WO2020085015A1 - Électrode et batterie secondaire au lithium-ion à semi-conducteur - Google Patents

Électrode et batterie secondaire au lithium-ion à semi-conducteur Download PDF

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WO2020085015A1
WO2020085015A1 PCT/JP2019/038835 JP2019038835W WO2020085015A1 WO 2020085015 A1 WO2020085015 A1 WO 2020085015A1 JP 2019038835 W JP2019038835 W JP 2019038835W WO 2020085015 A1 WO2020085015 A1 WO 2020085015A1
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lipo
electrode
oxide
active material
glass
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Japanese (ja)
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裕輔 山本
淳一 丹羽
明 後藤
武文 福本
町田　信也
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株式会社豊田自動織機
学校法人甲南学園
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 solid-state lithium-ion secondary battery and an electrode used in the solid-state lithium-ion secondary battery.
  • non-aqueous secondary batteries in which a resin separator is impregnated with a non-aqueous electrolytic solution containing an organic solvent are mainly used as secondary batteries.
  • the non-aqueous electrolyte containing the organic solvent is not completely fixed by the separator, the non-aqueous electrolyte may leak when the battery is damaged.
  • solid-state secondary batteries using solid electrolytes such as ceramics and polymers instead of non-aqueous electrolyte and resin separators are being actively researched and developed.
  • sulfides have the property that the conductivity of lithium ions, which are charge carriers, is relatively high.
  • the sulfide material is relatively soft, it has excellent moldability and has an advantage that it is easy to form an interface between the sulfide material and the active material used for the electrode.
  • the sulfide material and the active material can be brought into close contact with each other only by pressurizing a mixture thereof to form the above interface, so that a conduction path for lithium ions can be easily secured.
  • the oxide is made into a solid electrolyte through sintering at a high temperature.
  • the solid electrolyte made of an oxide has a high density and a dense structure, so that the problem of dendrite hardly occurs.
  • a solid electrolyte using an oxide is poor in moldability because it is hard and forms an interface between the oxide type solid electrolyte and the active material used for the electrode. Is relatively difficult.
  • the solid-type secondary electrolyte is sputtered by adhering the positive electrode active material to the oxide-type solid electrolyte by sputtering, or the sintering method by sintering the bonded product in which the positive-electrode active material is adhered to the oxide-type solid electrolyte. I had no choice but to manufacture batteries.
  • the thickness of the positive electrode is on the nano level, and it is difficult to increase the capacity of the solid secondary battery.
  • the positive electrode active material may be denatured due to heat.
  • Li 7 La 3 Zr 2 O 12 As described in Non-Patent Document 1, Weppner et al. Proposed Li 7 La 3 Zr 2 O 12 as a garnet-type oxide that exhibits high conductivity and is electrochemically stable. Li 7 La 3 Zr 2 O 12, which is this oxide type solid electrolyte, is generally produced at a temperature of 1000 ° C. or higher.
  • the positive electrode in this reason, to improve the adhesion between the Li 7 La 3 Zr 2 O 12 and the positive electrode active material, for example, the raw material powder of Li 7 La 3 Zr 2 powder O 12 or Li 7 La 3 Zr 2 O 12
  • heating at 1000 ° C. or higher is required.
  • the positive electrode active material may be denatured due to such temperature, it is practically difficult to adopt the sintering method.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a new electrode suitable for a solid-state lithium-ion secondary battery that includes an oxide-type solid electrolyte as a separator.
  • the present inventor has conceived a technique of bringing electrodes into close contact with a separator made of an oxide type solid electrolyte by utilizing the property of low melting point glass containing lithium. Specifically, by containing a low-melting-point glass containing lithium in the electrode active material layer in which the electrode active material is present, while ensuring movement of lithium ions inside the electrode active material layer, It was recalled that the moldability and the adhesiveness of the electrode active material layer and the separator made of the oxide type solid electrolyte are secured. Then, the present inventor has completed the present invention by paying attention to LiPO 3 —Li 2 SO 4 type glass as a low melting point glass containing lithium and conducting intensive studies.
  • the electrode of the present invention contains an oxide electrolyte and an electrode active material produced by melting and cooling a composition represented by (100- (x + y)) LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4. It is characterized by including an electrode active material layer and a current collector.
  • x and y satisfy x ⁇ 0, y ⁇ 0, and 0 ⁇ x + y ⁇ 60.
  • the solid-state lithium-ion secondary battery of the present invention includes the electrode of the present invention, a counter electrode, and a separator made of an oxide-type solid electrolyte as a material between the electrode and the counter electrode.
  • the electrode of the present invention is excellent in its own moldability and is also excellent in forming an interface with a separator using an oxide type solid electrolyte as a material.
  • 3 is a powder X-ray diffraction chart of Evaluation Example 1.
  • 3 is a DSC chart of LiPO 3 —Li 2 SO 4 type glass of Production Example
  • E. 3 is a charge / discharge curve of the lithium-ion secondary battery of Reference Example 1.
  • 3 is a schematic diagram of a solid-state lithium-ion secondary battery of Example 2.
  • FIG. 3 is a charging curve of the solid-state lithium-ion secondary battery of Example 2.
  • 3 is a discharge curve of the solid-state lithium-ion secondary battery of Example 2.
  • 5 is a charge / discharge curve of the solid-state lithium-ion secondary battery of Example 3. It is an overwriting of the Raman spectrum of the evaluation example 11.
  • 5 is a charge / discharge curve of the solid-state lithium-ion secondary battery of Example 5.
  • 9 is a charge / discharge curve of the solid-state lithium-ion secondary battery of Example 6.
  • the numerical range “ab” described in the present specification includes the lower limit a and the upper limit b in the range.
