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WO2017221499A1 - Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite - Google Patents

Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite Download PDF

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Publication number
WO2017221499A1
WO2017221499A1 PCT/JP2017/012435 JP2017012435W WO2017221499A1 WO 2017221499 A1 WO2017221499 A1 WO 2017221499A1 JP 2017012435 W JP2017012435 W JP 2017012435W WO 2017221499 A1 WO2017221499 A1 WO 2017221499A1
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WIPO (PCT)
Prior art keywords
functional layer
layer
ldh
porous substrate
thickness
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/JP2017/012435
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English (en)
Japanese (ja)
Inventor
翔 山本
昌平 横山
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
Priority claimed from PCT/JP2017/003333 external-priority patent/WO2017221451A1/fr
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to EP17814971.2A priority Critical patent/EP3477738B1/fr
Priority to CN201780038283.0A priority patent/CN109314215B/zh
Priority to JP2017535932A priority patent/JP6259548B1/ja
Priority to EP17815456.3A priority patent/EP3477739A4/fr
Priority to CN201780038255.9A priority patent/CN109314214B/zh
Priority to PCT/JP2017/022905 priority patent/WO2017221988A1/fr
Priority to JP2018524146A priority patent/JP6448861B2/ja
Publication of WO2017221499A1 publication Critical patent/WO2017221499A1/fr
Priority to JP2018226808A priority patent/JP6557771B2/ja
Priority to US16/227,469 priority patent/US10994511B2/en
Priority to US16/227,545 priority patent/US10940668B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • H01M50/491—Porosity
    • 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

Definitions

  • the present invention relates to a functional layer and a composite material containing a layered double hydroxide.
  • LDH Layered double hydroxide
  • LDH is also attracting attention as a material that conducts hydroxide ions, and its addition to the electrolyte of alkaline fuel cells and the catalyst layer of zinc-air cells is also being studied.
  • LDH as a solid electrolyte separator for alkaline secondary batteries such as nickel-zinc secondary batteries and zinc-air secondary batteries
  • an LDH-containing functional layer suitable for such separator applications is provided.
  • Composite materials are known.
  • Patent Document 1 International Publication No. 2015/098610 discloses a composite including a porous substrate and an LDH-containing functional layer that does not have water permeability and is formed on and / or in the porous substrate.
  • the LDH-containing functional layer has a general formula: M 2+ 1-x M 3+ x (OH) 2 A n ⁇ x / n ⁇ mH 2 O (where M 2+ is 2 such as Mg 2+) A valent cation, M 3+ is a trivalent cation such as Al 3+ , A n ⁇ is an n-valent anion such as OH ⁇ , CO 3 2 ⁇ , n is an integer of 1 or more, and x is 0. 1 to 0.4, and m is 0 or more).
  • Patent Document 2 International Publication No. 2016/076047 discloses a separator structure including an LDH separator combined with a porous substrate, and the LDH separator is gas-impermeable and / or It is disclosed to have high density enough to have water impermeability. This document also describes that LDH separators can have high density, which is evaluated as 10 cm / min ⁇ atm or less in terms of He permeability per unit area.
  • the present inventors have recently found that the alkali resistance of an LDH-containing layer is significantly improved by covering the surface of a dense LDH-containing layer composed of LDH fine particles with large LDH particles having a diameter of 0.05 ⁇ m or more. Obtained.
  • an object of the present invention is to provide an LDH-containing functional layer having significantly improved alkali resistance and a composite material including the same.
  • a functional layer comprising a layered double hydroxide (LDH) comprising: A first layer composed of LDH fine particles having a diameter of less than 0.05 ⁇ m and having a thickness of 0.10 ⁇ m or more; A second layer composed of LDH large particles having an average particle diameter of 0.05 ⁇ m or more, which is an outermost surface layer provided on the first layer; A functional layer is provided.
  • LDH layered double hydroxide
  • a porous substrate comprising:
  • a battery including the functional layer or the composite material as a separator is provided.
  • FIG. 6 is a conceptual diagram showing an example of a He permeability measurement system used in Examples 1 to 5. It is a schematic cross section of the sample holder used for the measurement system shown in FIG. 8A and its peripheral configuration.
  • the functional layer 14 of the present invention includes a layered double hydroxide (LDH), and includes a first layer 14a, a second layer 14b, And optionally has a third layer 14c. That is, the first layer 14a, the second layer 14b, and optionally the third layer 14c all contain LDH.
  • the first layer 14a is a layer having a thickness of 0.10 ⁇ m or more, which is composed of LDH fine particles having a diameter of less than 0.05 ⁇ m.
  • the second layer 14b is an outermost surface layer provided on the first layer 14a, and is a layer composed of large LDH particles having an average particle diameter of 0.05 ⁇ m or more.
  • the first layer 14a is filled with LDH fine particles having a diameter of less than 0.05 ⁇ m, it can be said that the first layer 14a is a dense layer, and therefore can function as an LDH separator.
