[go: up one dir, main page]

WO2018135117A1 - Structure de séparateur, batterie secondaire nickel-zinc et batterie secondaire zinc-air - Google Patents

Structure de séparateur, batterie secondaire nickel-zinc et batterie secondaire zinc-air Download PDF

Info

Publication number
WO2018135117A1
WO2018135117A1 PCT/JP2017/041082 JP2017041082W WO2018135117A1 WO 2018135117 A1 WO2018135117 A1 WO 2018135117A1 JP 2017041082 W JP2017041082 W JP 2017041082W WO 2018135117 A1 WO2018135117 A1 WO 2018135117A1
Authority
WO
WIPO (PCT)
Prior art keywords
ldh
separator
adhesive
porous substrate
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/041082
Other languages
English (en)
Japanese (ja)
Inventor
直美 橋本
雅晴 梶田
恵里 浅野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2018562900A priority Critical patent/JP6803927B2/ja
Publication of WO2018135117A1 publication Critical patent/WO2018135117A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • 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 separator structure, a nickel zinc secondary battery, and a zinc-air secondary battery.
  • zinc secondary batteries such as nickel zinc secondary battery and air zinc secondary battery
  • metallic zinc is deposited in a dendrite shape from the negative electrode during charging, and reaches the positive electrode through the voids of a separator such as a nonwoven fabric. It is known to cause a short circuit. Such short circuit due to zinc dendrite repeatedly shortens the charge / discharge life.
  • Patent Document 1 International Publication No. 2013/118561 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 density enough to have water impermeability.
  • an LDH separator is used in the form of a composite plate combined with a porous substrate.
  • Patent Document 3 International Publication No. 2016/039349 discloses a configuration in which an LDH separator is bonded to a resin outer frame via an adhesive.
  • epoxy resin adhesives from the viewpoint of adhesiveness and alkali resistance, epoxy resin adhesives, natural resin adhesives, modified olefin resins are used for resin outer frames made of ABS resin, modified polyphenylene ether, and polypropylene resin.
  • An adhesive selected from a base adhesive and a modified silicone resin adhesive is used.
  • the LDH separator as described above can effectively prevent a short circuit between positive and negative electrodes due to zinc dendrite in a nickel-zinc battery, but further improvement in the performance of the nickel-zinc battery is desired.
  • the bonding portion between the composite plate including the LDH separator and the porous substrate and the resin outer frame Improvement of airtightness or liquid tightness is desired.
  • the porous base material side of the composite plate and the concave portion of the resin outer frame are now used.
  • the inventors obtained knowledge that an LDH separator structure excellent in reliability and durability can be provided by facing the surface and deeply soaking the adhesive into the porous substrate.
  • an object of the present invention is to improve reliability and durability in a separator structure including an LDH separator with a porous substrate in a resin outer frame.
  • a separator structure for a zinc secondary battery A composite plate comprising a layered double hydroxide (LDH) separator and a porous substrate provided on one side of the LDH separator; A resin outer frame having an opening into which the composite plate is fitted; With The resin outer frame has a recess that locks the porous substrate side of the composite plate along its inner periphery, and the recess and the composite plate are sealed and bonded with an adhesive,
  • the porous substrate has a thickness of 100 ⁇ m or more, and a portion of the porous substrate that faces the recess is infiltrated with the adhesive over a depth of 100 ⁇ m or more from the surface of the porous substrate.
  • a separator structure is provided.
  • a positive electrode comprising nickel hydroxide and / or nickel oxyhydroxide
  • a negative electrode comprising zinc, a zinc alloy and / or zinc oxide
  • An electrolyte containing an alkali metal hydroxide aqueous solution Separating the positive electrode and the negative electrode so that hydroxide ions can be conducted; and
  • a nickel zinc secondary battery is provided.
  • an air electrode comprising zinc, a zinc alloy and / or zinc oxide
  • An electrolyte containing an alkali metal hydroxide aqueous solution The separator structure for separating the air electrode and the negative electrode so that hydroxide ions can be conducted; and A zinc-air secondary battery is provided.
  • FIG. 2 is an enlarged view microscopically illustrating an adhesion portion of the separator structure shown in FIG. 1. It is a SEM image which shows the surface microstructure of the functional layer produced in Example A1. It is a SEM image which shows the cross-sectional microstructure of the functional layer produced in Example A1. It is a cross-sectional SEM image of the porous base material soaked with the adhesive agent produced in Example B1. FIG. 3B is a cross-sectional SEM image obtained by magnifying and observing the penetration interface portion shown in FIG. 3A. It is the photograph which image
  • FIG. 4B is a cross-sectional SEM image obtained by magnifying and observing the penetration interface portion shown in FIG. 4A. It is the photograph which image
  • FIG. 5 is an exploded perspective view of a measurement sealed container used in a denseness determination test of Examples B1 to B5.
  • FIG. 3 is a schematic cross-sectional view of a measurement system used in a denseness determination test of Examples B1 to B5.
  • FIG. 8B is a schematic cross-sectional view of a sample holder used in the measurement system shown in FIG. It is a figure which shows the structure of the sample produced in the tensile strength test of Examples B1-B6. It is a schematic cross section which shows the conventional separator structure. It is an enlarged view of the adhesion part of the separator structure shown by FIG. 8A.
  • FIG. 8B is a schematic cross-sectional view showing a separator structure in which the directions of the LDH separator and the porous substrate are reversed in the separator structure shown in FIG. 8A. It is an enlarged view of the junction part of the separator structure shown by FIG. 9A.
  • the separator structure of the present invention is used for a zinc secondary battery.
  • the zinc secondary battery is a nickel zinc secondary battery, a silver zinc oxide secondary battery, a manganese zinc secondary battery, a zinc-air secondary battery, and various other types of alkaline zinc secondary batteries, such as LDH separators.
  • a nickel zinc secondary battery and a zinc-air secondary battery are preferable, and a nickel zinc battery is particularly preferable.
  • a battery to which the separator structure can be applied may be a unit battery having a pair of a positive electrode and a negative electrode, or a stacked battery including two or more pairs of a positive electrode and a negative electrode, that is, two or more unit cells. May be.
  • the stacked battery may be a series-type stacked battery or a parallel-type stacked battery.
  • a zinc secondary battery in which the separator structure of the present invention is incorporated includes a positive electrode, a negative electrode, an electrolytic solution, and a separator structure. What is necessary is just to select a positive electrode and a negative electrode suitably according to the kind of secondary battery, respectively.
  • the positive electrode includes nickel hydroxide and / or nickel oxyhydroxide
  • the negative electrode includes zinc, a zinc alloy, and / or zinc oxide.
  • the positive electrode is an air electrode