  • the upper limit value and the lower limit value, and the numerical values listed in Examples, Reference Examples, and the like can be arbitrarily combined to form a numerical value range. Further, numerical values arbitrarily selected from the numerical range can be set as upper and lower numerical values.
  • the electrode of the present invention is an oxide electrolyte prepared by melting and cooling a composition represented by (100- (x + y)) LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4 (in the present specification, " It may be referred to as "LiPO 3 -Li 2 SO 4 based glass"), an electrode active material layer containing an electrode active material, and a current collector.
  • x and y satisfy x ⁇ 0, y ⁇ 0, and 0 ⁇ x + y ⁇ 60.
  • the electrode of the present invention may be a positive electrode or a negative electrode.
  • the electrode of the present invention is preferably the positive electrode. If the electrode is a positive electrode, the electrode active material is the positive electrode active material and the electrode active material layer is the positive electrode active material layer. If the electrode is a negative electrode, the electrode active material is the negative electrode active material and the electrode active material layer is the negative electrode active material layer.
  • the positive electrode active material as long as it can be used as a positive electrode active material for a secondary battery, for example, the general formula of the layered rock salt structure: Li a Ni b Co c M d D e O f (M is Al and / or Mn, D is W, Mo, Re, Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, Rh, At least one element selected from Fe, Ge, Zn, Ru, Sc, Sn, In, Y, Bi, S, Si, Na, K, P and V.
  • Li 2 MnO 3 can be mentioned.
  • a spinel such as LiMn 2 O 4 , Li 2 Mn 2 O 4 and the like, and a solid solution composed of a mixture of a spinel and a layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (M in the formula: Are selected from at least one of Co, Ni, Mn, and Fe)) and the like.
  • tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal)
  • LiMPO 4 F such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal
  • Any of the metal oxides used as the positive electrode active material may have the above composition formula as a basic composition, and a metal element contained in the basic composition may be substituted with another metal element.
  • a positive electrode active material material that does not contain lithium ions that contribute to charge and discharge for example, simple substance of sulfur, a compound of sulfur and carbon, a metal sulfide such as TiS 2 , V 2 O 5 , MnO.
  • oxides such as 2 , polyaniline and anthraquinone, compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic compounds, and other known materials.
  • a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, or phenoxyl may be adopted as the positive electrode active material.
  • a positive electrode active material containing no lithium it is necessary to add ions to the positive electrode and / or the negative electrode by a known method in advance.
  • a metal or a compound containing the ion may be used.
  • the general formula of the layered rock salt structure Li a Ni b Co c M d D e O f (M is Al and / or Mn .D is W, Mo, Re , Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, Rh, Fe, Ge, Zn, Ru, Sc, Sn , In, Y, Bi, S, Si, Na, K, P, and V.
  • 0.2 ⁇ a ⁇ 2, b + c + d + e 1, 0 ⁇ e ⁇ 1, 1.7 ⁇
  • a lithium composite metal oxide represented by the formula: f ⁇ 3 is preferable.
  • the values of b, c, and d are not particularly limited as long as the above conditions are satisfied, but those satisfying 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1 Good, and at least one of b, c, d is in the range of 10/100 ⁇ b ⁇ 95/100, 1/100 ⁇ c ⁇ 60/100, 1/100 ⁇ d ⁇ 60/100.
  • the range of 40/100 ⁇ b ⁇ 90/100, 1/100 ⁇ c ⁇ 40/100, 1/100 ⁇ d ⁇ 40/100 is more preferable, and 60/100 ⁇ b ⁇ 85/100, The range of 1/100 ⁇ c ⁇ 20/100 and 1/100 ⁇ d ⁇ 20/100 is more preferable.
  • any numerical value within the range defined by the above general formula may be used, and preferably 0.5 ⁇ a ⁇ 1.5, 0 ⁇ e ⁇ 0.2, 1.8 ⁇ f ⁇ 2. 0.5, more preferably 0.8 ⁇ a ⁇ 1.3, 0 ⁇ e ⁇ 0.1, and 1.9 ⁇ f ⁇ 2.1, respectively.
  • the negative electrode active material a material capable of inserting and extracting lithium ions can be used. Therefore, there is no particular limitation as long as it is a simple substance, an alloy, or a compound capable of inserting and extracting lithium ions.
  • the negative electrode active material Li, Group 14 elements such as carbon, silicon, germanium, and tin, Group 13 elements such as aluminum and indium, Group 12 elements such as zinc and cadmium, Group 15 elements such as antimony and bismuth, and magnesium.
  • An alkaline earth metal such as calcium, or a Group 11 element such as silver or gold may be used alone.
  • the negative electrode active material When silicon or the like is used as the negative electrode active material, one atom of silicon reacts with a plurality of lithium, resulting in a high-capacity active material. However, there is a problem that the volume expansion and contraction accompanying lithium absorption and desorption becomes significant. Since this may occur, it is also preferable to employ an alloy or compound in which a simple substance such as silicon is combined with another element such as a transition metal as the negative electrode active material in order to reduce the possibility.
  • Specific examples of alloys or compounds include tin-based materials such as Ag—Sn alloys, Cu—Sn alloys, Co—Sn alloys, carbon-based materials such as various graphites, and SiO x (0.3 ⁇ x ⁇ 1.6).
  • a silicon-based material a silicon simple substance, or a composite of a silicon-based material and a carbon-based material.
  • LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4 which is a raw material of the LiPO 3 --Li 2 SO 4 system glass, are x ⁇ 0, y ⁇ 0, 0 ⁇ x + y ⁇ . Satisfy 60. Since x + y is within the range of 0 ⁇ x + y ⁇ 60, the LiPO 3 —Li 2 SO 4 based glass is in a glass state and exhibits a certain degree of conductivity. When LiPO 3 —Li 2 SO 4 system glass is measured by a powder X-ray diffractometer, a halo showing an amorphous state is observed.