  • the alkali secondary battery LDH is desired to have a high alkali resistance that hardly deteriorates even in a strong alkaline electrolyte.
  • the alkali resistance is significantly improved by covering the surface of the dense first layer 14a composed of LDH fine particles with large LDH particles having an average particle diameter of 0.05 ⁇ m or more. .
  • the large LDH particles constituting the second layer 14b tend to be chemically stable, and such large LDH particles cover the surface of the first layer 14a, thereby reducing the density of the first layer 14a. This is thought to be because the decrease is suppressed.
  • the LDH-containing functional layer is 3 in 70 ° C. in a potassium hydroxide aqueous solution having a predetermined concentration.
  • the density decreases when immersed for a week, but when the average particle size of the LDH particles constituting the outermost surface layer is larger than 0.05 ⁇ m, the LDH-containing functional layer is placed in an aqueous potassium hydroxide solution having a predetermined concentration. The denseness does not change even when immersed for 3 weeks at °C.
  • the first layer 14a is a layer composed of LDH fine particles.
  • the LDH fine particles are mainly composed of LDH and may contain other trace components such as titania. That is, the first layer 14a is a layer mainly made of LDH, not a composite layer incorporated in another member. Therefore, in the case of the composite material 10 in which a part of the functional layer 14 is incorporated in the porous substrate 12 as shown in FIG. 1, a part of the functional layer incorporated in the porous substrate 12 is the first layer. It is assumed that it is regarded as another third layer 14c, not 14a.
  • the first layer 14a is a layer formed on the outermost surface (which should also be referred to as a main surface) of the porous substrate 12, and is a third layer 14c in which LDH particles are incorporated in the porous substrate 12. Differentiated. In other words, it can be said that the first layer 14 a is a layer that does not include other members such as the porous substrate 12.
  • the diameter of the LDH fine particles constituting the first layer 14a is less than 0.05 ⁇ m, and preferably 0.025 ⁇ m or less. Since the smaller LDH fine particles are better, the lower limit of the diameter is not particularly limited, but the diameter of the LDH fine particles is typically 0.001 ⁇ m or more, more typically 0.003 ⁇ m or more.
  • the diameter of the LDH fine particles can be determined by obtaining the cross-sectional polished surface of the functional layer 14 using an ion milling apparatus and then observing the microstructure of the cross-sectional polished surface with a scanning transmission electron microscope (STEM).
  • the thickness of the first layer 14a is 0.10 ⁇ m or more, preferably 0.10 to 4.5 ⁇ m, more preferably 0.50 to 3.0 ⁇ m, and still more preferably 1.0 to 2.5 ⁇ m. Thus, the thickness of the first layer 14a is at least twice the diameter of the LDH fine particles.
  • the first layer 14a has a highly dense structure in which a plurality of LDH particles are stacked in the layer thickness direction, and is not a structure in which a plurality of LDH particles are simply connected in a plane. Means. Therefore, it can be said that a large number of LDH fine particles are three-dimensionally connected to each other to constitute one first layer 14a as a whole.
  • the second layer 14b is a layer composed of LDH large particles.
  • LDH large particles mainly consist of LDH and may contain other trace components such as titania. Since the second layer 14b is the outermost surface layer provided on the first layer 14a, it is a layer mainly composed of LDH that is not incorporated in other members such as the porous substrate 12 like the first layer 14a. is there.
  • the average particle diameter of the large LDH particles constituting the second layer 14b is 0.05 ⁇ m or more, preferably 0.05 to 5.0 ⁇ m, more preferably 0.1 to 5.0 ⁇ m.
  • the average particle diameter of the large LDH particles is measured by observing the surface of the second layer 14b with a scanning electron microscope (SEM) and measuring the longest distance of the particle size based on the obtained image.
  • SEM scanning electron microscope
  • the magnification of the electron microscope (SEM) image is set to 10,000 times or more, and all the obtained particle sizes are arranged in order, and the top 15 points and the bottom 15 points are arranged in order from the average value, and 30 per field in total. An average value for two fields of view can be calculated in terms of points to obtain an average particle size.
  • the length measurement function of SEM software may be used.
  • the thickness of the second layer 14b is not particularly limited, but is preferably 0.1 to 10 ⁇ m. Typically, the thickness of the second layer 14b corresponds to the height of one large LDH particle, but two or more large LDH particles may be stacked locally or entirely.
  • the functional layer 14 includes a layered double hydroxide (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 included in the functional layer is composed of an anion 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- .
  • the pH is about 14 and a strong alkaline KOH. It is desirable to use an aqueous solution. For this reason, LDH is desired to have a high alkali resistance that hardly deteriorates even in such a strong alkaline electrolyte. Therefore, the LDH in the present invention is preferably one that does not cause changes in the surface microstructure and crystal structure by the alkali resistance evaluation as described later, and its composition is not particularly limited. Further, as described above, LDH has excellent ionic conductivity due to its inherent properties.