  • the negative electrode contains zinc, a zinc alloy, and / or zinc oxide.
  • the separator structure is a structure including an LDH separator, and is provided so as to isolate the positive electrode and the negative electrode so as to conduct hydroxide ions.
  • a typical electrolyte includes an aqueous alkali metal hydroxide solution.
  • the separator structure 10 includes a composite plate 12 and a resin outer frame 18.
  • the composite plate 12 includes an LDH separator 14 and a porous substrate 16 provided on one side of the LDH separator 14.
  • the resin outer frame 18 includes an opening 18a, and the composite plate 12 is fitted into the opening 18a.
  • the resin outer frame 18 has a concave portion 18b that locks the porous substrate 16 side of the composite plate 12 along its inner periphery, and the concave portion 18b and the composite plate 12 are sealed and bonded with an adhesive 20. .
  • the porous substrate 16 has a thickness of 100 ⁇ m or more, and the portion facing the concave portion 18b of the porous substrate 16 is 100 ⁇ m from the surface of the porous substrate 16 as depicted in an enlarged view in FIG.
  • the adhesive 20 is soaked over the depth D described above.
  • the fact that the adhesive 20 soaks into the porous substrate 16 means that the pores in the porous substrate 16 are filled with the adhesive 20.
  • the composite plate 12 including the LDH separator 14 and the porous base material 16 is sealed and bonded to the resin outer frame 18 with the adhesive 20, the porous base material 16 side of the composite plate 12 is connected to the resin outer frame. Reliability and durability can be improved by facing the 18 recesses 18b and deeply soaking the adhesive 20 into the porous substrate 16.
  • FIG. 8A a separator structure in which the composite plate 12 is sealed and bonded to the resin outer frame 18 with the LDH separator 14 side facing the concave portion 18b of the resin outer frame 18 is already present.
  • It is known see, for example, Patent Document 2. That is, a structure in which the LDH separator 14 side of the composite plate 12 is positioned on the narrow side of the opening 18a and the porous substrate 16 side of the composite plate 12 is positioned on the wide side of the opening 18a is already known.
  • the LDH separator 14 and the resin outer frame 18 are bonded via the adhesive 20, so that a dense and excellent airtight or liquid-tight property as shown in FIG.
  • the direction of the composite plate 12 is reversed, specifically, the porous base material 16 side is opposed to the concave portion 18b of the resin outer frame 18.
  • a configuration in which the resin outer frame 18 is sealed and joined is conceivable. That is, the LDH separator 14 side of the composite plate 12 is positioned on the wide side of the opening 18a, and the porous substrate 16 side of the composite plate 12 is positioned on the narrow side of the opening 18a.
  • the zinc dendrite that develops from the negative electrode 24 during charging grows in a direction (compression direction; indicated by an arrow in FIG. 9A) that presses the bonded portion toward the concave portion 18b. improves.
  • FIG. 9A compression direction
  • the portion of the porous substrate 16 that faces the recess 18 b is the surface of the porous substrate 16.
  • the porous substrate 16 side of the composite plate 12 is opposed to the concave portion 18b of the resin outer frame 18, and the adhesive 20 is deeply soaked into the porous substrate 16, thereby improving reliability and durability.
  • the adhesive 20 (preferably an alkali-resistant resin) is deeply infiltrated into the porous substrate 16, the porous substrate 16 is porous even if the contact area between the LDH separator 14 and the adhesive 20 is extremely small. Airtightness and liquid-tightness can be ensured by the portion filled with the adhesive 20 of the base material 16, and high reliability of the bonded portion is ensured. In addition, since the adhesive 20 penetrates deeply into the porous base material 16, an improvement in the adhesive strength can be expected. Although this structure can be said to be a structure in which the adhesive 20 (preferably an alkali-resistant resin) has penetrated the end face of the porous substrate 16, the adhesive 20 is bonded to the composite plate 12 (especially the porous substrate 16).
  • the adhesion interface in the separator structure 10 of the present invention is not an interface where the surfaces are merely two-dimensionally bonded, but is more difficult to peel off due to a more three-dimensional adhesion structure due to the penetration of the adhesive. .
  • the composite plate composite plate 12 includes an LDH separator 14 and a porous substrate 16 provided on one side of the LDH separator 14.
  • the LDH separator 14 is a separator containing layered double hydroxide (LDH), and separates the positive electrode plate and the negative electrode plate so as to conduct hydroxide ions when incorporated in a zinc secondary battery. That is, the LDH separator 14 functions as a hydroxide ion conductive separator.
  • a preferred LDH separator 14 is gas impermeable and / or water impermeable. In other words, the LDH separator 14 is preferably so dense that it has impermeability and / or water impermeability.
  • “having gas impermeability” means that the gas impermeability is evaluated by the “denseness determination test” employed in the evaluation 4 of Example A1 described later or a method or configuration equivalent thereto.
  • “having water impermeability” means that water that contacts one surface side of the measurement object (for example, LDH separator) does not permeate the other surface side (see, for example, Patent Document 2). ). That is, the fact that the LDH separator 14 has gas impermeability and / or water impermeability means that the LDH separator 14 has a high degree of denseness that does not allow gas or water to pass through, and has water permeability.
  • the LDH separator 14 can selectively pass only hydroxide ions due to its hydroxide ion conductivity, and can exhibit a function as a battery separator. For this reason, it has a very effective configuration for physically preventing penetration of the separator by zinc dendrite generated during charging and preventing a short circuit between the positive and negative electrodes. Since the LDH separator 14 has hydroxide ion conductivity, it enables efficient transfer of necessary hydroxide ions between the positive electrode plate and the negative electrode plate, and realizes a charge / discharge reaction in the positive electrode plate and the negative electrode plate. Can do.
  • the LDH separator 14 preferably has a He permeability per unit area of 10 cm / min ⁇ atm or less, more preferably 5.0 cm / min ⁇ atm or less, and even more preferably 1.0 cm / min ⁇ atm or less. . It can be said that the LDH separator having the He permeability in such a range has extremely high density. Therefore, an LDH separator having a He permeability of 10 cm / min ⁇ atm or less can prevent substances other than hydroxide ions from passing at a high level when applied as a separator in a zinc secondary battery. For example, permeation of zinc ions and / or zincate ions in the electrolytic solution can be extremely effectively suppressed.
  • the He permeability a process of supplying He gas to one side of the separator or the functional layer to allow the He gas to pass through the separator or the functional layer, and calculating the He permeability to evaluate the density of the separator or the functional layer. It is measured through the process.
  • the He permeability is F / (P ⁇ S) using the He gas permeation amount F per unit time, the differential pressure P applied to the separator or functional layer when He gas permeates, and the membrane area S through which He gas permeates.
