WO2022038670A1 - リチウム２次電池 - Google Patents

リチウム２次電池 Download PDF

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Publication number
WO2022038670A1
WO2022038670A1 PCT/JP2020/031096 JP2020031096W WO2022038670A1 WO 2022038670 A1 WO2022038670 A1 WO 2022038670A1 JP 2020031096 W JP2020031096 W JP 2020031096W WO 2022038670 A1 WO2022038670 A1 WO 2022038670A1
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Prior art keywords
secondary battery
negative electrode
positive electrode
lithium secondary
lithium
Prior art date
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Ceased
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PCT/JP2020/031096
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English (en)
French (fr)
Japanese (ja)
Inventor
雅継 中野
健 緒方
浩 井本
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Terawatt Technology KK
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Terawatt Technology KK
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Application filed by Terawatt Technology KK filed Critical Terawatt Technology KK
Priority to PCT/JP2020/031096 priority Critical patent/WO2022038670A1/ja
Priority to JP2022543837A priority patent/JP7335024B2/ja
Priority to PCT/JP2020/033590 priority patent/WO2022038793A1/ja
Priority to JP2022543264A priority patent/JP7551169B2/ja
Priority to PCT/JP2021/016226 priority patent/WO2022038835A1/ja
Priority to KR1020237007436A priority patent/KR102807462B1/ko
Priority to JP2022543276A priority patent/JP7335022B2/ja
Priority to EP21857987.8A priority patent/EP4203090A4/en
Priority to CN202180056811.1A priority patent/CN116034494B/zh
Publication of WO2022038670A1 publication Critical patent/WO2022038670A1/ja
Priority to US18/111,339 priority patent/US20230216044A1/en
Priority to US18/111,334 priority patent/US20230207790A1/en
Priority to US18/111,337 priority patent/US20230395939A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • 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
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
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    • H01M4/64—Carriers or collectors
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    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
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    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
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    • 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
    • H01M50/431—Inorganic material
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    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
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    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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    • 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
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
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    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 lithium secondary battery.
  • a secondary battery that charges and discharges by moving metal ions between a positive electrode and a negative electrode is known to exhibit high voltage and high energy density, and is typically a lithium ion secondary battery. It has been known.
  • an active material capable of holding lithium is introduced into the positive electrode and the negative electrode, and charging / discharging is performed by exchanging lithium ions between the positive electrode active material and the negative electrode active material.
  • a lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode has been developed.
  • Patent Document 1 describes a high energy density, high power lithium metal anode having a volumetric energy density of greater than 1000 Wh / L and / or a mass energy density of greater than 350 Wh / kg when discharged at room temperature at a rate of at least 1 C. Secondary batteries are disclosed. Patent Document 1 discloses the use of an ultrathin lithium metal anode in order to realize such a lithium metal anode secondary battery.
  • Patent Document 2 in a lithium secondary battery including a positive electrode, a negative electrode, a separation film interposed between them, and an electrolyte, in the negative electrode, metal particles are formed on a negative electrode current collector, and the negative electrode is charged.
  • a lithium secondary battery that is moved from the positive electrode and forms a lithium metal on the negative electrode current collector in the negative electrode is disclosed.
  • Patent Document 2 provides a lithium secondary battery in which such a lithium secondary battery solves a problem caused by the reactivity of a lithium metal and a problem generated in the assembly process, and has improved performance and life. Discloses what can be done.
  • a typical secondary battery that charges and discharges by exchanging metal ions between a positive electrode active material and a negative electrode active material does not have sufficient energy density.
  • a conventional lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode as described in the above patent document has a dendrite shape on the surface of the negative electrode by repeating charging and discharging. Lithium metal is likely to be formed, and short circuit and capacity reduction are likely to occur. As a result, the cycle characteristics are not sufficient.
  • a method of applying a large physical pressure to the battery to keep the interface between the negative electrode and the separator at a high pressure has been developed in order to suppress discrete growth at the time of lithium metal precipitation.
  • the application of such a high voltage requires a large mechanical mechanism, the weight and volume of the battery as a whole become large, and the energy density decreases.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a lithium secondary battery having a high energy density and excellent cycle characteristics.
  • the lithium secondary battery according to the embodiment of the present invention is formed on a positive electrode, a negative electrode having no negative electrode active material, a separator arranged between the positive electrode and the negative electrode, and a surface facing the separator of the negative electrode. At least one selected from the group consisting of a metal layer and a buffering functional layer having fibrous or porous ionic conductivity and electrical conductivity formed on the surface of the separator facing the negative electrode.
  • a lithium-containing compound in which the positive electrode causes an oxidation reaction with the positive electrode active material in the charge / discharge potential range of the positive electrode active material and substantially does not cause a reduction reaction hereinafter, the lithium-containing compound is referred to as a “sacrificial positive electrode agent”. It is also called.), And includes.
  • the lithium secondary battery according to the embodiment of the present invention includes at least one of a metal layer and a buffer function layer.
  • the lithium secondary battery has a metal layer on the surface of the negative electrode, the electric field generated on the surface of the negative electrode becomes more uniform due to the electrical conductivity of the metal layer, and the lithium metal tends to be uniformly deposited on the surface of the negative electrode. (That is, the growth of dendrite-like lithium metal on the negative electrode is suppressed).