  • LDH contained in the functional layer 14 is immersed in a 6 mol / L potassium hydroxide aqueous solution containing zinc oxide at a concentration of 0.4 mol / L at 70 ° C. for 3 weeks (ie, 504 hours).
  • those which do not cause changes in the surface microstructure and crystal structure are preferred in terms of excellent alkali resistance.
  • the presence or absence of changes in the surface microstructure depends on the surface microstructure using an SEM (scanning electron microscope), and the presence or absence of changes in the crystal structure depends on crystal structure analysis using XRD (X-ray diffraction) (for example, (003) derived from LDH) This can be preferably performed depending on whether or not there is a peak shift.
  • Potassium hydroxide is a typical strong alkaline substance, and the composition of the potassium hydroxide aqueous solution corresponds to a typical strong alkaline electrolyte of an alkaline secondary battery. Therefore, it can be said that the above evaluation method of immersing in such a strong alkaline electrolyte at a high temperature of 70 ° C. for a long period of 3 weeks is a severe alkali resistance test.
  • the LDH for alkaline secondary batteries is desired to have high alkali resistance that hardly deteriorates even in a strong alkaline electrolyte.
  • the functional layer of this embodiment has excellent alkali resistance that the surface microstructure and crystal structure are not changed even by such severe alkali resistance test.
  • the functional layer of this embodiment can also exhibit high ionic conductivity suitable for use as a separator for an alkaline secondary battery due to the inherent properties of LDH. That is, according to this aspect, it is possible to provide an LDH-containing functional layer that is excellent not only in ion conductivity but also in alkali resistance.
  • the hydroxide base layer of LDH is 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 generally known alternate layered structure of LDH, but the functional layer of this embodiment is mainly composed of the hydroxide basic layer of LDH as Ni.
  • an element for example, Al
  • 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 base layer of LDH comprises Ni, Al, Ti and OH groups.
  • the intermediate layer is composed of an anion and H 2 O.
  • the alternating layered structure of the hydroxide basic layer and the intermediate layer itself is basically the same as the generally known layered structure of LDH, but the functional layer of this embodiment is configured such that the hydroxide basic layer of LDH is Ni, By comprising a predetermined element or ion containing Al, Ti and OH groups, excellent alkali resistance can be exhibited.
  • 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.
  • LDH for example, derived from raw materials and base materials.
  • 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 functional layer 14 (particularly LDH contained in the functional layer 14) preferably has hydroxide ion conductivity.
  • the functional layer preferably has an ionic conductivity of 0.1 mS / cm or more, more preferably 0.5 mS / cm or more, and more preferably 1.0 mS / cm or more.
  • the upper limit is not particularly limited, but is, for example, 10 mS / cm.
  • Such high ionic conductivity is particularly suitable for battery applications.
  • an LDH-containing functional layer having a low resistance can be provided. It is particularly advantageous in the application of LDH as a solid electrolyte separator for secondary batteries.
  • the functional layer 14 is provided on the porous substrate 12 and / or a part thereof is incorporated into the porous substrate 12. That is, according to a preferred aspect of the present invention, the porous substrate 12 and the functional layer 14 provided on the porous substrate 12 and / or partially incorporated in the porous substrate 12 are included.
  • a composite material 10 is provided. For example, like the composite material 10 shown in FIG. 1, a part of the functional layer 14 may be incorporated in the porous substrate 12 and the remaining part may be provided on the porous substrate 12. At this time, portions of the functional layer 14 on the porous substrate 12 are the first layer 14a and the second layer 14b, and a portion (composite layer) of the functional layer 14 incorporated into the porous substrate 12 is the third layer. Layer 14c.
  • the third layer 14c typically has a form in which the pores of the porous substrate 12 are filled with LDH.
  • the porous substrate 12 in the composite material 10 of the present invention is preferably capable of forming an LDH-containing functional layer on and / or in it, and the material and porous structure are not particularly limited.
  • the LDH-containing functional layer is formed on and / or in the porous substrate, but the LDH-containing functional layer is formed on the nonporous substrate, and then nonporous by various known methods.
  • the porous substrate may be made porous.
  • the porous base material has a porous structure having water permeability in that the electrolyte solution can reach the functional layer when incorporated in the battery as a battery separator.
  • the porous substrate 12 is preferably composed of at least one selected from the group consisting of ceramic materials, metal materials, and polymer materials, and more preferably selected from the group consisting of ceramic materials and polymer materials. And at least one kind. More preferably, the porous substrate is made of a ceramic material.
  • 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.
  • alumina e.g, yttria stabilized zirconia (YSZ)
  • YSZ yttria stabilized zirconia
  • 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. Any of the various preferred materials described above has alkali resistance as resistance to the electrolyte of the battery.