  • He gas permeability index defined by the above-described formula
  • objective evaluation regarding the denseness can be easily performed regardless of differences in various sample sizes and measurement conditions. In this way, it is possible to simply, safely and effectively evaluate whether the LDH separator has sufficiently high density suitable for a zinc secondary battery separator.
  • the measurement of He permeability can be preferably performed according to the procedure shown in Evaluation 5 of Example A1 described later.
  • the LDH separator 14 preferably contains a layered double hydroxide (LDH), more preferably LDH.
  • 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 intermediate layer of LDH is composed of anions and H 2 O.
  • the anion is a monovalent or higher anion, preferably a monovalent or divalent ion.
  • the anion in LDH comprises OH - and / or CO 3 2- .
  • LDH has excellent ionic conductivity due to its inherent properties.
  • LDH is M 2+ 1-x M 3+ x (OH) 2 A n ⁇ x / n ⁇ mH 2 O (where M 2+ is a divalent cation and M 3+ is a trivalent cation).
  • a 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 a representative.
  • M 2+ may be any divalent cation, and preferred examples include Mg 2+ , Ca 2+ and Zn 2+ , and more preferably Mg 2+ .
  • M 3+ may be any trivalent cation, but preferred examples include Al 3+ or Cr 3+ , and more preferred is Al 3+ .
  • a n- 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 which means 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 basic composition formula is merely a formula of “basic composition” that is typically exemplified with respect to LDH in general, and the constituent ions can be appropriately replaced.
  • the constituent ions can be appropriately replaced.
  • it may be replaced with some or all of the M 3+ tetravalent or higher valency cations in the basic formula, in which case, the anion A coefficient of n-x / n in the general formula May be changed as appropriate.
  • the hydroxide base layer of LDH may be composed of Ni, Ti, OH groups and possibly inevitable impurities.
  • the intermediate layer of LDH is composed of an anion and H 2 O.
  • the alternate layered structure of the hydroxide basic layer and the intermediate layer itself is basically the same as the commonly known alternate layered structure of LDH, but the LDH of this embodiment is mainly composed of Ni, By comprising Ti and OH groups, excellent alkali resistance can be exhibited.
  • an element for example, Al
  • the LDH of this embodiment can also exhibit high ionic conductivity suitable for use as a separator for an alkaline secondary battery.
  • Ni in LDH can take the form of nickel ions.
  • the nickel ions in LDH are typically considered to be Ni 2+ , but are not particularly limited because other valences such as Ni 3+ may also exist.
  • 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 because other valences such as Ti 3+ may also exist.
  • Inevitable impurities are optional elements that can be inevitably mixed in the manufacturing process, and can be mixed in LDH, for example, derived from raw materials and base materials.
  • 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-n-valent anion, n is an integer of 1 or more, preferably 1 or 2, 0 ⁇ x ⁇ 1, preferably 0.01 ⁇ x ⁇ 0.5, m is 0 or more, typically greater than 0 or 1 or more real number).
  • the hydroxide basic layer of LDH may contain Ni, Al, Ti and OH groups.
  • the intermediate layer is composed of an anion and H 2 O.
  • the alternate layered structure of the hydroxide basic layer and the intermediate layer itself is basically the same as the generally known alternate layered structure of LDH, but the LDH of this embodiment uses the basic hydroxide layer of LDH as Ni, Al.
  • the LDH of this embodiment uses the basic hydroxide layer of LDH as Ni, Al.
  • the LDH of this embodiment is thought to be because Al, which was previously thought to be easily eluted in an alkaline solution, is less likely to be eluted in an alkaline solution due to some interaction with Ni and Ti.
  • the LDH of this embodiment can also exhibit high ionic conductivity suitable for use as a separator for an alkaline secondary battery.
  • Ni in LDH can take the form of nickel ions.
  • the nickel ions in LDH are typically considered to be Ni 2+ , but are not particularly limited because other valences such as Ni 3+ may also exist.
  • Al in LDH can take the form of aluminum ions.
  • Aluminum ions in LDH are typically considered to be Al 3+ , but are not particularly limited because other valences are possible.
  • 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 because other valences such as Ti 3+ may also exist.
  • 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 is preferably mainly composed of Ni, Al, Ti and OH groups. Therefore, the hydroxide base layer is typically composed of Ni, Al, Ti, OH groups and possibly inevitable impurities. Inevitable impurities are optional elements that can be inevitably mixed in the manufacturing process, and can be mixed in LDH, for example, derived from raw materials and base materials. As described above, since the valences of Ni, Al, and Ti are not necessarily certain, it is impractical or impossible to specify LDH strictly by a general formula.
  • 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-xy Al 3+ x Ti 4+ y (OH) 2 A n ⁇ (x + 2y) / n ⁇ mH 2 O
  • 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, 0 ⁇ y ⁇ 1, preferably 0.01 ⁇ y ⁇ 0.5, 0 ⁇ x + y ⁇ 1, m is 0 or more, typically 0.
  • the LDH separator 14 is combined with the porous substrate 16. That is, the LDH separator 14 may be a composite material including an LDH film and a porous substrate, or may be a composite material in which LDH is filled in the pores of the porous substrate (in this case, LDH There may be no film). A combination of both may also be used. That is, a configuration in which part of the LDH film is incorporated in the pores of the porous substrate may be used. In this case, the functional layer exhibiting the separator function is composed of a film-shaped portion made of an LDH film and a composite portion made of LDH and a porous substrate.
  • the porous substrate 16 has water permeability, and therefore, when incorporated in a zinc secondary battery, the electrolyte solution can reach the LDH separator 14. As a result, the hydroxide ions can be stably held by the LDH separator 14. Further, since the strength can be imparted by the porous substrate 16, the LDH separator 14 can be made thin to reduce the resistance.
  • the thickness of the porous substrate is 100 ⁇ m or more, preferably 100 to 600 ⁇ m, more preferably 100 to 500 ⁇ m, still more preferably 100 to 400 ⁇ m, particularly preferably 100 to 350 ⁇ m, and most preferably 100 to 300 ⁇ m. With such a thickness, sufficient strength can be imparted, and a deeper penetration portion of the adhesive 20 can be secured, thereby improving the air tightness or liquid tightness of the adhesive portion.
  • the porous substrate 16 is preferably composed of at least one selected from the group consisting of a ceramic material, a metal material, and a polymer material, more preferably a ceramic material and / or a polymer material, still more preferably. It is a polymer material. More preferably, the porous substrate is made of a ceramic material. In this case, preferable examples of the ceramic material include alumina, zirconia, titania, magnesia, spinel, calcia, cordierite, zeolite, mullite, ferrite, zinc oxide, silicon carbide, and any combination thereof, and more preferable.
  • Preferred examples of the metal material include aluminum, zinc, and nickel.