  • lithium metal is deposited not only on the surface of the negative electrode but also inside the buffering function layer having fibrous or porous ionic conductivity and electrical conductivity. Therefore, the surface area of the reaction field of the lithium metal precipitation reaction is increased, and the reaction rate of the lithium metal precipitation reaction is moderately controlled. As a result, the growth of dendrite-like lithium metal on the negative electrode is suppressed.
  • the lithium secondary battery according to the embodiment of the present invention has not only the metal layer or the buffer function layer but also the sacrificial positive electrode agent as described above in the positive electrode.
  • the sacrificial positive electrode agent as described above causes an oxidation reaction (that is, releases lithium ions) during the initial charge of the lithium secondary battery, while substantially does not cause a reduction reaction (that is, discharge) during the subsequent discharge.
  • the previous lithium-containing compound is not formed.
  • the lithium element derived from the lithium-containing compound remains as a lithium metal on the surface of the negative electrode or the surface of the buffer function layer.
  • the lithium secondary battery having the sacrificial positive electrode agent all the lithium metals deposited on the surface of the negative electrode or the surface of the buffer function layer are not dissolved at the time of discharge, and some lithium is used even after the discharge is completed.
  • the metal remains on the surface of the negative electrode or on the surface of the buffer function layer. Therefore, in the lithium secondary battery according to the embodiment of the present invention having a metal layer or a buffer function layer in addition to the sacrificial positive electrode agent, a part of the lithium metal remains on the negative electrode even after the discharge is completed, and the residual lithium metal remains. It is considered that the lithium metal to be used remains uniformly on the surface of the negative electrode or the surface of the buffer function layer.
  • the residual lithium metal serves as a scaffold for further lithium metal to be deposited on the surface of the negative electrode or the surface of the buffer function layer during the subsequent charging, so that the lithium metal is on the surface of the negative electrode or on the surface of the negative electrode during the charging. It becomes easier to deposit more uniformly on the surface of the buffer function layer. Therefore, since the dendrite-like lithium metal is suppressed from growing on the negative electrode, the lithium secondary battery has excellent cycle characteristics.
  • a solid electrolyte may be used instead of the above separator.
  • the lithium secondary battery can be a solid-state battery, it can be a lithium secondary battery with higher safety.
  • the lithium secondary battery according to the embodiment of the present invention preferably includes both a metal layer and a buffer function layer. According to such an aspect, since both of the above-mentioned effects of the metal layer and the buffer function layer are exhibited, the growth of dendrite-like lithium metal on the negative electrode is further suppressed, and the lithium secondary battery has a lithium secondary battery. The cycle characteristics will be even better.
  • the ratio of the irreversible capacity of the lithium-containing compound is preferably 1% or more and 30% or less with respect to the cell capacity of the lithium secondary battery. According to such an embodiment, the amount of residual lithium remaining on the surface of the negative electrode or the surface of the buffer function layer after the completion of discharge becomes a more appropriate amount, so that the cycle characteristics and energy density of the lithium secondary battery are further improved.
  • the porosity of the buffer function layer is preferably 50% or more. According to such an embodiment, the effect of the buffer function layer described above is more effectively and reliably exerted, so that the cycle characteristics and energy density of the lithium secondary battery are further improved.
  • the buffer function layer may include a fibrous or porous ionic conductive layer and an electric conductive layer that covers the ionic conductive layer.
  • the average thickness of the metal layer is preferably 5 nm or more and 5000 nm or less. According to such an embodiment, the electric field generated on the surface of the negative electrode becomes more uniform, and the growth of dendrite-like lithium metal on the negative electrode is further suppressed.
  • the metal layer contains at least one selected from the group consisting of Si, Sn, Zn, Bi, Ag, In, Pb, Sb, and Al. According to such an embodiment, the affinity of the metal layer with lithium is further improved, so that the lithium metal deposited on the negative electrode is further suppressed from peeling off.
  • the lithium secondary battery is a lithium secondary battery in which lithium metal is deposited on the surface of a negative electrode and the deposited lithium is dissolved to charge and discharge the battery. According to such an embodiment, the energy density is further increased.
  • the negative electrode is preferably an electrode consisting of at least one selected from the group consisting of Cu, Ni, Ti, Fe, and other metals that do not react with Li, alloys thereof, and stainless steel (SUS). be. According to such an aspect, since it is not necessary to use a highly flammable lithium metal in the production, the safety and productivity are further improved. Moreover, since such a negative electrode is stable, the cycle characteristics of the secondary battery are further improved.
  • the lithium secondary battery preferably has no lithium foil formed on the surface of the negative electrode before the initial charge. According to such an aspect, since it is not necessary to use a highly flammable lithium metal in the production, the safety and productivity are further improved.
  • the lithium secondary battery preferably has an energy density of 350 Wh / kg or more.
  • FIG. 2 is a schematic cross-sectional view of a lithium secondary battery according to the second embodiment.
  • A shows the fiber-like cushioning function layer which is one Embodiment of the cushioning function layer
  • B is a fiber.
  • a precipitation mode in which lithium metal is deposited on the cushioning functional layer is shown, and
  • FIG. 3C shows an embodiment of a member constituting the fibrous cushioning functional layer.
  • 3 is a schematic cross-sectional view of a lithium secondary battery according to the third embodiment. It is the schematic sectional drawing of the lithium secondary battery which concerns on 4th present embodiment.
  • the present embodiments will be described in detail with reference to the drawings as necessary.
  • the same elements are designated by the same reference numerals, and duplicate description will be omitted.
  • the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified.
  • the dimensional ratios in the drawings are not limited to the ratios shown.