  • the porous substrate 12 preferably has an average pore size of at most 100 ⁇ m, more preferably at most 50 ⁇ m, for example, typically 0.001 to 1.5 ⁇ m, more typically 0.00. 001 to 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 average pore diameter can be measured by measuring the longest distance of the 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. All the 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, and 30 points per visual field are combined.
  • the average pore diameter can be obtained by calculating an average value for two visual fields.
  • a length measurement function of SEM software, image analysis software (for example, Photoshop, manufactured by Adobe) or the like can be used for the length measurement.
  • the porous substrate 12 preferably has a porosity of 10 to 60%, more preferably 15 to 55%, still more preferably 20 to 50%. By being within these ranges, it is possible to form an LDH-containing functional layer that is so dense that it does not have water permeability, while ensuring the desired water permeability and strength as a support for the porous substrate.
  • the porosity of the porous substrate can be preferably measured by the Archimedes method.
  • the functional layer 14 preferably does not have air permeability. That is, the functional layer is preferably densified with LDH to such an extent that it does not have air permeability.
  • “not breathable” means one surface of a measurement object (that is, a functional layer or a composite material) in water as described in Patent Document 2 (International Publication No. 2016/076047). This means that even when helium gas is brought into contact with the side at a differential pressure of 0.5 atm, no bubbles are generated due to helium gas from the other side. By doing so, the functional layer or the composite material as a whole can selectively pass only hydroxide ions due to its hydroxide ion conductivity, and can exhibit a function as a battery separator. .
  • LDH solid electrolyte separator for a battery
  • strength can be imparted by a porous substrate. Therefore, the LDH-containing functional layer can be thinned to reduce the resistance.
  • the porous substrate can have water permeability and air permeability, the electrolyte can reach the LDH-containing functional layer when used as a battery solid electrolyte separator.
  • the LDH-containing functional layer and composite material of the present invention are used as solid electrolyte separators applicable to various battery applications such as metal-air batteries (for example, zinc-air batteries) and other various zinc secondary batteries (for example, nickel-zinc batteries). It can be a very useful material.
  • the functional layer 14 or the composite material 10 including the functional layer 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 still more preferably 1. 0 cm / min ⁇ atm or less. It can be said that the functional layer having the He transmittance within such a range has extremely high density. Therefore, the functional layer having a He permeability of 10 cm / min ⁇ atm or less can prevent a high level of passage of substances other than hydroxide ions when applied as a separator in an alkaline secondary battery. For example, in the case of a zinc secondary battery, permeation of zinc ions or zincate ions in the electrolytic solution can be extremely effectively suppressed.
  • the He permeability is measured through a process of supplying He gas to one surface of the functional layer and allowing the He gas to pass through the functional layer, and a process of calculating the He permeability and evaluating the density of the functional layer.
  • the He permeability is expressed by the following formula: F / (P ⁇ S), using the He gas permeation amount F per unit time, the differential pressure P applied to the functional layer when He gas permeates, and the membrane area S through which He gas permeates.
  • H 2 gas is dangerous because it is a combustible gas.
  • 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 or not the functional layer has a sufficiently high density suitable for a zinc secondary battery separator.
  • the measurement of the He permeability can be preferably performed according to the procedure shown in Evaluation 4 of Examples described later.
  • the LDH that constitutes the second layer 14b includes an aggregate of a plurality of plate-like particles (that is, LDH plate-like particles), and the plurality of plate-like particles have a functional layer layer surface (the fine irregularities of the functional layer). It is preferably oriented in a direction that intersects perpendicularly or obliquely with the layer surface (when viewed macroscopically to a negligible level).
  • LDH crystals are known to have the form of plate-like particles having a layered structure, the above vertical or oblique orientation is a very advantageous characteristic for an LDH-containing functional layer (for example, an LDH dense film).
  • an oriented LDH-containing functional layer eg, an oriented LDH dense film
  • a hydroxide ion conductivity perpendicular to this in the direction in which the LDH plate-like particles are oriented ie, in a direction parallel to the LDH layer.
  • 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 vertical or oblique orientation in the LDH-containing functional layer maximizes the conductivity anisotropy that the LDH oriented body can have in the layer thickness direction (that is, the direction perpendicular to the surface of the functional layer or porous substrate). Alternatively, it can be significantly extracted, and as a result, the conductivity in the layer thickness direction can be maximized or significantly increased.
  • the LDH-containing functional layer has a layer form, lower resistance than that of the bulk form LDH can be realized.
  • the LDH-containing functional layer having such an orientation is easy to conduct hydroxide ions in the layer thickness direction.
  • the functional layer 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 15 ⁇ m or less. Such thinness can reduce the resistance of the functional layer.
  • the thickness of the functional layer 14 corresponds to the total thickness of the first layer 14a and the second layer 14b. Further, when the functional layer 14 is formed over and in the porous substrate 12, this corresponds to the total thickness of the first layer 14a, the second layer 14b, and the third layer 14c. In any case, when the thickness is as described above, a desired low resistance suitable for practical use in battery applications and the like can be realized.