  • Preferred examples of the polymer material include polystyrene, polyethersulfone, polypropylene, epoxy resin, polyphenylene sulfide, hydrophilic fluororesin (tetrafluorinated resin: PTFE, etc.), cellulose, nylon, polyethylene, and any combination thereof. Is mentioned. It is more preferable to appropriately select a material excellent in alkali resistance as the resistance to the battery electrolyte from the various preferable materials described above.
  • the LDH separator 14 has an LDH film composed of an aggregate of a plurality of LDH plate-like particles, and the plurality of LDH plate-like particles have their plate surfaces on the surface of the porous substrate 16 (with a porous structure). It is oriented in a direction that intersects perpendicularly or obliquely with the main surface of the porous substrate when macroscopic observations resulting from negligible microscopic unevenness are observed.
  • the LDH film may be at least partially incorporated in the pores of the porous base material 16, and in that case, LDH plate-like particles may also exist in the pores of the porous base material 16.
  • LDH crystals are known to have the form of plate-like particles having a layered structure
  • the vertical or oblique orientation is a very advantageous property for the LDH separator 14.
  • the oriented LDH-containing separator has a much higher hydroxide ion conductivity in the direction in which the LDH plate-like particles are oriented (that is, the direction parallel to the LDH layer) than the conductivity in the direction perpendicular thereto. This is because of the conductivity anisotropy.
  • the conductivity (S / cm) in the orientation direction is one digit higher than the conductivity (S / cm) in the direction perpendicular to the orientation direction.
  • the above vertical or oblique alignment maximizes or significantly extracts the conductivity anisotropy that the LDH alignment body can have in the layer thickness direction (that is, the direction perpendicular to the surface of the LDH film or the porous substrate 16).
  • the conductivity in the layer thickness direction can be maximized or significantly increased.
  • the LDH film since the LDH film has a film form, lower resistance than the bulk form LDH can be realized. An LDH film having such an orientation easily conducts hydroxide ions in the layer thickness direction.
  • the LDH separator 14 preferably has a thickness of 100 ⁇ m or less, more preferably 75 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 25 ⁇ m or less, and most preferably 5 ⁇ m or less.
  • the resistance of the LDH separator 14 can be reduced.
  • the lower limit of the thickness of the LDH separator 14 is not particularly limited because it varies depending on the application, but in order to ensure a certain degree of rigidity desired as a functional film such as a separator, the thickness is preferably 1 ⁇ m or more. Preferably it is 2 micrometers or more.
  • the manufacturing method of the composite plate 12, that is, the LDH separator 14 combined with the porous substrate 16 is not particularly limited, and is manufactured by referring to a known manufacturing method of an LDH separator (for example, Patent Documents 1 to 3). be able to.
  • the resin outer frame 18 has an opening 18a, and the composite plate 12 is fitted into the opening 18a. Moreover, the resin outer frame 18 has a recess 18b that locks the porous substrate 16 side of the composite plate 12 along its inner periphery. Accordingly, the size of the opening 18a is slightly smaller than that of the composite plate 12, but the size of the contour shape of the recess 18b is equal to or slightly larger than that of the composite plate 12. The presence of the resin outer frame 18 can reinforce the end of the composite plate 12, thereby preventing damage to the end of the composite plate 12 and improving reliability, and handling the composite plate 12. It becomes easy. Therefore, the assembly of the zinc secondary battery is facilitated. The resin outer frame 18 itself can also contribute to the prevention of zinc dendrite penetration and extension.
  • the resin constituting the resin outer frame 18 is preferably a resin having resistance to alkali metal hydroxide such as potassium hydroxide, more preferably polyolefin resin, ABS resin, polypropylene (PP) resin, polyethylene (PE).
  • a resin or a modified polyphenylene ether more preferably an ABS resin, a polypropylene (PP) resin, a polyethylene (PE) resin, or a modified polyphenylene ether, and particularly preferably an ABS resin or a modified polyphenylene from the viewpoint of alkali resistance and adhesiveness.
  • the modified polyphenylene ether may be a compound (for example, m-PPE / PS) combined with another polymer (for example, polystyrene).
  • the concave portion 18 b of the adhesive resin outer frame 18 and the composite plate 12 are sealed and bonded with an adhesive 20.
  • the portion of the porous substrate 16 that faces the concave portion 18b is infiltrated with the adhesive 20 from the surface of the porous substrate 16 over a predetermined depth D.
  • the penetration depth D of the adhesive 20 into the porous substrate 16 is 100 ⁇ m or more from the surface of the porous substrate 16, preferably 100 to 600 ⁇ m, more preferably 100 to 500 ⁇ m, still more preferably 100 to 400 ⁇ m, Particularly preferred is 100 to 350 ⁇ m, and most preferred is 100 to 300 ⁇ m.
  • Such a penetration depth can be realized by selecting an adhesive having a low viscosity.
  • the adhesive having a low viscosity can be, for example, an adhesive that does not contain a thickener or a filler (for example, Si component) or has a small content of the thickener or the filler.
  • the adhesive 20 preferably contains a resin having alkali resistance in order to prevent deterioration in an alkaline electrolyte.
  • the preferable adhesive 20 is at least one selected from the group consisting of an epoxy resin adhesive, a natural resin adhesive, a modified olefin resin adhesive, and a modified silicone resin adhesive. These adhesives are all excellent in adhesion to both ceramics and resin.
  • An epoxy resin adhesive is preferable because it is particularly excellent in alkali resistance.
  • the epoxy resin adhesive is not limited to what is called an epoxy adhesive as long as it is an adhesive mainly composed of an epoxy resin, and various epoxy adhesives such as an epoxy amide adhesive and an epoxy-modified silicone adhesive.
  • An agent may be used.
  • either a one-component type (heat curing type) or a two-component mixed type may be used.
  • Epoxy resins are generally high in crosslink density, and thus have low water absorption, and are considered to suppress reaction with an alkaline electrolyte (for example, KOH aqueous solution).
  • the epoxy resin-based adhesive preferably has a glass transition temperature Tg of 40 ° C. or higher, more preferably 43 ° C.
  • epoxy resin adhesives include epoxy amide adhesives, epoxy modified silicone adhesives, epoxy adhesives, epoxy modified amide adhesives, epoxy polysulfide adhesives, epoxy acid anhydride adhesives, and epoxy nitrile adhesives. However, epoxy amide adhesives and epoxy adhesives are particularly preferred.
  • the above-mentioned epoxy resin adhesive is a thermosetting adhesive, but a natural resin adhesive and / or a modified olefin resin adhesive can also be used as the thermoplastic resin adhesive.
  • the thermoplastic resin-based adhesive preferably has a softening point of 80 ° C. or higher (specifically, an R & B softening point), more preferably 90 ° C. or higher, and still more preferably 95 to 160 ° C.
  • the higher the softening point the more difficult it is to react. Therefore, the alkali resistance is improved at the above temperature.
  • the separator structure 10 as a whole can have gas impermeability and / or water impermeability.
