portion of the negative electrode current collection tab 18 a forms an exposed portion not covered by the LDH separator 22 and the liquid retaining member 20 (if present). Thereby, the negative electrode current collector 18 (particularly, the negative electrode current collection tab 18a) can be desirably connected to the negative electrode current collector plate and / or the negative electrode terminal through the exposed portion.
  • the entire negative electrode active material layer 17 be covered with the LDH separator 22. That is, the separation of the positive electrode and the negative electrode by the LDH separator in the conventional zinc secondary battery is cleverly and carefully sealed and joined using a resin frame, an adhesive and the like so as to ensure liquid tightness between the LDH separator and the battery container. It was easy to make the battery configuration and the manufacturing process complicated. Such complication of the battery configuration and the manufacturing process can be particularly remarkable in the case of constructing a laminated battery. In this respect, when the entire negative electrode active material layer 17 is covered with the LDH separator 22, the negative electrode plate 16 itself covered with the LDH separator 22 has a function capable of preventing a short circuit or the like due to zinc dendrite.
  • separation of the positive electrode plate 12 and the negative electrode plate 16 by the LDH separator can be realized only by laminating the positive electrode plate 12 and the negative electrode plate 16 (which is covered with the LDH separator 22).
  • the complicated sealing and bonding between the LDH separator 22 and the battery container is eliminated. It is possible to produce a zinc secondary battery (particularly, a laminated battery thereof) capable of preventing the extension of zinc dendrite extremely easily and with high productivity.
  • the negative electrode reaction suppression structure 19 can be configured by the LDH separator 22 itself. That is, the negative electrode reaction suppression structure 19 has a structure in which the LDH separator 22 and the end of the negative electrode active material layer 17 are in direct or indirect contact with each other, whereby the LDH separator 22 and the negative electrode active material layer 17 are It is preferable that there is no excess space between the end and the electrolyte solution. That is, as described with reference to FIG.
  • the negative electrode active material layer 17 (ZnO layer) is The shape change of the negative electrode plate 16 is caused by the metal Zn being intensively precipitated at the end and being diffused as Zn (OH) 4 2- at the time of the discharge reaction and being diffused as ZnO at the central portion of the negative electrode. It can cause. Therefore, by eliminating the excess space that allows electrolyte solution accumulation, it is possible to effectively prevent the shape change of the negative electrode plate 16 (particularly, the negative electrode active material layer 17) due to the repetition of charge and discharge.
  • a liquid retaining member 30 may be present between the LDH separator 22 and the end of the negative electrode active material layer 17 so as not to provide an excess space for allowing electrolyte solution accumulation.
  • the resin may be filled between the LDH separator 22 and the end of the negative electrode active material layer 17 to eliminate an excess space for allowing the electrolyte solution to be accumulated.
  • the LDH separator 22 includes LDH and a porous substrate.
  • the pores of the porous substrate are such that the LDH separator 22 exhibits hydroxide ion conductivity and gas impermeability (so that it functions as an LDH separator exhibiting hydroxide ion conductivity) Blocking
  • the porous substrate is preferably made of a polymeric material, and the LDH is particularly preferably incorporated throughout the thickness direction of the polymeric porous substrate. Various preferred embodiments of the LDH separator 22 will be described in detail later.
  • the LDH separator 22 has at least one side (preferably at least two sides) of its outer edge so as to wrap the negative electrode active material layer 17 as shown in FIG. It is a closed structure.
  • the closed side C of the outer edge of the LDH separator 22 be realized by bending the LDH separator 22 and / or sealing the LDH separators 22 with each other.
  • sealing techniques include adhesives, heat welding, ultrasonic welding, adhesive tapes, sealing tapes, and combinations thereof.
  • the outer edge is formed by forming the LDH separator 22 in a long shape and bending it.
  • one side C of the two forms a closed state.
  • heat welding and ultrasonic welding may be performed using a commercially available heat sealer or the like, in the case of sealing the LDH separators 22 with each other, the outer peripheral portion of the liquid retaining member 20 is sandwiched between the LDH separators 22 forming the outer peripheral portion. It is preferable to perform heat welding and ultrasonic welding in this manner in that more effective sealing can be performed.
  • an adhesive agent an adhesive tape, and a sealing tape
  • an adhesive agent an adhesive tape, and a sealing tape
  • preferable adhesives include epoxy resin adhesives, natural resin adhesives, modified olefin resin adhesives, and modified silicone resin adhesives, among which epoxy resin adhesives are resistant It is more preferable in that it is particularly excellent in alkalinity.
  • an epoxy adhesive Hysol registered trademark (manufactured by Henkel) may be mentioned.
  • the whole of the positive electrode active material layer 13 may be covered with the LDH separator 22.
  • the positive electrode plate 12 itself covered with the LDH separator 22 can have a function capable of preventing a short circuit or the like due to zinc dendrite.
  • the zinc secondary battery 10 preferably further includes a liquid retaining member 20 between the LDH separator 22 and the positive electrode active material layer 13, and the liquid retaining member 20 is impregnated with an electrolytic solution. Is preferred.
  • the electrolyte preferably comprises an aqueous alkali metal hydroxide solution.
  • the electrolytic solution is not shown, it is because it extends throughout the positive electrode plate 12 (particularly, the positive electrode active material layer 13) and the negative electrode plate 16 (particularly, the negative electrode active material layer 17).
  • the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide and the like, with potassium hydroxide being more preferred.
  • a zinc compound such as zinc oxide or zinc hydroxide may be added to the electrolytic solution.
  • the electrolytic solution may be mixed with the positive electrode active material and / or the negative electrode active material to be present in the form of a positive electrode mixture and / or a negative electrode mixture.
  • the electrolytic solution may be gelled.
  • the gelling agent it is desirable to use a polymer which absorbs the solvent of the electrolytic solution to swell, and polymers such as polyethylene oxide, polyvinyl alcohol, polyacrylamide and starch are used.
  • the zinc secondary battery 10 may further include a case (not shown) for housing the battery element 11.
  • the number of battery elements 11 may be two or more, and the two or more battery elements 11 may be housed together in a case.
  • the case for housing the battery element 11 is preferably made of resin.
  • the resin constituting the case is preferably a resin having resistance to an alkali metal hydroxide such as potassium hydroxide, more preferably a polyolefin resin, an ABS resin, or a modified polyphenylene ether, still more preferably an ABS resin or a modified resin It is polyphenylene ether.
  • a case group in which two or more cases are arranged may be accommodated in the outer frame, and the battery module may be configured.
  • a positive electrode plate including a positive electrode active material layer and a positive electrode current collector, A negative electrode plate comprising a negative electrode active material layer comprising at least one selected from the group consisting of zinc, zinc oxide, a zinc alloy and a zinc compound, and a negative electrode current collector, A layered double hydroxide (LDH) separator, which separates the positive electrode plate and the negative electrode plate so as to allow hydroxide ion conduction;
  • An electrolytic solution A zinc secondary battery provided with The size of the negative electrode active material layer is larger than the size of the positive electrode active material layer, whereby the negative electrode active material layer has an extra peripheral region along the outer periphery thereof not facing the positive electrode active material layer,
  • the zinc secondary battery has a positive electrode reaction suppression structure that suppresses an electrochemical reaction at an end of the positive electrode active material layer, and / or suppresses an electrochemical reaction in the surplus outer peripheral region of the negative electrode active material layer.
  • a zinc secondary battery having a negative electrode reaction suppression structure whereby the electrochemical activity in the end portion of the positive electrode active material layer and / or the extra peripheral region of the negative electrode active material layer is locally reduced.
  • It has both the positive electrode reaction suppression structure and the negative electrode reaction suppression structure, thereby locally reducing the electrochemical activity in both the end of the positive electrode active material layer and the surplus outer peripheral region of the negative electrode active material layer.
  • the zinc secondary battery according to Item B1.
  • the zinc secondary battery has the positive electrode reaction suppression structure adjacent to an end of the positive electrode active material layer, and the positive electrode reaction suppression structure is formed of an electrochemically inactive material.
  • the zinc secondary battery according to Item B2 comprising an active member, wherein the inactive member covers an end of the positive electrode active material layer.
  • the zinc secondary battery according to Item B4 The zinc secondary battery according to Item B3, wherein the inactive member forms a spacer that is adjacent to an end of the positive electrode plate and closes a region facing the extra peripheral region of the negative electrode plate.
  • the electrochemically inactive material is a polymer material.
  • the zinc secondary battery has the negative electrode reaction suppression structure adjacent to the surplus outer peripheral region of the negative electrode active material layer, and the negative electrode reaction suppression structure is made of an electrochemically inactive material.
  • the electrochemically inactive material is a polymer material.
  • the entire negative electrode active material layer is covered with the LDH separator,
  • the negative electrode reaction suppression structure has a structure in which the LDH separator and an end portion of the negative electrode active material layer are in direct or indirect contact with each other, thereby the ends of the LDH separator and the negative electrode active material layer
  • the zinc secondary battery further includes a liquid holding member between the LDH separator and the negative electrode active material layer, and the liquid holding member is impregnated with the electrolytic solution.
  • the zinc secondary battery according to Item B10 The zinc secondary battery according to Item B9, wherein the liquid retaining member is a non-woven fabric.
  • the zinc secondary battery according to any one of to B10.
  • [Section B12] The zinc secondary battery according to Item B11, wherein the porous substrate is made of a polymer material.
  • the positive electrode active material layer contains nickel hydroxide and / or nickel oxyhydroxide, whereby the zinc secondary battery constitutes a nickel zinc secondary battery. battery.
  • the positive electrode active material layer is an air electrode layer, whereby the zinc secondary battery forms an air zinc secondary battery.