  • LiPO 3 —Li 2 SO 4 type glass exhibits a glass transition temperature in a relatively low temperature region. Therefore, during the production of the electrode of the present invention, the mixture of the electrode active material and LiPO 3 -Li 2 SO 4 -based glass, by heating at a temperature above the glass transition temperature of LiPO 3 -Li 2 SO 4 -based glass, LiPO The 3- Li 2 SO 4 based glass can be softened and enter the gaps between the particles of the electrode active material. As a result, an electrode active material layer having a dense structure is formed.
  • x + y the lower the glass transition temperature of the LiPO 3 —Li 2 SO 4 based glass tends to be. From the viewpoint that the heating temperature at the time of manufacturing the electrode can be lowered, x + y is preferably large. Further, it is considered that the LiPO 3 —Li 2 SO 4 based glass using the raw material in which the value of x + y is in the range of 45 to 55 has the maximum value of electric conductivity of the LiPO 3 —Li 2 SO 4 based glass. On the other hand, when the value of x + y exceeds 60, crystals are likely to be generated, and it may be difficult to manufacture glass.
  • x + y preferably satisfies 40 ⁇ x + y ⁇ 60, more preferably 45 ⁇ x + y ⁇ 55, and further preferably 47 ⁇ x + y ⁇ 53. .
  • the LiPO 3 —Li 2 SO 4 system glass plays an important role for ensuring the denseness and formability of the electrode active material layer, and further, as a current collector. It plays an important role in ensuring the adhesiveness of the electrode active material layer.
  • the LiPO 3 —Li 2 SO 4 based glass plays an important role in ensuring the conductivity and the lithium ion conductivity of the electrode active material layer in terms of the function of the electrode of the present invention.
  • LiPO 3 —Li 2 SO 4 -based glass is a suitable interface between the electrode of the present invention and a separator using an oxide-type solid electrolyte as a material. Play an important role in forming the.
  • the mass ratio of the electrode active material and LiPO 3 —Li 2 SO 4 based glass is preferably in the range of 8: 2 to 3: 7, more preferably in the range of 7: 3 to 4: 6. preferable.
  • the LiPO 3 —Li 2 SO 4 based glass can be produced by heating and melting a mixture of LiPO 3 glass, Li 2 SO 4 and / or Li 2 WO 4 to form a liquid, and rapidly cooling the liquid.
  • the LiPO 3 glass can be manufactured by heating a mixture of a Li compound and a phosphoric acid compound into a liquid and rapidly cooling the liquid.
  • the present inventor also used (100- (x + y)) LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4 (x, which was used as a raw material, due to the melting temperature during the production of LiPO 3 --Li 2 SO 4 system glass.
  • y satisfy x ⁇ 0, y ⁇ 0, 0 ⁇ x + y ⁇ 60) and the composition in the LiPO 3 —Li 2 SO 4 based glass may be different from each other. I found out. Specifically, it was found that at the time of manufacturing, a part of S escapes from the system.
  • the LiPO 3 —Li 2 SO 4 type glass produced by removing a part of S out of the system at the time of production exhibits properties of excellent electrical conductivity and smooth movement of lithium ions. I also found out. It is considered that when S is released from the system, it is released as sulfur oxide along with oxygen.
  • the melting in the production of the LiPO 3 —Li 2 SO 4 type glass is performed in the atmosphere, that is, in the presence of oxygen, so that oxygen is abundant in the system. Therefore, since the amount of oxygen required for the production of a stable product is supplied, it is not expected that the amount of oxygen is unnaturally insufficient in the LiPO 3 —Li 2 SO 4 based glass.
  • the melting temperature in the above production method is preferably in the range of 650 to 950 ° C, more preferably in the range of 700 to 900 ° C, and even more preferably in the range of 750 to 850 ° C.
  • the melting temperature may be changed in multiple steps.
  • the holding time of the melting temperature in the above production method may be, for example, 0.5 to 5 hours, 1 to 4 hours, and 1.5 to 3 hours, although it depends on the melting temperature.
  • the LiPO 3 —Li 2 SO 4 system glass having a composition in which a part of S is separated from the elemental composition of the raw material is suitable for the performance as an electrolyte.
  • composition of LiPO 3 —Li 2 SO 4 system glass in which a part of S is desorbed from the elemental composition of the raw material is Li (100 + x + y) P (100- (x + y)) S x1 W y O (300 + x + y) (however, x1 ⁇ x is satisfied).
  • composition formula (1) corresponds to the composition formula of the raw material divided by about 100.
  • Li a P b S c W d O e a, b, c, d and e are 1 ⁇ a ⁇ 1.6, 0.4 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 0.6, 0 ⁇ d ⁇ 0.6, 0 ⁇ c + d ⁇ 0.6 , B + c + d ⁇ 1, 3 ⁇ e ⁇ 3.6 are satisfied.
  • the range of a is 1.2 ⁇ a ⁇ 1.6, 1.4 ⁇ a ⁇ 1.58, 1.45 ⁇ a ⁇ 1.57, 1.50 ⁇ a ⁇ 1.56, 1.51 ⁇
  • a ⁇ 1.55 can be exemplified.
  • Examples of the range of b include 0.4 ⁇ b ⁇ 0.8, 0.45 ⁇ b ⁇ 0.6, 0.47 ⁇ b ⁇ 0.55, and 0.48 ⁇ b ⁇ 0.52.
  • Examples of the range of c include 0.05 ⁇ c ⁇ 0.5, 0.1 ⁇ c ⁇ 0.4, 0.15 ⁇ c ⁇ 0.38, and 0.2 ⁇ c ⁇ 0.35.
  • Examples of the range of e include 3.01 ⁇ e ⁇ 3.4, 3.02 ⁇ e ⁇ 3.2, and 3.03 ⁇ e ⁇ 3.15.
