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WO2018150919A1 - Batterie secondaire au manganèse - Google Patents

Batterie secondaire au manganèse Download PDF

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Publication number
WO2018150919A1
WO2018150919A1 PCT/JP2018/003696 JP2018003696W WO2018150919A1 WO 2018150919 A1 WO2018150919 A1 WO 2018150919A1 JP 2018003696 W JP2018003696 W JP 2018003696W WO 2018150919 A1 WO2018150919 A1 WO 2018150919A1
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Prior art keywords
ldh
secondary battery
manganese
positive electrode
separator
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Ceased
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PCT/JP2018/003696
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English (en)
Japanese (ja)
Inventor
範之 園山
直美 橋本
直美 齊藤
鬼頭　賢信
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NGK Insulators Ltd
Nagoya Institute of Technology NUC
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NGK Insulators Ltd
Nagoya Institute of Technology NUC
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Priority to JP2018568114A priority Critical patent/JP6978007B2/ja
Publication of WO2018150919A1 publication Critical patent/WO2018150919A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—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
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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 manganese secondary battery.
  • Manganese dioxide (MnO 2 ) is widely used for manganese batteries. Manganese dioxide has the advantage of being an inexpensive cathode material. However, since manganese dioxide cannot be reversibly charged / discharged, any commercialized manganese battery remains a primary battery. That is, manganese secondary batteries such as manganese zinc secondary batteries have not been commercialized.
  • Non-Patent Document 1 (Chihiro Obayashi et al., "Preparation of the Electrochemically Precipitated Mn-Al LDHs and Their Electrochemical Behaviors", Electrochemistry, 80 (11), pp.879-882 (2012))
  • a layered double hydroxide (Mn-Al-LDH) containing Al as a constituent element has been disclosed, and its electrochemical characteristics have been reported.
  • Patent Document 1 International Publication No. 2013/118561 discloses that in a nickel zinc secondary battery, an LDH separator is provided between a positive electrode and a negative electrode for the purpose of preventing a short circuit due to zinc dendrite.
  • 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.
  • Mn-based layered double hydroxide Mn-LDH
  • Mn-LDH Mn-based layered double hydroxide
  • an object of the present invention is to realize a manganese secondary battery using a manganese-based positive electrode material that is inexpensive and rich in elemental resources.
  • a manganese secondary battery includes a positive electrode including a Mn-based layered double hydroxide (Mn-LDH), a negative electrode, and an electrolytic solution including an alkali metal hydroxide aqueous solution. Is done.
  • a positive electrode including a Mn-based layered double hydroxide (Mn-LDH)
  • a negative electrode including a negative electrode
  • an electrolytic solution including an alkali metal hydroxide aqueous solution. Is done.
  • 2 is an SEM image of the Mn—Al—LDH powder produced in Example 1 taken at a magnification suitable for primary particle observation (20000 times).
  • 4 is an SEM image of the Mn—Al—LDH powder produced in Example 1 taken at a magnification suitable for primary particle observation (40000 times).
  • 2 is an SEM image of the Mn—Al—LDH powder produced in Example 1 taken at a magnification (5000 times) suitable for secondary particle observation.
  • 2 is an SEM image of the Mn—Al—LDH powder produced in Example 1 taken at a magnification (5000 times) suitable for secondary particle observation.
  • FIG. 5 is a graph showing charge / discharge characteristics in the reversibility evaluation performed in Example 1.
  • FIG. 8 is a SEM image of the Ni—Mn—Al—LDH powder produced in Example 7 taken at a magnification suitable for primary particle observation (20000 times).
  • 8 is an SEM image of the Ni—Mn—Al—LDH powder produced in Example 7 taken at a magnification suitable for primary particle observation (40000 times).
  • 8 is an SEM image of the Ni—Mn—Al—LDH powder produced in Example 7 taken at a magnification suitable for secondary particle observation (5000 times).
  • 8 is an SEM image of the Ni—Mn—Al—LDH powder produced in Example 7 taken at a magnification suitable for secondary particle observation (5000 times).
  • FIG. 1 conceptually shows a manganese secondary battery according to the present invention.
  • the manganese secondary battery 10 includes a positive electrode 12, a negative electrode 14, and an electrolytic solution 16.
  • the positive electrode 12 includes Mn-based layered double hydroxide (Mn-LDH).
  • the electrolyte solution 16 includes an alkali metal hydroxide aqueous solution. According to such a configuration, by using Mn-LDH for the positive electrode, reversible charging / discharging can be performed, and thus a manganese secondary battery can be realized.
  • Mn-LDH Mn-based layered double hydroxide
  • the electrolyte solution 16 includes an alkali metal hydroxide aqueous solution.
  • Mn-LDH Mn-based layered double hydroxide
  • Mn-LDH Mn-based layered double hydroxide
  • the electrolyte solution 16 includes an alkali metal hydroxide aqueous solution.
  • Mn-LDH Mn-based layered double hydrox
  • the positive electrode 12 includes Mn—LDH.