  • FIG. 1 is a schematic cross-sectional view of a lithium secondary battery according to the first embodiment.
  • the lithium secondary battery 100 of the first embodiment has a positive electrode 110, a negative electrode 140 having no negative electrode active material, and a separator 120 arranged between the positive electrode 110 and the negative electrode 140. And a metal layer 130 formed on the surface of the negative electrode 140 facing the separator 120.
  • the positive electrode 110 has a positive electrode current collector 150 on a surface opposite to the surface facing the separator 120.
  • the negative electrode 140 does not have a negative electrode active material. It is difficult to increase the energy density of a lithium secondary battery including a negative electrode having a negative electrode active material due to the presence of the negative electrode active material. On the other hand, since the lithium secondary battery 100 of the present embodiment includes the negative electrode 140 having no negative electrode active material, such a problem does not occur. That is, the lithium secondary battery 100 of the present embodiment has a high energy density because lithium metal is deposited on the surface of the negative electrode 140 and the deposited lithium metal is electrolytically eluted to charge and discharge.
  • lithium metal precipitates on the surface of the negative electrode means that the surface of the negative electrode, the surface of the metal layer formed on the surface of the negative electrode, and the surface of the negative electrode and / or the metal layer will be described later. It means that the lithium metal is deposited on at least one place on the surface of the solid electrolyte interface (SEI) layer. In the lithium secondary battery of the present embodiment, the lithium metal is considered to be deposited mainly on the surface of the metal layer or the surface of the SEI layer formed on the surface of the metal layer, but the precipitation location is not limited to these. ..
  • the lithium metal may be deposited on the surface of the negative electrode 140 (the interface between the negative electrode 140 and the metal layer 130), for example, and the surface of the metal layer 130 (the metal layer 130 and the separator 120). It may be deposited on the interface).
  • negative electrode active material means a material for holding lithium ions or lithium metal (hereinafter, also referred to as “carrier metal”), which are charge carriers in a battery, in the negative electrode 140, and is a carrier metal. It may be paraphrased as the host substance of.
  • carrier metal lithium metal
  • the mechanism of such holding is not particularly limited, and examples thereof include intercalation, alloying, and occlusion of metal clusters.
  • the negative electrode active material is not particularly limited, and examples thereof include carbon-based substances, metal oxides, metals, alloys, and the like.
  • the carbon-based substance is not particularly limited, and examples thereof include graphene, graphite, hard carbon, mesoporous carbon, carbon nanotubes, and carbon nanohorns.
  • the metal oxide is not particularly limited, and examples thereof include titanium oxide-based compounds, tin oxide-based compounds, and cobalt oxide-based compounds.
  • the metal or alloy is not particularly limited as long as it can be alloyed with the carrier metal, and examples thereof include silicon, germanium, tin, lead, aluminum, gallium, and alloys containing these.
  • the negative electrode 140 is not particularly limited as long as it does not have a negative electrode active material and can be used as a current collector, but for example, Cu, Ni, Ti, Fe, and other metals that do not react with Li, and , These alloys, as well as those consisting of at least one selected from the group consisting of stainless steel (SUS).
  • SUS stainless steel
  • various conventionally known types of SUS can be used.
  • the negative electrode material as described above one type may be used alone or two or more types may be used in combination.
  • the “metal that does not react with Li” means a metal that does not react with lithium ions or lithium metal to form an alloy under the operating conditions of the lithium secondary battery.
  • the negative electrode 140 is preferably a lithium-free electrode. According to such an embodiment, since it is not necessary to use a highly flammable lithium metal in the production, the lithium secondary battery 100 is further excellent in safety and productivity. From the same viewpoint and from the viewpoint of improving the stability of the negative electrode 140, the negative electrode 140 is more preferably selected from the group consisting of Cu, Ni, and alloys thereof, and stainless steel (SUS). It consists of one kind. From the same viewpoint, the negative electrode 140 is more preferably made of Cu, Ni, or an alloy made of these, and particularly preferably made of Cu or Ni.
  • the negative electrode does not have a negative electrode active material
  • the content of the negative electrode active material in the negative electrode is 10% by mass or less with respect to the entire negative electrode.
  • the content of the negative electrode active material in the negative electrode is preferably 5.0% by mass or less, 1.0% by mass or less, or 0.1% by mass or less with respect to the entire negative electrode. , 0.0% by mass or less.
  • the fact that the lithium secondary battery 100 includes a negative electrode having no negative electrode active material means that the lithium secondary battery 100 is an anode-free secondary battery, a zero anode secondary battery, or an anode in the sense that it is generally used. It means that it is a less secondary battery.
  • the capacity of the negative electrode active material of the negative electrode is set to be about the same as the capacity of the positive electrode.
  • a metal layer 130 is formed on the surface of the negative electrode 140, and the metal layer may contain a metal capable of reacting with lithium, but its capacity is sufficiently smaller than that of the positive electrode. It can be said that the secondary battery 100 "includes a negative electrode having no negative electrode active material".
  • the total capacity of the negative electrode 140 and the metal layer 130 may be sufficiently smaller than the capacity of the positive electrode 110, for example, 20% or less, 15% or less, 10% or less, or 5% or less.
  • the capacities of the positive electrode 110, the negative electrode 140, and the metal layer 130 can be measured by a conventionally known method.
  • the average thickness of the negative electrode 140 is preferably 4 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 18 ⁇ m or less, and further preferably 6 ⁇ m or more and 15 ⁇ m or less. According to such an embodiment, the volume occupied by the negative electrode 140 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
  • the lithium secondary battery 100 Since the positive electrode 110 contains a positive electrode active material, the lithium secondary battery 100 has excellent stability and a high output voltage.