  • a solid electrolyte other than LiPO 3 —Li 2 SO 4 based glass and known additives such as a conduction aid are blended within a range not departing from the gist of the present invention. May be.
  • the conduction aid is added to enhance the conductivity of the electrode. Therefore, the conductive additive may be optionally added when the conductivity of the electrode is insufficient, and may not be added when the conductivity of the electrode is sufficiently excellent.
  • the electrically conductive auxiliary agent may be a chemically inert electronic high conductor, and carbonaceous fine particles such as carbon black, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber), and various metal particles are exemplified. It Examples of carbon black include acetylene black, Ketjen black (registered trademark), furnace black, channel black and the like. These conductive aids can be added to the active material layer either individually or in combination of two or more.
  • Current collector refers to a chemically inactive electron high conductor that keeps current flowing through the electrodes during discharging or charging of the solid-state lithium-ion secondary battery.
  • As the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, stainless steel, etc. A metal material can be illustrated.
  • the current collector may be covered with a known protective layer. You may use what collected the surface of the collector by a well-known method as a collector.
  • the current collector can take the form of foil, sheet, film, wire, rod, mesh, or the like. Therefore, as the current collector, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, or a stainless steel foil can be preferably used. When the current collector is in the form of foil, sheet or film, its thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the method for producing the electrode of the present invention includes: A composition represented by (100- (x + y)) LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4 (where x and y satisfy x ⁇ 0, y ⁇ 0, 0 ⁇ x + y ⁇ 60).
  • a step of mixing the oxide type electrolyte produced by melting and cooling and the electrode active material to form a mixture (hereinafter sometimes referred to as a mixing step), Heating the mixture at a temperature in the range above the glass transition temperature and below the crystallization temperature of the oxide-type electrolyte in the state where the mixture and the current collector are in contact with each other (hereinafter sometimes referred to as a heating step);
  • the manufacturing method having
  • a general mixer such as a mixing stirrer, a ball mill, a sand mill, a bead mill, a disperser, an ultrasonic disperser, a homogenizer, a homomixer, and a planetary mixer may be adopted.
  • the heating temperature in the heating step is too high, the LiPO 3 —Li 2 SO 4 based glass may be crystallized, which is inconvenient. Furthermore, the electrode active material may be deteriorated or deteriorated. From these points, the upper limit of the heating temperature is preferably less than 400 ° C.
  • the heating temperature in the heating step is preferably a glass transition temperature (hereinafter sometimes abbreviated as Tg) of LiPO 3 —Li 2 SO 4 based glass or more and less than 400 ° C., more preferably Tg or more and 350 ° C. or less, and more than Tg or more.
  • Tg glass transition temperature
  • the temperature is more preferably 330 ° C. or lower, particularly preferably Tg or higher and 310 ° C.
  • the heating temperature in the heating step may be Tg + 5 ° C. to Tg + 40 ° C., Tg + 5 ° C. to Tg + 30 ° C., or Tg + 5 ° C. to Tg + 20 ° C.
  • the heating step it is preferable to secure the time and environment for the softened LiPO 3 —Li 2 SO 4 based glass to flow into the gaps between the particles of the electrode active material during heating.
  • the time and environment for the softened LiPO 3 —Li 2 SO 4 based glass it is preferable to maintain the condition for applying and / or reducing the external pressure to the mixture for a certain period of time.
  • the heating step is preferably performed in an atmosphere that suppresses deterioration of the electrode active material and the LiPO 3 —Li 2 SO 4 based glass, and is performed in an atmosphere of an inert gas such as helium, argon, or nitrogen. preferable.
  • a heating device used in the heating step a pressurizing-heating device (hot press etc.) capable of pressurizing is preferable, and further, a discharge plasma sintering device capable of pressurizing and heating while energizing can also be used. it can.
  • the solid-state lithium-ion secondary battery of the present invention includes the electrode of the present invention, a counter electrode, and a separator made of an oxide solid electrolyte as a material between the electrode and the counter electrode.
  • the counter electrode may be the electrode of the present invention or a conventional general electrode.
  • oxide type solid electrolyte one that does not react with lithium during the operation of the solid state lithium ion secondary battery and does not cause a reduction reaction during the operation of the solid state lithium ion secondary battery is selected.
  • oxide type solid electrolyte examples include garnet type oxide, NASICON type oxide, and LISICON type oxide.
  • oxide type solid electrolyte an oxide containing no transition metal in the composition is desirable in view of the potential window. The reason is that when an oxide containing a transition metal is used as the solid electrolyte, when a material having a low potential is used for the negative electrode, the transition metal in the solid electrolyte is reduced before the negative electrode reaction, and therefore the applied current is This is because it is used not for the reaction but for the reductive decomposition of the electrolyte.
  • a composition formula Li a M 1 3 M 2 2 O 12 5 ⁇ a ⁇ 7, M 1 is Y, La, Pr, Nd, Sm, Lu, Mg, Ca, or One or more elements selected from Sr or Ba, M 2 is an oxide represented by one or more elements selected from Zr, Hf, Nb or Ta, and Li and M of the composition formula.
  • some of 1 or M 2 can be exemplified oxides substituted with Li, M 1 or M 2. More specific garnet-type oxides, Li 7 La 3 Zr 2 O 12, Li 5 La 3 Nb 2 O 12, Li 5 La 3 Ta 2 O 12, Li 5 La 3 (Nb, Ta) 2 O 12 , Li 6 BaLa 2 Ta 2 O 12 can be mentioned.
  • the garnet-type oxide is particularly preferable because it has the advantage that it does not react even under a high potential condition of 5 V or 6 V between the positive electrode and the negative electrode in addition to the advantage that it does not react under a condition where the potential with respect to lithium is 0 V or lower. .