  • the lower limit of the thickness of the LDH alignment film is not particularly limited because it varies depending on the application, but in order to ensure a certain degree of hardness 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 LDH-containing functional layer and the composite material is not particularly limited, and the LDH-containing functional layer and the composite material are manufactured by appropriately changing various conditions of the LDH-containing functional layer and the composite material manufacturing method (see, for example, Patent Documents 1 to 3). be able to.
  • a porous substrate is prepared, (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, (3) 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 form the LDH-containing functional layer as the porous base material.
  • the LDH-containing functional layer and the composite material can be produced.
  • the raw material of LDH can be provided, but it can also function as a starting point for LDH crystal growth.
  • the LDH-containing functional layer highly densified on the surface can be uniformly formed without unevenness.
  • the presence of urea in the above step (3) raises the pH value due to the generation of ammonia in the solution utilizing the hydrolysis of urea, and the coexisting metal ions form hydroxides. LDH can be obtained. Further, since carbon dioxide is generated in the hydrolysis, LDH in which the anion is carbonate ion type can be obtained.
  • Particularly preferred LDH-containing functional layers and methods for producing composite materials have the following characteristics, and these characteristics are considered to contribute to the realization of various characteristics of the functional layer of the present invention.
  • some kind of mixed sol for example, amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.)
  • titanium oxide sol solution M6, Taki Chemical
  • the heat treatment temperature of the sol applied to the porous substrate is relatively low, preferably 70 to 300 ° C.
  • the sol is applied by spin coating a plurality of times to thicken the spin coat layer (for example, the spin coat layer thickness is 5 ⁇ m), d)
  • nickel ions Ni 2+
  • the urea / NO 3 — molar ratio is preferably 8 to 32 (for example, 16) adding urea so that e) Hydrothermal treatment in the above step (4) is at a relatively low temperature, preferably 70 to 150 ° C.
  • the functional layer is washed with ion-exchanged water, and then the functional layer is dried at a relatively low temperature, preferably from room temperature to 70 ° C. (for example, room temperature). To do.
  • Example 1 (Comparison) Various functional layers and composite materials containing Ni, Al and Ti-containing LDH were prepared and evaluated by the following procedures.
  • porous substrate 70 parts by weight of a dispersion medium (xylene: butanol 1: 1) and binder (polyvinyl butyral: Sekisui Chemical Co., Ltd.) with respect to 100 parts by weight of zirconia powder (manufactured by Tosoh Corporation, TZ-8YS) 11.1 parts by weight of BM-2 manufactured by Co., Ltd., 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 Roslurry was obtained by mixing and defoaming the mixture by stirring under reduced pressure.
  • 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 baked at 1100 ° C. for 2 hours to obtain a zirconia 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 0.2 ⁇ 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.
  • the length measurement function of SEM software was used.
  • Alumina / titania sol coat on porous substrate Amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) and titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) have a weight ratio of 1 : 1 to prepare a mixed sol.
  • 0.2 ml of the mixed sol was applied onto the zirconia porous substrate obtained in (1) above by spin coating. In spin coating, the mixed sol was dropped onto the substrate rotated at 8000 rpm, and the rotation was stopped 5 seconds later. The substrate was allowed to stand on a hot plate heated to 100 ° C. and dried for 1 minute. Thereafter, heat treatment was performed at 150 ° C. in an electric furnace. The thickness of the layer thus formed was about 1 ⁇ m.
  • Nickel nitrate hexahydrate Ni (NO 3 ) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed so as to be 0.015 mol / L, put into a beaker, and ion-exchanged water was added thereto to make a total volume of 75 ml.
  • Urea weighed in a ratio of urea / NO 3 ⁇ (molar ratio) 16 was added thereto, and further stirred to obtain a raw material aqueous solution.
  • the substrate is taken out of the sealed container, washed with ion-exchanged water, allowed to stand at room temperature for 12 hours, dried, and a part of the functional layer containing LDH is incorporated into the porous substrate. Obtained in the form.
  • the thickness of the obtained functional layer was about 5 ⁇ m (including the thickness of the portion incorporated in the porous substrate).
  • Example 2 A functional layer and a composite material were produced in the same procedure as in Example 1 except that the hydrothermal treatment time in the film forming step by hydrothermal treatment was 8 hours.
  • Example 3 A functional layer and a composite material were produced in the same procedure as in Example 1 except that the hydrothermal treatment time of the film forming step by hydrothermal treatment was 16 hours.
  • Example 4 A functional layer and a composite material were produced in the same procedure as in Example 1 except that the hydrothermal treatment time of the film-forming process by hydrothermal treatment was 30 hours.