  • the “positive electrode active material” means a substance for retaining lithium ions in the positive electrode 110, and may be paraphrased as a host material for lithium ions. Examples of such a positive electrode active material include, but are not limited to, metal oxides and metal phosphates.
  • the metal oxide is not particularly limited, and examples thereof include a cobalt oxide-based compound, a manganese oxide-based compound, and a nickel oxide-based compound.
  • the metal phosphate is not particularly limited, and examples thereof include iron phosphate compounds and cobalt phosphate compounds.
  • the positive electrode active material as described above one type may be used alone or two or more types may be used in combination.
  • the positive electrode 110 contains a lithium-containing compound (that is, a sacrificial positive electrode agent) that causes an oxidation reaction in the charge / discharge potential range of the positive electrode active material and substantially does not cause a reduction reaction.
  • a lithium-containing compound that is, a sacrificial positive electrode agent
  • the positive electrode active material and the sacrificial positive electrode agent release lithium ions and cause an oxidation reaction, and emit electrons to the negative electrode 140 through an external circuit.
  • lithium ions derived from the positive electrode active material and the sacrificial positive electrode agent are deposited on the surface of the negative electrode.
  • the lithium secondary battery 100 when such a lithium secondary battery 100 is discharged (that is, initially discharged) after the initial charge is completed, the lithium metal deposited on the surface of the negative electrode is electrolytically eluted, and electrons move from the negative electrode 140 to the positive electrode 110 through an external circuit. do.
  • the positive electrode active material receives lithium ions and causes a reduction reaction, while the sacrificial positive electrode agent substantially does not cause a reduction reaction within the range of the discharge potential of the positive electrode active material, and before the oxidation reaction occurs. It is virtually impossible to return to the state.
  • the "initial charge” means the first charge step after assembling the battery.
  • the lithium secondary battery 100 when the lithium secondary battery 100 is discharged after the initial charge, most of the lithium metal derived from the positive electrode active material is electrolytically eluted from the negative electrode, whereas most of the lithium metal derived from the sacrificial positive electrode agent is on the negative electrode. Even after the battery is completely discharged, a part of the lithium metal remains on the negative electrode. Since the residual lithium metal serves as a scaffold for further lithium metal to be deposited on the negative electrode in the charging step following the initial discharge, the lithium metal is likely to be uniformly deposited on the negative electrode in the charging step after the initial discharge. .. As a result, the growth of dendrite-like lithium metal on the negative electrode is suppressed, so that the lithium secondary battery 100 has excellent cycle characteristics.
  • the sacrificial positive electrode agent in the positive electrode 110 is a lithium-containing compound that causes an oxidation reaction in the charge / discharge potential range of the positive electrode active material and substantially does not cause a reduction reaction.
  • causing an oxidation reaction in the charge / discharge potential range of the positive electrode active material means that an oxidation reaction is generated in the charge / discharge potential range of the positive electrode active material to release lithium ions and electrons (by the oxidation reaction). It means that it can be decomposed and release lithium ions.).
  • substantially no reduction reaction occurs in the charge / discharge potential range of the positive electrode active material means that a reduction reaction occurs in the charge / discharge potential range of the positive electrode active material under normal reaction conditions for those skilled in the art.
  • the "normal reaction conditions for those skilled in the art” mean, for example, the conditions for discharging a lithium secondary battery.
  • “it is practically impossible for the sacrificial positive electrode agent to undergo a reduction reaction to receive lithium ions and electrons, or to be generated through the reduction reaction” is a sacrifice oxidized by charging the battery.
  • the positive electrode agents 80% or more (for example, 80% or more, 85% or more, 90% or more, 95% or more, 99% or more, or 100%) of the sacrificial positive electrode agents cause a reduction reaction. It means that it cannot receive lithium ions and electrons, or it cannot be generated through a reduction reaction.
  • the capacity of the initial discharge with respect to the capacity of the initial charge in the sacrificial positive electrode agent is 20% or less (for example, 20% or less, 15% or less, 10% or less, 5% or less, 1% or less, or 0%). ..
  • the "charge / discharge potential range of the positive electrode active material” means the potential range in which the oxidation reaction and the reduction reaction of the positive electrode active material contained in the positive electrode 110 can be performed.
  • the specific value depends on the type of positive electrode active material contained in the positive electrode 110, but is typically 2.5 V or higher, 2.7 V or higher, or 3.0 V or higher with respect to the Li + / Li reference electrode. 3.2V or more, or 3.5V or more, and 4.5V or less, 4.4V or less, 4.3V or less, 4.2V or less, 4.1V or less, or 4.0V or less.
  • the typical range of charge / discharge potential range of the positive electrode active material is 3.0 V or more and 4.2 V or less (vs.
  • the operating voltage range of the lithium secondary battery 100 may be referred to.
  • the operating voltage of the lithium secondary battery 100 is 3.0 V or more.
  • the charge / discharge potential range of the positive electrode active material with respect to the Li + / Li reference electrode can be estimated to be 3.0 V or more and 4.2 V or less. That is, the sacrificial positive electrode agent may be paraphrased as "a lithium-containing compound that causes an oxidation reaction and substantially no reduction reaction in the operating voltage range of the lithium secondary battery".