  • Example A1 Production of composite plate containing LDH separator and porous substrate A functional layer containing LDH and a composite material were produced and evaluated by the following procedure.
  • the functional layer in this example is a layer corresponding to an “LDH separator”, specifically, a layer including an LDH film and LDH in a porous substrate.
  • the composite material in this example corresponds to a “composite plate”.
  • porous substrate 70 parts by weight of a dispersion medium (xylene: butanol 1: 1) and binder (polyvinyl butyral: Sekisui Chemical) with respect to 100 parts by weight of alumina powder (AES-12, manufactured by Sumitomo Chemical Co., Ltd.) BM-2 manufactured by Kogyo Co., Ltd. 11.1 parts by weight, 5.5 parts by weight of a plasticizer (DOP: manufactured by Kurokin Kasei Co., Ltd.), and 2.9 parts by weight of a dispersant (Rheodor SP-O30 manufactured by Kao Corporation)
  • a dispersant Rosodor SP-O30 manufactured by Kao Corporation
  • the slurry was molded into a sheet shape on a PET film using a tape molding machine so that the film thickness after drying was 220 ⁇ m to obtain a sheet molded body.
  • the obtained molded body was cut out to have a size of 2.0 cm ⁇ 2.0 cm ⁇ thickness 0.022 cm and fired at 1300 ° C. for 2 hours to obtain an alumina porous substrate.
  • the porosity of the porous substrate was measured by the Archimedes method and found to be 40%.
  • the average pore diameter of the porous substrate was measured, it was 0.3 ⁇ m.
  • the average pore diameter was measured by measuring the longest distance of the pores based on an electron microscope (SEM) image of the surface of the porous substrate. The magnification of the electron microscope (SEM) image used for this measurement is 20000 times. All obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points are arranged in order from the average value. An average value for two visual fields was calculated at 30 points to obtain an average pore diameter. For length measurement, the length measurement function of SEM software was used.
  • magnesium nitrate hexahydrate (Mg (NO 3) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc.), aluminum nitrate nonahydrate (Al (NO 3) 3 ⁇ 9H 2 O, manufactured by Kanto Chemical Co., Ltd.) and urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich) were prepared.
  • Mg (NO 3) 2 ⁇ 6H 2 O manufactured by Kanto Chemical Co., Inc.
  • Al (NO 3) 3 ⁇ 9H 2 O manufactured by Kanto Chemical Co., Ltd.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich)
  • ion exchange water was added to make a total volume of 70 ml.
  • the substrate was taken out from the sealed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and a part of the functional layer containing LDH was incorporated into the porous substrate. Got in shape.
  • the thickness of the functional layer obtained was about 3 ⁇ m (including the thickness of the portion incorporated in the porous substrate).
  • Evaluation 1 Identification of functional layer
  • the crystal phase of the functional layer was measured with an X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation) under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10 to 70 °.
  • an XRD profile was obtained.
  • JCPDS card NO. Identification was performed using a diffraction peak of LDH (hydrotalcite compound) described in 35-0964. As a result, it was identified from the obtained XRD profile that the functional layer was LDH (hydrotalcite compound).
  • Evaluation 2 Observation of microstructure
  • the surface microstructure of the functional layer was observed with a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL) at an acceleration voltage of 10 to 20 kV. Further, after obtaining a cross-sectional polished surface of a functional layer (a film-shaped portion made of an LDH film and a composite portion made of LDH and a base material) with an ion milling device (manufactured by Hitachi High-Technologies Corporation, IM4000) The structure was observed by SEM under the same conditions as the observation of the surface microstructure, and as a result, the SEM images of the surface microstructure and the cross-sectional microstructure of the functional layer were as shown in FIGS.
  • SEM scanning electron microscope
  • the functional layer was composed of a film-shaped portion made of an LDH film and a composite portion made of LDH and a porous substrate located under the film-shaped portion.
  • the LDH constituting the part is composed of an aggregate of a plurality of plate-like particles, and the plurality of plate-like particles are such that the plate surface is negligible on the surface of the porous substrate (fine irregularities due to the porous structure can be ignored).
  • Macroscopic view The surface of the porous substrate is oriented perpendicularly or obliquely to the surface of the porous substrate.On the other hand, the composite portion is filled with LDH in the pores of the porous substrate to form a dense layer. It was composed.
  • Evaluation 3 Elemental analysis evaluation (EDS) Polishing was performed with a cross section polisher (CP) so that the cross-section polished surface of the functional layer (a film-like portion made of an LDH film and a composite portion made of LDH and a substrate) could be observed.
  • FE-SEM ULTRA55, manufactured by Carl Zeiss
  • a cross-sectional image of the functional layer was obtained in one field of view at a magnification of 10,000 times.
  • Examples B1 to B5 (1) Production of porous substrate An alumina porous substrate was produced in the same manner as in Example A1. The porosity of the obtained porous substrate was 40%. The average pore diameter of the porous substrate was 0.3 ⁇ m.
  • Adhesive A Epoxy two-component adhesive (Henkel Japan, Hysol E30CL)
  • Adhesive B Epoxy two-component adhesive (viscosity adjusted using bisphenol A type epoxy resin as the main agent and modified alicyclic polyamine as the curing agent)
  • Adhesive C Epoxy two-component adhesive (viscosity adjusted using bisphenol A type epoxy resin as the main agent and modified alicyclic polyamine as the curing agent)
  • Adhesive D Epoxy 1-pack type adhesive (Cemedine, Inc., Cemedine EP171)
  • Adhesive E Epoxy two-component adhesive (Cemedine, Inc., Cemedine EP008)
  • the epoxy two-component adhesive includes an epoxy resin as a main agent and a polyamine type as a curing agent.
  • the epoxy one-part adhesive includes a mixture of an epoxy resin and an epoxy curing agent.
  • the viscosity of the main agent and the viscosity of the curing agent shown in Table 1 are values described in the product catalog of each adhesive, and the viscosity after mixing shown in Table 1 is manually mixed for 3 minutes and then allowed to stand for 5 minutes. The displayed value is 120 seconds after the sample is put into the viscometer receiver and the measurement is started.
  • the mixing ratio, pot life, and curing conditions shown in Table 1 adopt values described in the product catalog of each adhesive.
  • Adhesives A, B, C, or E were weighed so as to have the mixing ratio shown in Table 1, mixed with a spatula for 1 minute, and then defoamed with a defoamer at 2000 rpm for 1 minute.
  • the adhesive 20 was applied to the recess 18b of the resin outer frame 18 with a spatula, and the alumina porous substrate 16 was placed thereon.
  • the resin outer frame 18 is made of modified polyphenylene ether (ZYRON (registered trademark) EV103).
  • the four corners of the porous substrate 16 were lightly pressed toward the resin outer frame 18 so that the adhesive 20 was attached to the end face of the alumina porous substrate 16. Then, the adhesive 20 was cured by allowing to stand under the curing conditions shown in Table 1. After the adhesive 20 was cured, the bonded portion of the obtained sample was cut out and the cross section was mechanically polished. The polished cross section was observed with an SEM, and the depth from the surface of the porous substrate 16 where the adhesive 20 soaked (that is, the soaking depth) was measured. The measured penetration depth was as shown in Table 1.