  • NASICON-type oxide a composition formula Li a M 3 b M 4 c P d O e (0.5 ⁇ a ⁇ 5, 0 ⁇ b ⁇ 3, 0.5 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 3, 2 ⁇ b + d ⁇ 4, 3 ⁇ e ⁇ 12, M 3 is one or more elements selected from B, Al, Ga, In, C, Si, Ge, Sn, Sb, or Se, and M 4 is Ti or Zr. , Hf, Ge, In, Ga, Sn, or one or more elements selected from Al).
  • Suitable NASICON-type oxides include those in which M 3 is Al and M 4 is Ge, and specifically, Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 can be exemplified.
  • LISICON-type oxide is an oxide represented by the composition formula Li 4-2x Zn x GeO 4 (0 ⁇ x ⁇ 1).
  • LiPON which part of oxygen in the Li 3 PO 4, Li 3 PO 4 was replaced by nitrogen, can be exemplified Li 3 BO 3.
  • a composition represented by (100- (x + y)) LiPO 3 .xLi 2 SO 4 .yLi 2 WO 4 (where x and y satisfy x ⁇ 0, y ⁇ 0, 0 ⁇ x + y ⁇ 60).
  • An oxide type electrolyte produced by melting and cooling the composition represented may be adopted as an oxide type solid electrolyte as a separator.
  • a composition represented by LiPO 3 —Li 2 SO 4 based glass in the electrode of the present invention and (100-x) LiPO 3 ⁇ xLi 2 SO 4 (x satisfies 0 ⁇ x ⁇ 60) in the separator is prepared.
  • the oxide electrolytes produced by melting and cooling may be different or the same.
  • the thickness (t) of the separator made of the oxide solid electrolyte is preferably 0.1 ⁇ m ⁇ t ⁇ 2000 ⁇ m, more preferably 0.5 ⁇ m ⁇ t ⁇ 1500 ⁇ m, and further preferably 1 ⁇ m ⁇ t ⁇ 300 ⁇ m. If t is too thick, the resistance increases, which makes it difficult to operate as a battery, and there is a concern that the solid-state lithium-ion secondary battery may increase in size. On the other hand, if t is too thin, manufacturing work may be difficult.
  • a state in which LiPO 3 —Li 2 SO 4 -based glass exists between the current collector of the electrode and the separator made of the oxide-type solid electrolyte it is preferable to perform the step of heating at a temperature within the range of the glass transition temperature of the LiPO 3 —Li 2 SO 4 based glass or more and less than the crystallization temperature (hereinafter, sometimes referred to as an electrode-separator adhesion step).
  • the electrode-separator adhesion step include a state in which an electrode active material layer is sandwiched between a current collector and a separator made of an oxide solid electrolyte, or an electrode active material and LiPO 3 -Li. while sandwiching a mixture of 2 SO 4 -based glass, it may be mentioned the step of heating at a temperature of LiPO 3 -Li within 2 SO 4 system range below the glass transition temperature or higher and the crystallization temperature of the glass.
  • the LiPO 3 —Li 2 SO 4 based glass is softened, and the electrode active material layer can be appropriately adhered to the separator made of the oxide solid electrolyte. Therefore, the interface formed between the electrode and the separator of the present invention is extremely suitable.
  • the electrode of the present invention having a current collector and an electrode active material layer may be used, or the electrode active material and LiPO 3 —Li 2 SO 2 may be used. Alternatively, the electrode active material layer may be used after separately manufacturing the electrode active material layer containing the 4 system glass.
  • the electrode of the present invention is produced and the electrode of the present invention and oxide are produced in one step.
  • a laminated body in which a separator made of a solid electrolyte is closely attached is manufactured.
  • the heating temperature in the electrode-separator contact step is preferably the glass transition temperature of LiPO 3 —Li 2 SO 4 glass or higher and lower than 400 ° C., more preferably Tg or higher and 350 ° C. or lower, still more preferably Tg or higher and 330 ° C. or lower, and Tg or lower. It is particularly preferable that the temperature is 310 ° C. or lower and Tg is 300 ° C. or lower.
  • the heating temperature in the electrode-separator contacting step may be Tg + 5 ° C. to Tg + 40 ° C., Tg + 5 ° C. to Tg + 30 ° C., or Tg + 5 ° C. to Tg + 20 ° C.
  • the electrode-separator contacting step it is preferable to apply an external pressure in the stacking direction of the current collector and the separator during heating.
  • the electrode-separator contacting step is preferably carried out in an atmosphere that suppresses the deterioration of the electrode active material and the LiPO 3 —Li 2 SO 4 based glass.
  • the solid-state lithium-ion secondary battery of the present invention due to its configuration, the electrode active material layer and the separator made of the oxide-type solid electrolyte can be suitably bonded, so that a lithium-ion conduction path is preferably secured. it can. Furthermore, since the solid-state lithium-ion secondary battery of the present invention employs a separator made of an oxide-type solid electrolyte, dendrite formation can be suitably suppressed.
  • the shape of the solid-state lithium-ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylinder type, a square type, a coin type and a laminated type can be adopted.
  • the solid-state lithium-ion secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be any vehicle that uses electric energy from the secondary battery for all or part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle.
  • a solid-state lithium-ion secondary battery is mounted on a vehicle, it is advisable to connect a plurality of solid-state lithium-ion secondary batteries in series to form an assembled battery.
  • Examples of devices equipped with the solid-state lithium-ion secondary battery include, in addition to vehicles, personal computers, portable communication devices, and other battery-driven home appliances, office devices, industrial devices, and the like.