  • the sacrificial positive electrode agent are not particularly limited, and are, for example, a lithium oxide such as Li 2 O 2 ; a lithium nitride such as Li 3 N; Li 2 SP 2 S 5 , Li 2 S-LiCl. , Li 2 S-LiBr, and lithium sulfide-based solid solutions such as Li 2 S-Li I; iron-based lithium oxides such as Li 5 FeO 4 and the like.
  • a lithium oxide such as Li 2 O 2
  • a lithium nitride such as Li 3 N
  • Li 2 SP 2 S 5 Li 2 S-LiCl. , Li 2 S-LiBr, and lithium sulfide-based solid solutions
  • Li 2 S-Li I iron-based lithium oxides
  • iron-based lithium oxides such as Li 5 FeO 4 and the like.
  • the positive electrode 110 may contain components other than the positive electrode active material and the sacrificial positive electrode agent. Such components include, but are not limited to, known conductive aids, binders, solid polymer electrolytes, and inorganic solid electrolytes.
  • the conductive auxiliary agent in the positive electrode 110 is not particularly limited, and examples thereof include carbon black, single-wall carbon nanotubes (SWCNT), multi-wall carbon nanotubes (MWCNT), carbon nanofibers (CF), and acetylene black.
  • the binder is not particularly limited, and examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, acrylic resin, and polyimide resin.
  • the above-mentioned conductive aids and binders one type may be used alone or two or more types may be used in combination.
  • the solid polymer electrolyte the same ones as exemplified as the solid electrolyte described later can be used.
  • the total content of the positive electrode active material and the sacrificial positive electrode agent in the positive electrode 110 may be, for example, 50% by mass or more and 100% by mass or less with respect to the entire positive electrode 110.
  • the total content of the positive electrode active material and the sacrificial positive electrode agent is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, based on the entire positive electrode 110. Even more preferably, it is 90% by mass or more.
  • the total content of the positive electrode active material and the sacrificial positive electrode agent is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less with respect to the entire positive electrode 110.
  • the content of the sacrificial positive electrode agent is preferably defined by the ratio of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the lithium secondary battery 100.
  • the "cell capacity of the lithium secondary battery” means a value obtained by calculating the total charge capacity of the positive electrode active material and the sacrificial positive electrode agent contained in the positive electrode 110.
  • the cell capacity of the lithium secondary battery 100 is such that for each positive electrode active material and each sacrificial positive electrode agent, a cell having a positive electrode active material or a sacrificial positive electrode agent as a positive electrode and a lithium metal foil as a negative electrode is used as lithium 2.
  • the product of the charge capacity density (mAh / g) obtained by charging / discharging at the drive voltage of the next battery 100 (for example, 3.0 V or more and 4.2 V or less) and the mass (g) contained in the positive electrode 110 is calculated.
  • the sum of the above products for all the positive electrode active materials and the sacrificial positive electrode agent contained in the positive electrode 110 is obtained.
  • the “irreversible capacity of the sacrificial positive electrode agent” means that for each sacrificial positive electrode agent, a cell having the sacrificial positive electrode agent as the positive electrode and the lithium metal foil as the negative electrode is used as the driving voltage of the lithium secondary battery 100 (for example, 3.
  • the irreversible capacity density A (mAh / g), which is the difference (A1-A2) between the charge capacity density A1 and the discharge capacity density A2, is obtained. It is obtained by calculating the product with the mass (g) contained in the positive electrode 110 and obtaining the sum of the above products for all the sacrificial positive electrode agents contained in the positive electrode 110.
  • the ratio X of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the lithium secondary battery 100 is the charge capacity density A1 k (mAh / g) of each positive electrode active material and each sacrificial positive electrode agent and the content x k (mass) in the positive electrode 110. %) To the sum of the products of the irreversible volume density A j (mAh / g) of each sacrificial positive electrode agent and the content x j (mass%) in the positive electrode 110, as the ratio of the product of the following formula (1). You may ask according to.
  • the known values may be used.
  • the charge capacity density, the discharge capacity density, and the content in the positive electrode 110 of each positive electrode active material and each sacrificial positive electrode agent can be measured by a conventionally known method, and the charge capacity density and the discharge capacity density are shown in Examples. It may be measured by the method described in 1.
  • the content in the positive electrode 110 can be measured, for example, by X-ray diffraction measurement (XRD).
  • the content of the sacrificial positive electrode agent is preferably adjusted so that the ratio of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the lithium secondary battery 100 is 0.3% or more and 50% or less, preferably 0.5% or more. It is more preferably adjusted to be 40% or less, further preferably adjusted to be 1% or more and 35% or less, and even more preferably adjusted to be 1% or more and 30% or less. preferable.
  • the ratio of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the lithium secondary battery 100 the lithium metal remaining after the initial discharge with respect to the total amount of the lithium metal deposited by the initial charge in the lithium secondary battery 100. Since it is presumed that the ratio can be controlled, if the ratio of the irreversible capacity is within the above range, the amount of the residual lithium metal becomes appropriate, and the cycle characteristics and energy density of the lithium secondary battery 100 become appropriate. It will be even better.
  • the content of the conductive auxiliary agent may be, for example, 0.5% by mass, 30% by mass or less, 1% by mass, 20% by mass or less, or 1.5% by mass, 10% by mass, based on the entire positive electrode 110.
  • the following may be present.
  • the content of the binder may be, for example, 0.5% by mass, 30% by mass or less, 1% by mass, 20% by mass or less, or 1.5% by mass, 10% by mass or less, based on the entire positive electrode 110. You may.