  • FIG. 3A shows a cross-sectional SEM image of the sample obtained in Example B1
  • FIG. 3B shows a cross-sectional SEM image obtained by observing the penetration interface portion in an enlarged manner.
  • the adhesive A is sufficiently infiltrated into the alumina porous substrate over a depth of 170 ⁇ m.
  • FIG. 3C shows the photograph which image
  • FIG. 4A the cross-sectional SEM image of the sample obtained in Comparative Example B5 is shown in FIG. 4A, while the cross-sectional SEM image obtained by magnifying and observing the penetration interface portion is shown in FIG. 4B.
  • the penetration of the adhesive E into the alumina porous substrate was as shallow as about 50 ⁇ m in depth.
  • FIG. 4C the photograph which image
  • the square white area shown in FIG. 4C is a porous substrate, but no noticeable discoloration due to penetration of the adhesive A was observed in the outer peripheral portion of the porous substrate. From this point, it can be said that the penetration of the adhesive into the porous substrate was insufficient.
  • Example B4 As shown in FIGS. 1A and 1B, the adhesive D was applied to the recess 18b of the resin outer frame 18 with a spatula, and the alumina porous substrate 16 was placed thereon.
  • the resin outer frame 18 is made of modified polyphenylene ether (ZYRON (registered trademark) EV103).
  • ZYRON registered trademark
  • the four corners of the porous base material 16 were lightly pressed toward the resin outer frame 17 so that the adhesive 20 was attached to the end face of the alumina porous base material 16.
  • the adhesive 20 was cured by allowing to stand under the curing conditions shown in Table 1. After the adhesive 20 was cured, the bonded portion of the obtained sample was cut out and the cross section was mechanically polished. The polished cross section was observed with an SEM, and the depth from the surface of the porous substrate 16 where the adhesive 20 soaked (that is, the soaking depth) was measured. The measured penetration depth was as shown in Table 1.
  • Example A1 composite plate comprising an LDH separator and a porous substrate
  • Example A1 composite plate comprising an LDH separator and a porous substrate
  • the composite plate 12 was bonded to the resin outer frame 18 to obtain the separator structure 10.
  • Ten separator structure samples were prepared for each adhesive. The following denseness determination test and He permeability measurement were performed, and the ratio of the samples in which the airtightness was confirmed in 10 samples for each adhesive was determined, and was defined as the airtightness securing ratio.
  • the obtained airtightness securing ratio was as shown in Table 1.
  • a density determination test was performed as follows. First, as shown in FIGS. 5A and 5B, an acrylic container 130 without a lid and a separator structure 10 having a shape and size that can function as a lid for the acrylic container 130 were prepared. The acrylic container 130 is formed with a gas supply port 130a for supplying gas therein. Then, the separator structure 10 was adhered to the upper end of the acrylic container 130 in a gas-tight and liquid-tight manner using a silicone adhesive 138 so as to completely close the open portion of the acrylic container 130, thereby obtaining a measurement sealed container 140. .
  • the measurement sealed container 140 was placed in a water tank 142, and the gas supply port 130 a of the acrylic container 130 was connected to a pressure gauge 144 and a flow meter 146 so that helium gas could be supplied into the acrylic container 130.
  • Water 143 was put into the water tank 142 and the measurement sealed container 140 was completely submerged.
  • the inside of the measurement container 140 is sufficiently airtight and liquid-tight, and the LDH separator 14 side of the separator structure 10 is exposed to the internal space of the measurement container 140, while the porous substrate 140 The material 16 side is in contact with the water in the water tank 142.
  • helium gas was introduced into the measurement sealed container 140 into the acrylic container 130 via the gas supply port 130a.
  • the pressure gauge 144 and the flow meter 146 are controlled so that the differential pressure inside and outside the LDH separator 14 becomes 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 or not helium gas bubbles were generated in the water from the separator structure 10. As a result, when generation
  • He transmission measurement> In order to evaluate the denseness and airtightness of the separator structure 10 from the viewpoint of He permeability, a He permeation test was performed as follows. First, the He transmittance measurement system 310 shown in FIGS. 6A and 6B was constructed.
  • the He permeability measurement system 310 is a separator in which He gas from a gas cylinder filled with He gas is supplied to a sample holder 316 via a pressure gauge 312 and a flow meter 314 (digital flow meter), and is held by the sample holder 316.
  • the structure 10 is configured to be transmitted from one surface to the other surface and discharged.
  • the sample holder 316 has a structure including a gas supply port 316a, a sealed space 316b, and a gas discharge port 316c, and was assembled as follows.
  • Support members 328a and 328b (made of PTFE) provided with gaskets made of butyl rubber as sealing members 326a and 326b at the upper and lower ends of the separator structure 10 and further provided with openings made of flanges from the outside of the sealing members 326a and 326b. ).
  • the sealed space 316b was partitioned by the separator structure 10, the sealing member 326a, and the support member 328a.
  • the separator structure 10 was arrange
  • the support members 328a and 328b were firmly fastened to each other by fastening means 330 using screws so that He gas leakage did not occur from a portion other than the gas discharge port 316c.
  • a gas supply pipe 334 was connected to the gas supply port 316 a of the sample holder 316 assembled in this way via a joint 332.
  • He gas was supplied to the He permeability measurement system 310 via the gas supply pipe 334 and permeated through the separator structure 10 held in the sample holder 316.
  • the gas supply pressure and the flow rate were monitored by the pressure gauge 312 and the flow meter 314.
  • the He permeability was calculated. The calculation of the He permeability is based on the permeation amount F (cm 3 / min) of He gas per unit time, the differential pressure P (atm) applied to the LDH separator 14 during He gas permeation, and the membrane area S ( cm 2 ) and calculated by the formula of F / (P ⁇ S).
  • the permeation amount F (cm 3 / min) of He gas was directly read from the flow meter 314. Further, as the differential pressure P, the gauge pressure read from the pressure gauge 312 was used. The He gas was supplied so that the differential pressure P was in the range of 0.05 to 0.90 atm. As a result, when the He permeability of the separator structure 10 was less than 1.0 cm / min ⁇ atm, it was determined that the separator structure 10 had extremely high density and airtightness.
  • Example B4 As shown in Table 1, in Examples B1 to B4, the penetration depth of the adhesive reached 100 ⁇ m or more, and as a result, the airtightness securing ratio was 10 out of 10 samples, that is, 100%. On the other hand, in Example B5 which is a comparative example, the penetration depth of the adhesive did not reach 100 ⁇ m, and as a result, the airtightness securing ratio was 7 out of 10 samples, that is, 70%.