  • Example 5 In the alumina / titania sol coating process, spin coating was performed at a rotational speed of 4000 rpm, the same spin coating was repeated three times to increase the thickness of the spin coating layer, and the hydrothermal treatment time of the film formation process by hydrothermal treatment was set to 45 hours. Except for the above, a functional layer and a composite material were produced in the same procedure as in Example 1. The spin coat layer had a thickness of 5 ⁇ m, and the obtained functional layer had a thickness of about 10 ⁇ m.
  • Evaluation 1 Observation of surface microstructure and measurement of average particle diameter of large particles 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. did.
  • SEM scanning electron microscope
  • JSM-6610LV manufactured by JEOL
  • FIGS. 2, 3 and 5 show surface SEM images of the functional layers of Example 1 (comparative), Example 3 and Example 4, respectively. Therefore, the average particle size of the functional layers of Examples 2 to 5 was measured by the following procedure.
  • the average particle size of the large particles constituting the second layer was measured by measuring the longest distance of the particle size based on the surface electron microscope (SEM) image of the functional layer.
  • the magnification of the electron microscope (SEM) image used for this measurement is 10,000 times or more. All the obtained particle sizes are arranged in order, and the top 15 points and the bottom 15 points are arranged in order from the average value. An average value for two fields of view was calculated at 30 points to obtain an average particle size.
  • the length measurement function of SEM software was used. The results were as shown in Table 1.
  • Evaluation 2 Cross-sectional microstructure observation and thickness measurement Ion milling device (manufactured by Hitachi High-Technologies Corporation, IM4000) After obtaining the cross-sectional polished surface of the functional layer, the microstructure of the cross-sectional polished surface is observed with the surface microstructure.
  • the functional layers of Examples 2 to 5 were composed of fine particles and were not incorporated into the porous substrate (that is, formed on the outermost surface of the porous substrate).
  • the thickness was 1.0 ⁇ m (Example 1), 0.8 ⁇ m (Example 2), 0.7 ⁇ m (Example 3), 0.8 ⁇ m (Example 4), and 0.8 ⁇ m (Example 5).
  • the thickness of each was as shown in Table 1.
  • Evaluation 3 Fine particle observation by STEM and measurement of fine particle diameter
  • STEM atomic resolution transmission scanning electron microscope
  • the microstructure of the cross-sectional polished surface is analyzed by an atomic resolution transmission scanning electron microscope (STEM, JEOL). Observation was performed at an acceleration voltage of 200 kV using a JEM-ARM200F).
  • FIG. 7 shows a STEM image of the cross-sectional polished surface of the first layer in the functional layer obtained in Example 4.
  • the He permeability measurement system 310 is a function in which He gas from a gas cylinder filled with He gas is supplied to the sample holder 316 via the pressure gauge 312 and the flow meter 314 (digital flow meter), and is held in the sample holder 316.
  • the layer 318 was 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. First, an adhesive 322 was applied along the outer periphery of the functional layer 318 and attached to a jig 324 (made of ABS resin) having an opening at the center. 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 jig 324 and further provided with openings formed from flanges from the outside of the sealing members 326a and 326b. ).
  • the sealed space 316b was partitioned by the functional layer 318, the jig 324, the sealing member 326a, and the support member 328a.
  • the functional layer 318 is in the form of a composite material formed on the porous substrate 320, but the functional layer 318 is disposed so that the functional layer 318 side faces the gas supply port 316a.
  • 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.
  • the gas supply pipe 34 was connected to the gas supply port 316a 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 functional layer 318 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 of He gas per unit time F (cm 3 / min), the differential pressure P (atm) applied to the functional layer 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. The results were as shown in Table 1.
  • Evaluation 5 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.
  • the functional layers obtained in Examples 1 to 5 were all identified as LDH (hydrotalcite compound).
  • the obtained sample was observed for microstructure by SEM and crystal structure by XRD. At this time, the change in the crystal structure was determined by the presence or absence of a shift in the (003) peak derived from LDH in the XRD profile. As a result, in any of Examples 1 to 5, no change was observed in the surface microstructure and crystal structure.
  • Evaluation 7 Elemental analysis evaluation (EDS) The cross section of the functional layer was polished by a cross section polisher (CP). Using FE-SEM (ULTRA55, manufactured by Carl Zeiss), a cross-sectional image of the functional layer was acquired with one field of view at a magnification of 10,000 times. The elemental analysis of the LDH film on the substrate surface of this cross-sectional image and the LDH portion (point analysis) inside the substrate was performed with an EDS analyzer (NORAN System SIX, manufactured by Thermo Fisher Scientific) under the condition of an acceleration voltage of 15 kV. went. As a result, LDH constituent elements C, Al, Ti and Ni were detected from the LDH contained in the functional layers obtained in Examples 1 to 5. That is, Al, Ti and Ni are constituent elements of the hydroxide basic layer, while C corresponds to CO 3 2 ⁇ which is an anion constituting the intermediate layer of LDH.