  • the solid-state lithium-ion secondary battery of the present invention is a power storage device and power smoothing device for wind power generation, solar power generation, hydroelectric power generation and other power systems, power supply for ships and / or power supply for auxiliary machinery, Power supply source for aircraft and spacecraft and / or auxiliary machinery, auxiliary power supply for vehicles that do not use electricity as power source, mobile home robot power supply, system backup power supply, uninterruptible power supply It may be used as a power storage device or a power storage device that temporarily stores electric power required for charging in a charging station for electric vehicles.
  • Production Example B A transparent LiPO 3 —Li 2 SO 4 based glass of Production Example B was produced in the same manner as in Production Example A, except that LiPO 3 glass and Li 2 SO 4 ⁇ H 2 O were used at a molar ratio of 60:40. did.
  • Production Example D A transparent LiPO 3 —Li 2 SO 4 based glass of Production Example D was produced in the same manner as in Production Example A, except that LiPO 3 glass and Li 2 SO 4 ⁇ H 2 O were used at a molar ratio of 50:50. did.
  • Production Example K A transparent LiPO 3 -Li of Production Example K was prepared in the same manner as in Production Example A, except that LiPO 3 glass, Li 2 SO 4 .H 2 O and Li 2 WO 4 were used at a molar ratio of 50:30:20. 2 SO 4 type glass was manufactured.
  • LiPO 3 -Li of Preparation Example O was prepared in the same manner as in Preparation Example A, except that LiPO 3 glass, Li 2 SO 4 .H 2 O and Li 2 WO 4 were used at a molar ratio of 50:10:40. 2 SO 4 type glass was manufactured.
  • LiPO 3 -Li of Preparation Example R was prepared in the same manner as in Preparation Example A, except that LiPO 3 glass, Li 2 SO 4 .H 2 O and Li 2 WO 4 were used at a molar ratio of 60:20:20. 2 SO 4 type glass was manufactured.
  • LiPO 3 glass except for using the Li 2 SO 4 ⁇ H 2 O and Li 2 WO 4 in a molar ratio 30:35:35 are in Production Example A similar method, LiPO 3 -Li 2 SO of Preparation T 4 series glass was manufactured. White turbidity was observed in the LiPO 3 —Li 2 SO 4 based glass of Production Example T. Such cloudiness is considered to be crystals.
  • Table 1 shows a list of the produced LiPO 3 —Li 2 SO 4 based glasses.
  • FIG. 2 shows a DSC chart of the LiPO 3 —Li 2 SO 4 based glass of Production Example E.
  • the difference between Tc and Tg is almost constant in any LiPO 3 —Li 2 SO 4 based glass.
  • Tg tends to increase as the value of y increases.
  • x (or x + y) in the raw material of the LiPO 3 —Li 2 SO 4 system glass is preferably 45 ⁇ x (or x + y) ⁇ 55. , 47 ⁇ x (or x + y) ⁇ 53 is more preferable.
  • An annular insulating synthetic resin was placed on the copper foil.
  • the insulating synthetic resin was filled with the LiPO 3 —Li 2 SO 4 system glass of Production Example D in the ring, and a small amount of a mixed solvent of ethylene carbonate and diethyl carbonate was added.
  • a cell for evaluation in which the LiPO 3 —Li 2 SO 4 system glass of Production Example D was sandwiched between the copper foil and the lithium foil was produced.
  • the evaluation cell was subjected to a cyclic voltammetry (hereinafter sometimes abbreviated as CV) test in which a voltage of 0 to 2 V was applied. did.
  • CV cyclic voltammetry
  • Example 1 59 parts by mass of LiCoO 2 as a positive electrode active material, 39 parts by mass of LiPO 3 —Li 2 SO 4 based glass of Production Example D, and 2 parts by mass of acetylene black as a conductive additive were mixed to form a positive electrode active material layer.
  • a manufacturing composition was prepared. The composition for producing a positive electrode active material layer was placed in a pressure-heating device under a nitrogen atmosphere. The composition for producing the positive electrode active material layer was heated to 300 ° C. and held for 15 minutes. Then, the composition for producing a positive electrode active material layer heated at 300 ° C. was pressurized at 100 MPa, and the heated / pressurized state was maintained for 30 minutes, and then cooled to room temperature to obtain the positive electrode active material layer of Example 1. Manufactured.
  • a foil made of stainless steel (corresponding to SUS316) having a diameter of 15.5 mm and a thickness of 1 mm was prepared as a current collector.
  • paste-like graphite powder-dispersed water was prepared as a binder between the current collector and the positive electrode active material layer of Example 1.
  • Graphite powder-dispersed water was applied to the surface of the current collector, and the positive electrode active material layer of Example 1 was placed thereon to form a laminate.
  • the positive electrode of Example 1 was manufactured by drying a laminated body and removing water.
  • a metal lithium foil having a thickness of 500 ⁇ m was cut into a diameter of 16 mm to obtain a negative electrode.
  • a glass filter having a diameter of 16 mm and a thickness of 1 mm was prepared as a separator.
  • LiPF 6 was dissolved at a concentration of 1 mol / L in an organic solvent in which ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate were mixed at a volume ratio of 3: 4: 4 to obtain an electrolytic solution.
  • the separator was sandwiched between the positive electrode and the negative electrode of Example 1 to form an electrode body.
  • This electrode body was housed in a coin type battery case CR2032 (Hosen Co., Ltd.), and an electrolytic solution was further injected to obtain a coin type battery. This was used as the lithium-ion secondary battery of Reference Example 1.
  • Example 2 40 parts by mass of a layered rock salt structure lithium nickel cobalt manganese composite oxide as a positive electrode active material, 58 parts by mass of LiPO 3 —Li 2 SO 4 based glass of Production Example D, and 2 parts by mass of acetylene black as a conductive additive. Were mixed to obtain a composition for producing a positive electrode active material layer.