  • Mn-LDH is a layered double hydroxide (LDH) containing Mn as a constituent element. That is, as is generally known, 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- . Accordingly, Mn-LDH contains Mn or ions thereof as a part of the metal element constituting the hydroxide base layer.
  • Mn-LDH preferably has a particulate form. By being in the form of particles, the surface area is increased and it is possible to cope with a large current discharge.
  • the particulate form of Mn-LDH preferably has an average primary particle size of 0.1 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m, still more preferably 0.1 to 0.7 ⁇ m, and particularly preferably 0.8. 1 to 0.5 ⁇ m. Since LDH is generally poor in conductivity, it is considered that the particulate form (particularly, the one having a small primary particle size as described above) is more reactive than the film-like microstructure.
  • the primary particle diameter is the longest distance of the diameter of Mn-LDH primary particles (plate-like particles), and is observed with a scanning electron microscope (SEM) at a magnification (for example, 40000 times) at which primary particles can be observed. It can be measured using the length measurement function of SEM software.
  • the average primary particle size is determined by measuring the primary particle size of 10 primary particles per field of view, and by calculating the average value of the primary particle sizes for two fields of view (that is, a total of 20 primary particles). It is desirable to decide.
  • Mn-LDH preferably contains Al as a constituent element. That is, Mn-LDH is preferably Mn-Al-LDH containing Mn and Al. In this case, the metal element constituting the hydroxide basic layer of LDH contains Mn and Al. This makes it easy to produce Mn—Al—LDH powder having a desired composition and improves the discharge capacity when used for the positive electrode 12 of the manganese secondary battery 10. From these viewpoints, the molar ratio of Al / (Mn + Al) is preferably 0.15 to 0.85, more preferably 0.20 to 0.80, still more preferably 0.25 to 0.75, and particularly preferably. It is 0.30 to 0.70. Within these ranges, the discharge capacity can be further improved when used for the positive electrode 12 of the manganese secondary battery 10 such as a manganese zinc secondary battery.
  • Mn—Al—LDH powder can be preferably produced by the following procedure. 1) Add and mix Mn (II) metal salt and Al (III) metal salt in distilled water at an arbitrary ratio, and bubbling with an inert gas to degas dissolved oxygen to obtain a metal ion solution. .
  • Arbitrary metal salts such as a chloride and nitrate, can be used for a metal salt. 2) Degas the dissolved oxygen by bubbling an alkaline solution with an inert gas.
  • Mn-LDH further contains Ni as a constituent element in addition to Al. That is, the Mn-LDH is more preferably Ni—Mn—Al—LDH containing Mn, Al and Ni.
  • the metal element constituting the hydroxide basic layer of LDH contains Mn, Al and Ni.
  • the molar ratio of Al / (Ni + Mn + Al) is preferably 0.15 to 0.85, more preferably 0.15 to 0.50, still more preferably 0.15 to 0.40, and particularly preferably 0.00. 20 to 0.30.
  • the molar ratio of Ni / (Ni + Mn + Al) is preferably 0.15 to 0.85, more preferably 0.15 to 0.70, still more preferably 0.15 to 0.50, and particularly preferably 0.20. ⁇ 0.50. Within these ranges, the discharge capacity can be further improved when used for the positive electrode 12 of the manganese secondary battery 10 such as a manganese zinc secondary battery.
  • the method for producing the Ni—Mn—Al—LDH powder is not particularly limited.
  • the Ni—Mn—Al—LDH powder can be preferably produced by the following procedure. 1) A metal salt of Ni (II), a metal salt of Mn (II), and a metal salt of aluminum (III) is added and mixed in distilled water at an arbitrary ratio to obtain a metal ion solution. Arbitrary metal salts, such as a chloride and nitrate, can be used for a metal salt. 2) Ethylene glycol, aqueous ammonia and sodium carbonate solution are mixed to obtain a mixed solvent.
  • the negative electrode 14 is not particularly limited as long as it has a chargeable / dischargeable characteristic in combination with the positive electrode 12 and the electrolytic solution 16.
  • the active material contained in the negative electrode 14 include zinc and / or zinc oxide, hydrogen storage alloy, iron, and cadmium, and more preferably zinc and / or zinc oxide.
  • the manganese secondary battery 10 is a manganese zinc secondary battery.
  • Zinc may be contained in any form of zinc metal, zinc compound and zinc alloy as long as it has an electrochemical activity suitable for the negative electrode.
  • the negative electrode material include zinc oxide, zinc metal, calcium zincate and the like, and a mixture of zinc metal and zinc oxide is more preferable.
  • the negative electrode 14 may be configured in a gel form, or may be mixed with the electrolytic solution 16 to form a negative electrode mixture.
  • the shape of the negative electrode material is not particularly limited, but it is preferably a powder form, which increases the surface area and can cope with a large current discharge.
  • the electrolytic solution 16 includes an alkali metal hydroxide aqueous solution. That is, an aqueous solution containing an alkali metal hydroxide is used as the electrolyte solution 16 (for example, the positive electrode electrolyte solution 16a and the negative electrode electrolyte solution 16b).
  • the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide and the like, and potassium hydroxide is more preferable.