  • the total content of the solid polymer electrolyte and the inorganic solid electrolyte may be, for example, 0.5% by mass, 30% by mass or less, or 1% by mass, 20% by mass or less, based on the entire positive electrode 110. It may be 5.5% by mass or less than 10% by mass.
  • a positive electrode current collector 150 is formed on one side of the positive electrode 110.
  • the positive electrode current collector 150 is not particularly limited as long as it is a conductor that does not react with lithium ions in the battery. Examples of such a positive electrode current collector include aluminum.
  • the average thickness of the positive electrode current collector 150 is preferably 4 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 18 ⁇ m or less, and further preferably 6 ⁇ m or more and 15 ⁇ m or less. According to such an embodiment, the volume occupied by the positive electrode current collector 150 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
  • the lithium secondary battery 100 includes a metal layer 130 formed on the surface of the negative electrode 140 facing the separator 120.
  • a conventional lithium secondary battery it is difficult for the lithium metal deposited on the surface of the negative electrode to grow uniformly in the plane direction, and as a result, the lithium metal deposited on the surface of the negative electrode tends to grow like a dendrite, and the battery The cycle characteristics will be inferior.
  • the present inventors have found that even if a sacrificial positive electrode agent as disclosed in the present specification is added to the positive electrode of a conventional lithium secondary battery, the lithium metal remaining after the initial discharge remains on the negative electrode surface.
  • the conductivity of the negative electrode surface is further improved and the flatness is further improved, so that the electric field generated on the negative electrode surface is a surface. It is considered that the material becomes more uniform in the direction, and the reactivity of the precipitation reaction of metallic lithium becomes more uniform on the surface of the negative electrode regardless of the location.
  • the lithium secondary battery 100 containing the sacrificial positive electrode agent in the positive electrode 110 the lithium metal uniformly grown in the surface direction remains on the surface of the negative electrode after the initial discharge, and the residual lithium metal uniformly grown in the surface direction remains.
  • the lithium metal may be deposited at the interface between the negative electrode 140 and the metal layer 130, or may be deposited at the interface between the metal layer 130 and the separator 120.
  • “suppressing the growth of lithium metal in a dendrite shape” means that the lithium metal formed on the surface of the negative electrode becomes dendrite-like by charging / discharging or repeating the lithium secondary battery. Means to suppress. In other words, it means that the lithium metal formed on the surface of the negative electrode by charging / discharging or repeating the charging / discharging of the lithium secondary battery is induced to grow like a non-dendrite.
  • the “non-dendritic shape” is not particularly limited, but is typically a plate shape, a valley shape, or a hill shape.
  • the metal layer 130 is not particularly limited as long as it is a layer made of metal, but preferably at least one metal selected from the group consisting of Si, Sn, Zn, Bi, Ag, In, Pb, Sb, and Al. Is included. According to such an aspect, the surface of the metal layer 130 becomes more excellent in affinity with the lithium metal, and the lithium metal deposited on the surface of the negative electrode can be further suppressed from peeling off. Generally, in a lithium secondary battery in which lithium metal is deposited on the surface of a negative electrode and the deposited lithium is electrolytically eluted to charge and discharge, the precipitated lithium metal is peeled off to cause a lithium secondary battery. It is known that the capacity of the battery is reduced.
  • the peeling of the precipitated lithium metal deteriorates the cycle characteristics of the lithium secondary battery. Therefore, when the metal layer 130 contains the above-mentioned metal, it is possible to further suppress the lithium metal deposited on the surface of the negative electrode from peeling off, and the cycle characteristics of the lithium secondary battery are further improved.
  • the average thickness of the metal layer 130 is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more. When the thickness of the metal layer is within the above range, the effect of the above-mentioned metal layer tends to be effectively and surely exhibited.
  • the average thickness of the metal layer 130 is preferably 5000 nm or less, more preferably 3000 nm or less, still more preferably 1000 nm or less, still more preferably 500 nm or less, still more preferably 300 nm or less. Yes, and particularly preferably 200 nm or less. When the average thickness of the metal layer is within the above range, the electric resistance inside the lithium secondary battery is further reduced, and the occupied volume of the metal layer in the battery is further reduced. It tends to have higher energy density and better cycle characteristics.
  • the thickness of the metal layer 130 can be measured by a known measuring method. For example, it can be measured by cutting the lithium secondary battery 100 in the thickness direction and observing the metal layer 130 on the exposed cut surface by SEM or TEM. The average thickness of the metal layer 130 is obtained by calculating the arithmetic mean of the measured values 3 times or more, preferably 10 times or more.
  • the separator 120 is a member for ensuring the ionic conductivity of lithium ions, which are charge carriers between the positive electrode 110 and the negative electrode 140, while preventing the battery from short-circuiting by separating the positive electrode 110 and the negative electrode 140. It is made of a material that does not have electron conductivity and does not react with lithium ions. The separator 120 also plays a role of holding the electrolytic solution. The separator 120 is not limited as long as it plays the above role, but is composed of, for example, porous polyethylene (PE), polypropylene (PP), or a laminated structure thereof.
  • PE porous polyethylene
  • PP polypropylene
  • the separator 120 may be covered with a separator coating layer.
  • the separator coating layer may cover both sides of the separator 120, or may cover only one side.
  • the separator coating layer is not particularly limited as long as it is a member having ionic conductivity and does not react with lithium ions, but it is preferable that the separator 120 and the layer adjacent to the separator 120 can be firmly adhered to each other. ..