Landscapes

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

Abstract

L'invention concerne une structure de séparateur pour une batterie secondaire au zinc. Cette structure de séparateur comprend : une plaque composite comprenant un séparateur hydroxyde double stratifié (LDH) et un substrat poreux disposé sur un côté du séparateur LDH; et un cadre externe en résine ayant une ouverture dans laquelle la plaque composite doit être ajustée. Le cadre externe en résine a un renfoncement pour verrouiller le côté substrat poreux de la plaque composite le long de la périphérie interne du cadre externe en résine, et le renfoncement et la plaque composite sont joints de manière étanche avec un adhésif. Le substrat poreux a une épaisseur d'au moins 100 µm, et la partie du substrat poreux qui fait face au renfoncement est imprégnée avec l'adhésif jusqu'à une profondeur d'au moins 100 µm à partir de la surface du substrat poreux. La présente invention permet d'améliorer la fiabilité et la durabilité d'une structure de séparateur dans laquelle un séparateur LDH équipé d'un substrat poreux est disposé dans un cadre externe en résine.
PCT/JP2017/041082 2017-01-19 2017-11-15 Structure de séparateur, batterie secondaire nickel-zinc et batterie secondaire zinc-air Ceased WO2018135117A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018562900A JP6803927B2 (ja) 2017-01-19 2017-11-15 セパレータ構造体、ニッケル亜鉛二次電池及び亜鉛空気二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-007984 2017-01-19
JP2017007984 2017-01-19

Publications (1)

Publication Number Publication Date
WO2018135117A1 true WO2018135117A1 (fr) 2018-07-26

Family

ID=62908702

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/041082 Ceased WO2018135117A1 (fr) 2017-01-19 2017-11-15 Structure de séparateur, batterie secondaire nickel-zinc et batterie secondaire zinc-air

Country Status (2)