  • the electrolyte solution 16 may include a positive electrode electrolyte solution 16a in which the positive electrode 12 is immersed and a negative electrode electrolyte solution 16b in which the negative electrode 14 is immersed.
  • the electrolyte solution 16 is preferably separated into a positive electrode electrolyte solution 16a and a negative electrode electrolyte solution 16b.
  • This configuration is extremely advantageous in a manganese zinc secondary battery. That is, Zn dissolved in the electrolyte and Mn of LDH may react to form heterolite on the electrode surface.
  • Al is dissolved in the positive electrode electrolyte 16a.
  • concentration of Al dissolved in the positive electrode electrolyte solution 16a is preferably 0.02 to 1.5 mol / L, more preferably 0.02 to 1.2 mol / L, still more preferably 0.05 to 1.0 mol. / L.
  • a zinc compound such as zinc oxide or zinc hydroxide to the negative electrode electrolyte 16b in order to suppress self-dissolution of zinc and / or zinc oxide.
  • the positive electrode electrolyte solution 16a and the negative electrode electrolyte solution 16b may be mixed with the positive electrode 12 and / or the negative electrode 14 to be present in the form of a positive electrode mixture and / or a negative electrode mixture. Further, the electrolytic solution may be gelled in order to prevent leakage of the electrolytic solution.
  • the positive electrode 12 and the positive electrode electrolyte solution 16a are separated by the negative electrode 14, the negative electrode electrolyte solution 16b, and the layered double hydroxide (LDH) separator 28.
  • the oxide ions are isolated so as to be conductive.
  • the LDH separator 28 is known as a dense separator having hydroxide ion conductivity in the field of zinc secondary batteries, and a preferred embodiment thereof will be described below.
  • the LDH separator 28 is a ceramic separator containing layered double hydroxide (LDH), and isolates the positive electrode 12 and the negative electrode 14 so that hydroxide ions can be conducted.
  • a preferred LDH separator 28 is gas impermeable and / or water impermeable.
  • the LDH separator 28 is preferably so dense that it has gas impermeability and / or water impermeability.
  • “having gas impermeability” means that an object to be measured (that is, LDH separator 28 and / or porous material) in water as described in Patent Document 2 (International Publication No. 2016/076047).
  • “having water impermeability” means a measurement object (for example, an LDH film and / or a porous substrate) as described in Patent Document 2 (International Publication No. 2016/076047). ) Means that water that contacts one side does not permeate the other side. That is, the fact that the LDH separator 28 has gas impermeability and / or water impermeability means that the LDH separator 28 has a high degree of denseness that does not allow gas or water to pass through, and has water permeability.
  • the LDH separator 28 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 the zinc dendrite that is generated and propagated from the negative electrode 14 during charging to prevent a short circuit between the positive and negative electrodes.
  • the LDH separator 28 may be combined with the porous substrate 30 as shown in FIG. In any case, since the LDH separator 28 has hydroxide ion conductivity, the required hydroxide ions can be efficiently transferred between the positive electrode electrolyte solution 16a and the negative electrode electrolyte solution 16b. 14 can be realized.
  • the LDH separator 28 includes a layered double hydroxide (LDH), and is preferably composed of LDH.
  • LDH includes 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 LDH separator 28 may be in a plate shape, a film shape, or a layer shape.
  • the film or layer LDH separator 28 is combined with the porous substrate 30.
  • it is preferably formed on or in the porous substrate 30.
  • the plate-like form is used, sufficient hardness can be secured and penetration of zinc dendrites can be more effectively prevented.
  • the film or layer form is thinner than the plate, there is an advantage that the resistance of the separator can be significantly reduced while ensuring the minimum necessary hardness to prevent the penetration of zinc dendrite. is there.
  • a preferable thickness of the plate-like LDH separator 28 is 0.01 to 0.5 mm, more preferably 0.02 to 0.2 mm, and still more preferably 0.05 to 0.1 mm.
  • the hydroxide ion conductivity of the LDH separator 28 is preferably as high as possible, but typically has a conductivity of 10 ⁇ 4 to 10 ⁇ 1 S / m.
  • the thickness is preferably 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 28 can be reduced.
  • the lower limit of the thickness is not particularly limited because it varies depending on the application, but in order to ensure a certain degree of rigidity desired as a separator film or layer, the thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. is there.
  • the LDH separator 28 is preferably combined with the porous substrate 30.
  • the porous substrate 30 may be provided on one side or both sides of the LDH separator 28.
  • the porous substrate 30 may be provided on the surface of the LDH separator 28 on the negative electrode 14 side or on the surface of the LDH separator 28 on the positive electrode 12 side. Also good.
  • the porous base material 30 has water permeability, and therefore the positive electrode electrolyte solution 16a and the negative electrode electrolyte solution 16b can reach the LDH separator 28. It is also possible to hold hydroxide ions more stably on the separator 28.