  • LiPO 3 —Li 2 SO 4 glass of Production Example D 50 mg was pressed at 130 MPa under room temperature conditions to obtain an oxide solid electrolyte having a diameter of 10 mm and a thickness of 0.5 mm. This was used as a separator.
  • a lithium foil having a diameter of 6 mm and a mass of 58.8 mg was prepared.
  • composition for producing a positive electrode active material layer 2.5 mg was placed on an Al foil as a current collector, and a separator was placed thereon. These are heated at 300 ° C. and pressurized at 130 MPa, and the heated / pressurized state is maintained for 30 minutes to form a positive electrode active material layer having a thickness of 0.0148 mm, and a current collector and a positive electrode active material layer.
  • a laminated body was manufactured in which an oxide type solid electrolyte as a separator was integrated. Further, a lithium foil and a Cu foil as a current collector were laminated on the oxide type solid electrolyte and pressed to manufacture a solid type lithium ion secondary battery of Example 2.
  • a cylindrical side molding die made of ceramics and having an inner diameter of 10 mm, and an upper portion made of stainless steel (corresponding to SUS316).
  • a molding apparatus including a molding die and a lower molding die was used.
  • FIG. 4 shows a schematic diagram of the solid-state lithium-ion secondary battery of Example 2 immediately after production.
  • a positive electrode 1 in which a current collector and a positive electrode active material layer are laminated, an oxide solid electrolyte 2 as a separator, a lithium foil 3, and a Cu foil 4 are laminated in this order on a lower mold 10.
  • the upper mold 11 is arranged on the Cu foil 4, and the positive electrode 1, the oxide solid electrolyte 2, the lithium foil 3 and the Cu foil 4 are pressed by the upper mold 11 and the lower mold 10.
  • Reference numeral 5 is a side molding die made of ceramics and having an inner diameter of 10 mm.
  • the theoretical capacity of the positive electrode active material used is about 180 mAh / g. From the discharge capacity of the discharge curve in FIG. 6, it can be said that the solid-state lithium-ion secondary battery of Example 2 exhibited a substantially quantitative capacity.
  • Example 3 As a positive electrode active material, 59.8 parts by mass of a lithium nickel cobalt manganese composite oxide having a layered rock salt structure, 38 parts by mass of LiPO 3 —Li 2 SO 4 based glass of Production Example L, and 2.2 parts by mass as a conduction aid. Part of acetylene black was mixed with a ball mill at 100 rpm for 72 hours to obtain a composition for producing a positive electrode active material layer.
  • LiPO 3 —Li 2 SO 4 type glass of Production Example D 51.3 mg was pressed at 130 MPa under room temperature conditions to obtain an oxide solid electrolyte having a diameter of 10 mm and a thickness of 0.5 mm. This was used as a separator.
  • a lithium foil having a diameter of 4 mm and an indium foil having a diameter of 6 mm were prepared.
  • 1.4 mg of the positive electrode active material layer-producing composition was placed on an Al foil as a current collector, and a separator was placed thereon. These are heated at 300 ° C. and pressurized at 130 MPa, and the heated / pressurized state is maintained for 30 minutes to form a positive electrode active material layer and to oxidize the current collector, the positive electrode active material layer, and the separator. A laminate in which the physical solid electrolyte was integrated was manufactured. Further, a lithium foil and an indium foil were laminated on the oxide type solid electrolyte and pressed to manufacture a solid type lithium ion secondary battery of Example 3.
  • a cylindrical side forming die made of ceramics and having an inner diameter of 10 mm, and an upper portion made of stainless steel (corresponding to SUS316) were used.
  • a molding apparatus including a molding die and a lower molding die was used.
  • Example 4 Using a ball mill, 30 parts by mass of Li 4 Ti 5 O 12 as a negative electrode active material, 60 parts by mass of LiPO 3 —Li 2 SO 4 based glass of Production Example D, and 10 parts by mass of acetylene black as a conductive additive were used. And mixed at 100 rpm for 72 hours to obtain a composition for producing a negative electrode active material layer.
  • LiPO 3 —Li 2 SO 4 glass of Production Example D 50 mg was pressed at 130 MPa under room temperature conditions to obtain an oxide solid electrolyte having a diameter of 10 mm and a thickness of 0.5 mm. This was used as a separator.
  • composition for producing a negative electrode active material layer was placed on an Al foil as a current collector, and a separator was placed thereon. These are heated at 300 ° C. and pressurized at 130 MPa, and the heated / pressurized state is maintained for 30 minutes to form a negative electrode active material layer, and at the same time, to oxidize the current collector, the negative electrode active material layer, and the separator.
  • a laminate in which the physical solid electrolyte was integrated was manufactured. Further, a lithium foil and a Cu foil as a current collector were laminated on the oxide type solid electrolyte and pressed to manufacture a solid type lithium ion secondary battery of Example 4.
  • a cylindrical side forming die made of ceramics and having an inner diameter of 10 mm, and an upper portion made of stainless steel (corresponding to SUS316) were used.
  • a molding apparatus including a molding die and a lower molding die was used.
  • the liquid was rapidly cooled and solidified to produce a transparent bulk LiPO 3 —Li 2 SO 4 based glass of Production Example U. Further, by pulverizing the bulk LiPO 3 -Li 2 SO 4 glass of Preparation U, to produce a powdery LiPO 3 -Li 2 SO 4 glass of Preparation U.
  • Production Example V Transparent bulk of Production Example V was prepared in the same manner as in Production Example U, except that the melting conditions were changed to heating at 500 ° C. for 1 hour, heating at 600 ° C. for 1 hour, heating at 700 ° C. for 1 hour, and heating at 800 ° C. for 2 hours.
  • the LiPO 3 —Li 2 SO 4 based glass and the powdery LiPO 3 —Li 2 SO 4 based glass of Production Example V were produced.