  • the separator coating layer is not particularly limited, and is, for example, polyvinylidene fluoride (PVDF), a mixture of styrene-butadiene rubber and carboxymethyl cellulose (SBR-CMC), polyacrylic acid (PAA), and lithium polyacrylic acid.
  • Examples include those containing binders such as (Li-PAA), polyimide (PI), polyamideimide (PAI), and aramid.
  • binders such as (Li-PAA), polyimide (PI), polyamideimide (PAI), and aramid.
  • inorganic particles such as silica, alumina, titania, zirconia, magnesium oxide, magnesium hydroxide, and lithium nitrate may be added to the binder.
  • the average thickness of the separator 120 is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, and further preferably 15 ⁇ m or less. According to such an embodiment, the volume occupied by the separator 120 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
  • the average thickness of the separator 120 is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more. According to such an aspect, the positive electrode 110 and the negative electrode 140 can be more reliably isolated, and the short circuit of the battery can be further suppressed.
  • the lithium secondary battery 100 may have an electrolytic solution.
  • the electrolytic solution may be infiltrated into the separator 120, or the electrolytic solution may be sealed together with the lithium secondary battery 100 as a finished product.
  • the electrolytic solution is a solution containing an electrolyte and a solvent and having ionic conductivity, and acts as a conductive path for lithium ions. Therefore, in the lithium secondary battery 100 having an electrolytic solution, the internal resistance is further reduced, and the energy density, capacity, and cycle characteristics are further improved.
  • the electrolyte is not particularly limited as long as it is a salt, and examples thereof include salts of Li, Na, K, Ca, and Mg.
  • a lithium salt is preferably used as the electrolyte.
  • the lithium salt is not particularly limited, but LiI, LiCl, LiBr, LiF, LiBF 4 , LiPF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN.
  • the lithium salt is preferably LiN (SO2 F) 2 .
  • the above lithium salts may be used alone or in combination of two or more.
  • the solvent is not particularly limited, but is not particularly limited, for example, dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, difluoroethylene.
  • FIG. 2 shows one usage mode of the lithium secondary battery of the present embodiment.
  • a positive electrode terminal 220 and a negative electrode terminal 210 for connecting the lithium secondary battery 200 to an external circuit are bonded to the positive electrode current collector 150 and the negative electrode 140, respectively.
  • the lithium secondary battery 200 is charged and discharged by connecting the negative electrode terminal 210 to one end of the external circuit and the positive electrode terminal 220 to the other end of the external circuit.
  • a solid electrolyte interface layer may be formed at the interface between the metal layer 130 and the separator 120 by initial charging.
  • the SEI layer may not be formed, and may be formed at the interface between the negative electrode 140 and the metal layer 130.
  • the SEI layer to be formed is not particularly limited, but may contain, for example, an inorganic compound containing lithium, an organic compound containing lithium, and the like.
  • the typical average thickness of the SEI layer is 1 nm or more and 10 ⁇ m or less.
  • the lithium secondary battery 200 is charged by applying a voltage between the positive electrode terminal 220 and the negative electrode terminal 210 so that a current flows from the negative electrode terminal 210 to the positive electrode terminal 220 through an external circuit. Charging the lithium secondary battery 200 causes precipitation of lithium metal on the surface of the negative electrode. The precipitation of the lithium metal occurs at at least one place at the interface between the negative electrode 140 and the metal layer 130 and the interface between the metal layer 130 and the separator 120.
  • the lithium secondary battery 200 when the positive electrode terminal 220 and the negative electrode terminal 210 are connected, the lithium secondary battery 200 is discharged. As a result, the precipitation of lithium metal generated on the surface of the negative electrode is electrolytically eluted.
  • the method for manufacturing the lithium secondary battery 100 as shown in FIG. 1 is not particularly limited as long as it can manufacture a lithium secondary battery having the above configuration, and examples thereof include the following methods. ..
  • the positive electrode 110 is formed on the positive electrode current collector 150, for example, as follows.
  • the above-mentioned positive electrode active material, sacrificial positive electrode agent, known conductive auxiliary agent, and known binder are mixed to obtain a positive electrode mixture.
  • the blending ratio may be appropriately adjusted so that the contents of the positive electrode active material, the sacrificial positive electrode agent, the conductive auxiliary agent, and the binder are within the above-mentioned range.
  • the lithium secondary battery 100 It is possible to control the ratio of the irreversible volume of the sacrificial positive electrode agent to the cell volume of the cell.
  • the obtained positive electrode mixture is applied to one side of a metal foil (for example, Al foil) as a positive electrode current collector having a predetermined thickness (for example, 5 ⁇ m or more and 1 mm or less), and press-molded.
  • the obtained molded body is punched to a predetermined size by punching to obtain a positive electrode 110.
  • the separator 120 may be manufactured by a conventionally known method, or a commercially available one may be used.
  • the above-mentioned negative electrode material for example, a metal foil of 1 ⁇ m or more and 1 mm or less (for example, an electrolytic Cu foil) is washed with a solvent containing sulfamic acid, punched to a predetermined size, and further ultrasonically washed with ethanol.
  • the negative electrode 140 is obtained by drying.
  • the metal layer 130 is formed on one side of the negative electrode 140.
  • the method for forming the metal layer include an electroless plating method, an electrolytic plating method, a thin film deposition method, a sputtering method, a laser film forming process (PLD) method, and a metal nanoparticle coating method.