  • the LDH separator 28 can be thinned to reduce the resistance.
  • a dense film or dense layer of LDH can be formed on or in the porous substrate 30.
  • the porous substrate 30 is provided over the entire surface of one side of the LDH separator 28, but may be provided only on a part of one side of the LDH separator 28 (for example, a region involved in charge / discharge reaction).
  • the porous substrate 30 is provided over the entire surface of one side of the LDH separator 28 due to the manufacturing method. It is typical.
  • the porous base material 30 is retrofitted only on a part of one side of the LDH separator 28 (for example, a region involved in the charge / discharge reaction).
  • the porous substrate 30 may be retrofitted over the entire surface of one side.
  • the LDH separator 28 may be provided on either the positive electrode 12 side or the negative electrode 14 side of the porous substrate 30.
  • the LDH separator 28 is preferably provided on the negative electrode 14 side of the porous substrate 30.
  • the porous substrate 30 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 28 is 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 30 (ignoring fine irregularities caused by the porous structure). The orientation is such that it intersects perpendicularly or diagonally with the main surface of the porous substrate when observed macroscopically as much as possible.
  • the LDH separator 28 may be at least partially incorporated in the pores of the porous substrate 30, and in that case, LDH plate-like particles may also exist in the pores of the porous substrate 30.
  • the manufacturing method of the LDH separator 28, for example, the LDH separator 28 combined with the porous substrate 30, is not particularly limited, and is manufactured by referring to a known manufacturing method of the LDH separator (for example, Patent Documents 1 and 2). be able to.
  • II manganese
  • MnCl 2 .4H 2 O manufactured by Kishida Chemical Co., Ltd., special grade
  • aluminum chloride (III) hexahydrate AlCl 3 .6H 2 O, Kishida Chemical
  • the metal ion solution was placed in an oil bath at 130 ° C., and the sodium hydroxide solution was added dropwise under an inert atmosphere with stirring until the pH reached 11.0 to precipitate a precipitate.
  • the precipitate-containing solution thus obtained was centrifuged to collect the precipitate.
  • the collected LDH precipitate was washed with water, further washed with ethanol, and then dried in vacuum at 80 ° C. to obtain a Mn—Al—LDH powder.
  • the obtained Mn-Al-LDH powder was observed with a scanning electron microscope (SEM) (JSMOL, JSM-6610LV).
  • SEM scanning electron microscope
  • 2A and 2B show SEM images of the LDH powder taken at magnifications (20000 times and 40000 times) suitable for primary particle observation.
  • the primary particle size of the Mn—Al—LDH powder was 0.2 to 0.6 ⁇ m.
  • the average primary particle size of the Mn—Al—LDH powder was 0.36 ⁇ m.
  • the average primary particle size was measured by measuring the longest distance of the diameter of the plate-like particle in the SEM image.
  • the magnification of the SEM image used for this measurement is 40000 times, and the primary particle size is measured for 10 primary particles per field of view. An average value was calculated to obtain an average primary particle size.
  • the length measurement function of SEM software was used for length measurement.
  • FIGS. 3A and 3B show SEM images of the Mn-Al-LDH powder taken at a magnification (5000 times) suitable for secondary particle observation. From the results shown in FIGS. 3A and 3B, the secondary particle size of the Mn—Al—LDH powder was 0.5 to 5 ⁇ m.
  • Examples 2-5 Manganese zinc secondary batteries were fabricated and evaluated in the same manner as in Example 1 except that the Mn—Al—LDH composition was changed so that the Mn: Al ratio (molar ratio) shown in Table 3 was obtained. The results were as shown in Table 2. Note that the average primary particle diameter of the Mn—Al—LDH powder was in the range of 0.1 to 3 ⁇ m.
  • Example 6 Manganese zinc secondary batteries were fabricated and evaluated in the same manner as in Example 1 except that MnO 2 powder was used instead of Mn—Al—LDH powder. The results were as shown in Table 3.
  • nickel chloride (II) hexahydrate NiCl 2 ⁇ 6H 2 O, Wako Pure Chemical Industries, special grade
  • manganese chloride (II) tetrahydrate Mn
  • FIGS. 5A and 5B show SEM images of Ni—Mn—Al—LDH powder taken at magnifications suitable for primary particle observation (20000 times and 40000 times).
  • the primary particle size of the Ni—Mn—Al—LDH powder was 0.1 to 0.4 ⁇ m.
  • the average primary particle size of the Ni—Mn—Al—LDH powder was 0.19 ⁇ m.
  • FIGS. 6A and 6B show SEM images of Ni—Mn—Al—LDH powder taken at a magnification suitable for secondary particle observation (5000 times). From the results shown in FIGS. 6A and 6B, the secondary particle size of the Ni—Mn—Al—LDH powder was 1 to 5 ⁇ m.
  • Evaluation A It was determined that there was no heterogeneous phase.
  • Evaluation B It was determined that the phase was a heterogeneous phase with LDH.
  • Evaluation C It was determined that only a different phase was present.
  • Examples 8 and 9 Manufacture and evaluation of a manganese zinc secondary battery were performed in the same manner as in Example 7 except that the Ni—Mn—Al—LDH composition was changed so that the Ni: Mn: Al ratio (molar ratio) shown in Table 3 was obtained. went. The results were as shown in Table 3.