  • EDS Elemental analysis evaluation

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Abstract

L'invention concerne : une couche fonctionnelle comprenant un hydroxyde double stratifié (LDH), ladite couche fonctionnelle ayant une résistance aux alcalis significativement améliorée; et un matériau composite comprenant ladite couche fonctionnelle. Cette couche fonctionnelle comprend un LDH, et comporte : une première couche qui a une épaisseur d'au moins 0,10 µm, et qui est formée à partir de microparticules de LDH ayant un diamètre inférieur à 0,05 µm; et une seconde couche qui est disposée sur la première couche, est la couche la plus à l'extérieur, et est formée à partir de grandes particules de LDH ayant un diamètre de particule moyen d'au moins 0,05 µm.
PCT/JP2017/012435 2016-06-24 2017-03-27 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite Ceased WO2017221499A1 (fr)

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EP17814971.2A EP3477738B1 (fr) 2016-06-24 2017-03-27 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
CN201780038283.0A CN109314215B (zh) 2016-06-24 2017-03-27 包含层状双氢氧化物的功能层及复合材料
JP2017535932A JP6259548B1 (ja) 2016-06-24 2017-03-27 層状複水酸化物を含む機能層及び複合材料
JP2018524146A JP6448861B2 (ja) 2016-06-24 2017-06-21 層状複水酸化物を含む機能層及び複合材料
CN201780038255.9A CN109314214B (zh) 2016-06-24 2017-06-21 包含层状双氢氧化物的功能层及复合材料
EP17815456.3A EP3477739A4 (fr) 2016-06-24 2017-06-21 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
PCT/JP2017/022905 WO2017221988A1 (fr) 2016-06-24 2017-06-21 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
JP2018226808A JP6557771B2 (ja) 2016-06-24 2018-12-03 層状複水酸化物を含む機能層及び複合材料
US16/227,469 US10994511B2 (en) 2016-06-24 2018-12-20 Functional layer including layered double hydroxide, and composite material
US16/227,545 US10940668B2 (en) 2016-06-24 2018-12-20 Functional layer including layered double hydroxide, and composite material

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021512463A (ja) * 2018-02-01 2021-05-13 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｃａｌｉｆｏｒｎｉａ レドックスおよびイオン吸着電極ならびにエネルギー貯蔵デバイス
JP2023506018A (ja) * 2019-12-12 2023-02-14 ネルンボ・インコーポレイテッド 機能化テキスタイル組成物及び製品

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6721762B2 (ja) * 2018-06-15 2020-07-15 日本碍子株式会社 電気化学セル
JP6721763B2 (ja) * 2018-06-15 2020-07-15 日本碍子株式会社 電気化学セル
JP6771071B2 (ja) * 2018-06-15 2020-10-21 日本碍子株式会社 電気化学セル用電解質及び電気化学セル
US12249734B2 (en) * 2018-11-22 2025-03-11 Phinergy Ltd. Separators with layered double hydroxides for electrochemical cells
WO2020121673A1 (fr) * 2018-12-13 2020-06-18 日本碍子株式会社 Séparateur au hdl et accumulateur au zinc
WO2020255856A1 (fr) 2019-06-19 2020-12-24 日本碍子株式会社 Séparateur conducteur d'ions hydroxyde et batterie secondaire au zinc
CN115151512B (zh) 2020-03-02 2024-02-06 日本碍子株式会社 层状双氢氧化物及其制造方法、以及采用了该层状双氢氧化物的空气极及金属空气二次电池
JP7441309B2 (ja) * 2020-05-11 2024-02-29 日本碍子株式会社 Ｌｄｈセパレータ及び亜鉛二次電池
DE112021001633T5 (de) 2020-05-11 2022-12-29 Ngk Insulators, Ltd. Ldh-separator und zinksekundärelement
CN117460701A (zh) 2021-07-02 2024-01-26 日本碍子株式会社 层状双氢氧化物、层状双氢氧化物的制造方法、空气极以及金属空气二次电池
WO2023058268A1 (fr) * 2021-10-06 2023-04-13 日本碍子株式会社 Séparateur ldh, procédé de fabrication de celui-ci, et batterie rechargeable au zinc

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089277A (ja) * 2003-09-19 2005-04-07 Toda Kogyo Corp ハイドロタルサイト類化合物粒子粉末及び該ハイドロタルサイト類化合物粒子粉末を含有する水系分散体
JP2010059005A (ja) * 2008-09-02 2010-03-18 Kanazawa Inst Of Technology 複合体および複合体の製造方法
JP2015095286A (ja) * 2013-11-08 2015-05-18 株式会社日本触媒 アニオン伝導膜及び電池