Country Link
JP (1) JP6803927B2 (fr)
WO (1) WO2018135117A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020121673A1 (fr) * 2018-12-13 2020-06-18 日本碍子株式会社 Séparateur au hdl et accumulateur au zinc
JP2021125386A (ja) * 2020-02-06 2021-08-30 日本碍子株式会社 電解質材料及びアルカリ形燃料電池
CN115461923A (zh) * 2020-05-11 2022-12-09 日本碍子株式会社 Ldh隔板及锌二次电池
CN116905039A (zh) * 2023-08-15 2023-10-20 山西迎润新能源有限公司 一种双功能电解水催化剂及其制备方法和应用
JP2024526055A (ja) * 2022-02-18 2024-07-17 エルジー エナジー ソリューション リミテッド 多孔性複合セラミック分離膜、これを含む電気化学素子、及び前記多孔性複合セラミック分離膜の製造方法
WO2024181657A1 (fr) * 2023-02-27 2024-09-06 공주대학교 산학협력단 Support gonflant de membrane échangeuse d'ions homogène et dispositif à membrane échangeuse d'ions le comprenant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3219288A1 (fr) * 2022-05-02 2023-09-11 Lg Energy Solution, Ltd. Element de decharge de gaz et batterie secondaire le comprenant

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5596576U (fr) * 1978-12-26 1980-07-04
JPH0896787A (ja) * 1994-09-22 1996-04-12 Yuasa Corp 電池用セパレータの製造方法
JPH10172525A (ja) * 1996-12-12 1998-06-26 Toshiba Battery Co Ltd アルカリ乾電池
JP2003123712A (ja) * 2001-10-12 2003-04-25 Matsushita Electric Ind Co Ltd 電解質を含む電気化学素子
JP2007030175A (ja) * 2005-07-22 2007-02-08 Japan Vilene Co Ltd 積層体及び濾過材
JP2009503840A (ja) * 2005-07-27 2009-01-29 セラジー リミテッド 多層電気化学エネルギー貯蔵装置およびその製造方法
WO2016039349A1 (fr) * 2014-09-10 2016-03-17 日本碍子株式会社 Pile rechargeable utilisant un séparateur céramique conducteur d'ions hydroxyde
WO2016051934A1 (fr) * 2014-10-01 2016-04-07 日本碍子株式会社 Batterie utilisant un hydroxyde lamellaire

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5596576U (fr) * 1978-12-26 1980-07-04
JPH0896787A (ja) * 1994-09-22 1996-04-12 Yuasa Corp 電池用セパレータの製造方法
JPH10172525A (ja) * 1996-12-12 1998-06-26 Toshiba Battery Co Ltd アルカリ乾電池
JP2003123712A (ja) * 2001-10-12 2003-04-25 Matsushita Electric Ind Co Ltd 電解質を含む電気化学素子
JP2007030175A (ja) * 2005-07-22 2007-02-08 Japan Vilene Co Ltd 積層体及び濾過材
JP2009503840A (ja) * 2005-07-27 2009-01-29 セラジー リミテッド 多層電気化学エネルギー貯蔵装置およびその製造方法
WO2016039349A1 (fr) * 2014-09-10 2016-03-17 日本碍子株式会社 Pile rechargeable utilisant un séparateur céramique conducteur d'ions hydroxyde
WO2016051934A1 (fr) * 2014-10-01 2016-04-07 日本碍子株式会社 Batterie utilisant un hydroxyde lamellaire

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020121673A1 (fr) * 2018-12-13 2020-06-18 日本碍子株式会社 Séparateur au hdl et accumulateur au zinc
JPWO2020121673A1 (ja) * 2018-12-13 2021-03-11 日本碍子株式会社 Ｌｄｈセパレータ及び亜鉛二次電池
US11211672B2 (en) 2018-12-13 2021-12-28 Ngk Insulators, Ltd. LDH separator and zinc secondary battery
JP2021125386A (ja) * 2020-02-06 2021-08-30 日本碍子株式会社 電解質材料及びアルカリ形燃料電池
CN115461923A (zh) * 2020-05-11 2022-12-09 日本碍子株式会社 Ldh隔板及锌二次电池
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
JP2024526055A (ja) * 2022-02-18 2024-07-17 エルジー エナジー ソリューション リミテッド 多孔性複合セラミック分離膜、これを含む電気化学素子、及び前記多孔性複合セラミック分離膜の製造方法
JP7709556B2 (ja) 2022-02-18 2025-07-16 エルジー エナジー ソリューション リミテッド 多孔性複合セラミック分離膜、これを含む電気化学素子、及び前記多孔性複合セラミック分離膜の製造方法
WO2024181657A1 (fr) * 2023-02-27 2024-09-06 공주대학교 산학협력단 Support gonflant de membrane échangeuse d'ions homogène et dispositif à membrane échangeuse d'ions le comprenant
CN116905039A (zh) * 2023-08-15 2023-10-20 山西迎润新能源有限公司 一种双功能电解水催化剂及其制备方法和应用

Also Published As

Publication number Publication date
JPWO2018135117A1 (ja) 2019-11-07
JP6803927B2 (ja) 2020-12-23

Similar Documents

Publication Publication Date Title
JP6617200B2 (ja) 層状複水酸化物を含む機能層及び複合材料
WO2018135117A1 (fr) Structure de séparateur, batterie secondaire nickel-zinc et batterie secondaire zinc-air
JP6262815B2 (ja) 亜鉛二次電池に用いられるセパレータ構造体
WO2017221989A1 (fr) Couche fonctionnelle comprenant un hydroxyde double stratifié et matériau composite
JP6677820B2 (ja) 電極／セパレータ積層体及びそれを備えたニッケル亜鉛電池
WO2017086278A1 (fr) Cartouche d'électrode et pile rechargeable au zinc l'utilisant
JP2018026205A (ja) 負極構造体及びそれを備えた亜鉛二次電池
JP6864758B2 (ja) 層状複水酸化物を含む機能層及び複合材料
JP6949142B2 (ja) Ｌｄｈセパレータ及び亜鉛二次電池
WO2017221531A1 (fr) Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
JP6243583B1 (ja) 層状複水酸化物を含む機能層及び複合材料
WO2017221988A1 (fr) Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
JP6454555B2 (ja) 水酸化物イオン伝導緻密膜の評価方法
JP6586221B2 (ja) アルカリ二次電池の製造に適した接着剤の選定方法、及びアルカリ二次電池
JP6441693B2 (ja) 水酸化物イオン伝導緻密膜の評価方法
WO2017221526A1 (fr) Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
JP6614728B2 (ja) 層状複水酸化物含有複合材料及び電池

Legal Events

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

Ref document number: 17893322

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018562900

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17893322

Country of ref document: EP

Kind code of ref document: A1