  • generation of white smoke was observed during melting at 700 ° C., and generation of a small amount of white smoke was also observed during melting at 800 ° C.
  • Production Example X Transparent, in the same manner as in Production Example U, except that the melting conditions were changed to heating at 500 ° C. for 1 hour, heating at 600 ° C. for 1 hour, heating at 700 ° C. for 1 hour, heating at 800 ° C. for 1 hour, and heating at 900 ° C. for 2 hours.
  • the bulk LiPO 3 —Li 2 SO 4 based glass of Production Example X and the powdery LiPO 3 —Li 2 SO 4 based glass of Production Example X were produced. Although white smoke was observed to be generated during melting at 700 ° C and 800 ° C, almost no white smoke was observed during melting at 900 ° C.
  • Production Example Y Transparent, in the same manner as in Production Example U, except that the melting conditions were changed to heating at 500 ° C. for 1 hour, heating at 600 ° C. for 1 hour, heating at 700 ° C. for 1 hour, heating at 800 ° C. for 1 hour, and heating at 900 ° C. for 4 hours.
  • the bulk LiPO 3 —Li 2 SO 4 based glass of Production Example Y and the powdery LiPO 3 —Li 2 SO 4 based glass of Production Example Y were produced. Although white smoke was observed to be generated during melting at 700 ° C and 800 ° C, almost no white smoke was observed during melting at 900 ° C.
  • the activation energy here means substantially the energy required for the lithium ions to move. Therefore, the smaller the activation energy is, the less the lithium ions contained in the LiPO 3 —Li 2 SO 4 system glass are. It can be said that the function as a charge carrier is easily exhibited. From the results of Table 5, it can be said that the higher the heating temperature at the time of melting, the higher the electrical conductivity of the bulk LiPO 3 —Li 2 SO 4 based glass and the more the activation energy tends to decrease.
  • the powdery (pellet) LiPO 3 —Li 2 SO 4 type glass showed similar electrical conductivity regardless of the manufacturing conditions, but the activation energy tended to decrease as the heating temperature during melting increased. It can be said that there is.
  • the activation energy in the powder form (pellet) was not significantly increased as compared with the bulk form. That is, since the energy when ions move in the bulk and powder (pellet) LiPO3-Li2SO4 type glass does not fluctuate significantly, the bulk LiPO 3 -Li 2 SO 4 type glass is once powdered and re-molded. Even so, the conduction mechanisms of the two do not seem to change significantly.
  • the peaks derived from the SO 4 structure were clearly observed in the Raman spectra of the powdery LiPO 3 —Li 2 SO 4 based glasses of Production Example U, Production Example V, and Production Example X, the PO 3 structure was clearly observed. Almost no peak derived from was observed. Further, from the Raman spectra of the powdery LiPO 3 —Li 2 SO 4 type glasses of Production Example U, Production Example V, and Production Example X, the peak derived from the O 3 PO—PO 3 structure was around 1050 cm ⁇ 1. It was slightly observed near 760 cm ⁇ 1 , and the strength was strong in the order of Production Example U ⁇ Production Example V ⁇ Production Example X. It can be said that the higher the melting temperature, the stronger the intensity of the peak derived from the O 3 PO—PO 3 structure.
  • Example 5 As the positive electrode active material, 59 parts by mass of LiNi 1/3 Co 1/3 Mn 1/3 O 2 having a layered rock salt structure, 39 parts by mass of powdered LiPO 3 —Li 2 SO 4 system glass of Production Example V, and conductive 2 parts by mass of acetylene black was mixed as an auxiliary agent to obtain a composition for producing a positive electrode active material layer.
  • pelletized Li 4.4 Si was prepared.
  • Example 5 a solid lithium ion secondary battery of Example 5 was manufactured by disposing pelletized Li 4.4 Si on the oxide solid electrolyte in the integrated laminated body and applying pressure at 380 MPa. .
  • Example 6 As a negative electrode active material, a lithium foil having a diameter of 4 mm and an indium foil having a diameter of 6 mm were prepared. Using the negative electrode active material described above, changing the pressure when manufacturing a laminate in which the current collector, the positive electrode active material layer, and the oxide-type solid electrolyte as a separator are integrated to 400 MPa, and integrating The solid-state lithium ion of Example 6 was manufactured in the same manner as in Example 5, except that the pressure at the time of manufacturing the solid-state lithium-ion secondary battery by pressing the laminated body and the negative electrode active material was changed to 100 MPa. A secondary battery was manufactured.

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Abstract

Le but de la présente invention est de fournir une nouvelle électrode qui est appropriée pour une batterie secondaire au lithium-ion à semi-conducteur qui a un électrolyte d'oxyde solide en tant que séparateur. Cette électrode est caractérisée en ce qu'elle comprend un collecteur et une couche de matériau actif d'électrode qui contient un matériau actif d'électrode et un électrolyte à base d'oxyde obtenu par fusion et refroidissement d'une composition représentée par (100−(x+y))LiPO3∙xLi2SO4∙yLi2WO4. Dans la composition, x et y satisfont à x ≥ 0, y ≥ 0, et 0 < x+y ≤ 60.
PCT/JP2019/038835 2018-10-26 2019-10-02 Électrode et batterie secondaire au lithium-ion à semi-conducteur WO2020085015A1 (fr)

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JP2000011996A (ja) * 1998-06-25 2000-01-14 Shin Kobe Electric Mach Co Ltd 非水電解液二次電池
JP2005038843A (ja) * 2003-06-27 2005-02-10 Matsushita Electric Ind Co Ltd 固体電解質およびそれを用いた全固体電池
US20150207171A1 (en) * 2012-08-16 2015-07-23 The Regents Of The University Of California Thin film electrolyte based 3d micro-batteries
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