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Abstract

L'invention concerne une structure d'électrode négative qui permet de préparer, avec une simplicité et une productivité élevées, une batterie secondaire au zinc (en particulier, une batterie stratifiée de celle-ci) capable d'empêcher l'extension de dendrite de zinc. La structure d'électrode négative selon la présente invention comprend : une couche de matériau actif d'électrode négative qui contient au moins un type choisi dans le groupe constitué par le zinc, l'oxyde de zinc, un alliage de zinc et un composé de zinc ; et une couche composite qui contient soit un élément de retenue de liquide et un hydroxyde double lamellaire (LDH), ou un élément de retenue de liquide, un hydroxyde double lamellaire (LDH), et un substrat poreux, et recouvre ou enveloppe la totalité de la couche de matériau actif d'électrode négative. Le LDH remplit au moins une partie des pores de l'élément de retenue de liquide et/ou du substrat poreux de manière à fonctionner comme séparateur LDH, au moins une partie de la couche composite dans le sens de l'épaisseur présentant une conductivité d'ions hydroxyde et une imperméabilité au gaz.
PCT/JP2018/035647 2017-10-03 2018-09-26 Structure d'électrode négative pour batterie secondaire au zinc WO2019069760A1 (fr)

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CN115461923B (zh) * 2020-05-11 2024-02-06 日本碍子株式会社 Ldh隔板及锌二次电池
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CN115020706B (zh) * 2022-05-30 2023-06-09 西南科技大学 水系锌离子电池、辊压锂皂石@锌负极材料及其制备方法

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