WO2015098610A1 (fr) 2013-12-27 2015-07-02 日本碍子株式会社 Matériau composite contenant un hydroxyde double lamellaire et son procédé de production
WO2016051934A1 (fr) 2014-10-01 2016-04-07 日本碍子株式会社 Batterie utilisant un hydroxyde lamellaire
WO2016076047A1 (fr) 2014-11-13 2016-05-19 日本碍子株式会社 Corps de structure de séparateur destiné à être utilisé dans une batterie secondaire au zinc
WO2016098513A1 (fr) * 2014-12-17 2016-06-23 日本碍子株式会社 Film d'hydroxyde double lamellaire et matériau composte contenant un hydroxyde double lamellaire

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541129B1 (en) * 2004-01-07 2013-09-24 U.S. Department Of Energy Active membrane having uniform physico-chemically functionalized ion channels
WO2008075621A1 (fr) * 2006-12-20 2008-06-26 Kyowa Chemical Industry Co., Ltd. Antiacide
DE102007047764A1 (de) * 2007-10-04 2009-04-09 Süd-Chemie AG Entfernung unerwünschter Begleitstoffe aus Pflanzenproteinextrakten
CA3224506A1 (fr) * 2010-05-12 2011-11-17 Unicycive Therapeutics, Inc. Hydroxyde de carbonate de lanthane, oxycarbonate de lanthane, et procedes pour leur fabrication et methodes pour leur utilisation
WO2013118561A1 (fr) * 2012-02-06 2013-08-15 日本碍子株式会社 Pile rechargeable au zinc
JP5953576B2 (ja) * 2012-03-26 2016-07-20 国立大学法人北海道大学 金属−空気二次電池用空気極触媒層
PT106256A (pt) * 2012-04-17 2013-10-17 Chemetall Gmbh Processo de revestimento de superfícies metálicas com revestimentos contendo partículas de hidróxido duplo lamelar.
GB201217348D0 (en) * 2012-09-28 2012-11-14 Scg Chemicals Co Ltd Modification of layered double hydroxides
CN103964391B (zh) * 2013-01-28 2015-10-14 北京化工大学 一种片状结构层状复合氢氧化物及其制备方法
CN104969384B (zh) * 2013-02-01 2019-01-08 株式会社日本触媒 阴离子传导性材料和电池
WO2014156578A1 (fr) * 2013-03-25 2014-10-02 日本碍子株式会社 Hydroxyde double lamellaire dense et son procédé de production
WO2015098612A1 (fr) * 2013-12-27 2015-07-02 日本碍子株式会社 Film orienté d'hydroxyde bicouche et son procédé de fabrication
JP2016084263A (ja) * 2014-10-28 2016-05-19 日本碍子株式会社 層状複水酸化物緻密膜の形成方法
EP3667807B1 (fr) * 2014-12-02 2021-07-28 NGK Insulators, Ltd. Batterie secondaire zinc-air
JP6429378B2 (ja) * 2014-12-15 2018-11-28 日本碍子株式会社 水酸化物イオン伝導性セラミックスセパレータを用いた二次電池
CN105170076B (zh) * 2015-07-14 2018-07-03 江苏城市职业学院 一种蒙脱石基层状双氢氧化物聚合纳米材料、制备及应用
JP6765855B2 (ja) * 2015-10-29 2020-10-07 株式会社日本触媒 アニオン伝導性膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089277A (ja) * 2003-09-19 2005-04-07 Toda Kogyo Corp ハイドロタルサイト類化合物粒子粉末及び該ハイドロタルサイト類化合物粒子粉末を含有する水系分散体
JP2010059005A (ja) * 2008-09-02 2010-03-18 Kanazawa Inst Of Technology 複合体および複合体の製造方法
JP2015095286A (ja) * 2013-11-08 2015-05-18 株式会社日本触媒 アニオン伝導膜及び電池
WO2015098610A1 (fr) 2013-12-27 2015-07-02 日本碍子株式会社 Matériau composite contenant un hydroxyde double lamellaire et son procédé de production
WO2016051934A1 (fr) 2014-10-01 2016-04-07 日本碍子株式会社 Batterie utilisant un hydroxyde lamellaire
WO2016076047A1 (fr) 2014-11-13 2016-05-19 日本碍子株式会社 Corps de structure de séparateur destiné à être utilisé dans une batterie secondaire au zinc
WO2016098513A1 (fr) * 2014-12-17 2016-06-23 日本碍子株式会社 Film d'hydroxyde double lamellaire et matériau composte contenant un hydroxyde double lamellaire

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021512463A (ja) * 2018-02-01 2021-05-13 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｃａｌｉｆｏｒｎｉａ レドックスおよびイオン吸着電極ならびにエネルギー貯蔵デバイス
JP7390030B2 (ja) 2018-02-01 2023-12-01 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア レドックスおよびイオン吸着電極ならびにエネルギー貯蔵デバイス
JP2023506018A (ja) * 2019-12-12 2023-02-14 ネルンボ・インコーポレイテッド 機能化テキスタイル組成物及び製品

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