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Abstract

L'invention concerne une batterie secondaire au manganèse comprenant une électrode positive contenant un hydroxyde double lamellaire à base de Mn (Mn-LDH), une électrode négative, ainsi qu'une solution électrolytique contenant une solution aqueuse d'hydroxyde de métal alcalin. La présente invention permet d'obtenir une batterie secondaire au manganèse au moyen d'un matériau d'électrode positive à base de manganèse.
PCT/JP2018/003696 2017-02-17 2018-02-02 Batterie secondaire au manganèse Ceased WO2018150919A1 (fr)

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JP2018568114A JP6978007B2 (ja) 2017-02-17 2018-02-02 マンガン二次電池

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JP2017028021 2017-02-17
JP2017-028021 2017-02-17

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WO2018150919A1 true WO2018150919A1 (fr) 2018-08-23

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CN116325247A (zh) * 2020-11-30 2023-06-23 日本碍子株式会社 类ldh化合物隔板及锌二次电池
CN117712515A (zh) * 2024-01-04 2024-03-15 德之昭科技(苏州)有限公司 一种碱性铁锰蓄电池

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Publication number Priority date Publication date Assignee Title
CN116325247A (zh) * 2020-11-30 2023-06-23 日本碍子株式会社 类ldh化合物隔板及锌二次电池
CN117712515A (zh) * 2024-01-04 2024-03-15 德之昭科技(苏州)有限公司 一种碱性铁锰蓄电池
CN117712515B (zh) * 2024-01-04 2025-03-28 德之昭科技(苏州)有限公司 一种碱性铁锰蓄电池

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