  • Examples of the electroless plating method include a method using a plating solution containing metal ions and a reducing agent. Specific examples thereof include a method of immersing the negative electrode 140 in the plating solution, a method of applying the plating solution to the negative electrode 140 by spin coating, and the like. A metal layer having a desired thickness can be obtained by appropriately adjusting the immersion time in the plating solution and the concentrations of the metal ions and the reducing agent.
  • Examples of the electrolytic plating method include a method of electrolytic plating using the negative electrode 140 as a working electrode in an electrolytic plating solution containing metal ions. By appropriately adjusting the electrolysis conditions and the electrolysis time, a metal layer having a desired thickness can be obtained.
  • Examples of the vapor deposition method include a method of obtaining a metal layer by depositing a metal on the negative electrode 140. By appropriately adjusting the vapor deposition time and the vapor deposition conditions, a metal layer having a desired thickness can be obtained.
  • the positive electrode 110, the separator 120, and the negative electrode 140 on which the metal layer 130 is formed are laminated in this order so that the metal layer 130 faces the separator 120 to obtain a laminated body.
  • the lithium secondary battery 100 can be obtained by enclosing the obtained laminate together with the electrolytic solution in a closed container.
  • the closed container is not particularly limited, and examples thereof include a laminated film.
  • FIG. 3 is a schematic cross-sectional view of the lithium secondary battery according to the second embodiment.
  • the lithium secondary battery 300 of the second embodiment has a positive electrode 110, a negative electrode 140 having no negative electrode active material, and a separator 120 arranged between the positive electrode 110 and the negative electrode 140.
  • a buffer function layer 310 having fibrous or porous ionic conductivity and electrical conductivity formed on the surface of the separator 120 facing the negative electrode 140.
  • the positive electrode 110 has a positive electrode current collector 150 on a surface opposite to the surface facing the separator 120.
  • the configurations of the positive electrode current collector 150, the positive electrode 110, the separator 120, and the negative electrode 140 and their preferred embodiments are the same as those of the lithium secondary battery 100 of the first embodiment except for the points described later, and these configurations are the same as those of the lithium secondary battery 100.
  • the secondary battery 300 has the same effect as the lithium secondary battery 100. Further, the lithium secondary battery 300 may contain the electrolytic solution as described above, similarly to the lithium secondary battery 100.
  • the buffer function layer 310 is formed on the surface of the separator 120 facing the negative electrode 140, and the buffer function layer has fibrous or porous ionic conductivity and electrical conductivity. ..
  • the buffer function layer 310 since the buffer function layer 310 is located between the separator 120 and the negative electrode 140, when the lithium secondary battery 300 is charged, electrons from the negative electrode 140 are generated on the surface and / or inside of the buffer function layer 310. , Separator 120 and / or lithium ions from the electrolyte are supplied.
  • the buffer function layer 310 is fibrous or porous, it has a solid portion having ionic conductivity and electrical conductivity, and a pore portion formed by a gap between the solid portions.
  • the electrons and lithium ions supplied as described above react on the surface of the solid portion inside the buffer function layer, and the lithium metal is deposited on the pores.
  • the "solid portion" in the buffer function layer includes a semi-solid such as a gel.
  • the place where the lithium metal is deposited is limited to the surface of the negative electrode, so that the growth direction of the lithium metal is limited to the direction of the separator from the surface of the negative electrode, and the lithium metal tends to grow like a dendrite. ..
  • a lithium secondary battery provided with a buffer function layer such as the lithium secondary battery 300 of the present embodiment
  • lithium metal can be deposited not only on the surface of the negative electrode but also on the surface of the solid portion of the buffer function layer. , The surface area of the reaction field of the lithium metal precipitation reaction increases.
  • the reaction rate of the lithium metal precipitation reaction is slowly controlled, so that the heterogeneous growth of the lithium metal, that is, the formation of the lithium metal grown in a dendrite shape is suppressed. Inferred.
  • the present inventors have found that in a lithium secondary battery containing a sacrificial positive electrode agent in the positive electrode, when the above-mentioned buffer function layer is introduced, the effect of the above-mentioned sacrificial positive electrode agent is remarkably exhibited. I found it.
  • lithium metal uniform in the surface direction was deposited on the surface of the solid portion of the buffer function layer and the surface of the negative electrode by the above mechanism, and even after the initial discharge, it grew uniformly in the surface direction. Since the lithium metal remains, it is presumed that the residual lithium metal that has grown uniformly in the plane direction serves as a scaffold for the precipitation of the lithium metal in the subsequent charging, and the growth of the lithium metal in a dendrite shape is suppressed. ..
  • the factors are not limited to the above.
  • lithium metal precipitates on the negative electrode means that, unless otherwise specified, the surface of the negative electrode, the surface of the solid portion of the buffer function layer, and the negative electrode and / or the buffer function layer. It means that the lithium metal is deposited on at least one place on the surface of the SEI layer formed on the surface of the solid portion. Therefore, in the lithium secondary battery 300, the lithium metal may be deposited, for example, on the surface of the negative electrode 140 (the interface between the negative electrode 140 and the buffer function layer 310), and may be deposited inside the buffer function layer 310 (solid of the buffer function layer). It may be deposited on the surface of the portion).
  • the lithium metal is not only deposited on the surface of the negative electrode, but also deposited on the surface of the solid portion of the buffer function layer so as to fill the pores of the buffer function layer 310. do. Therefore, the buffer function layer 310 also functions as a buffer layer in the lithium secondary battery 300 to alleviate the volume expansion of the battery due to charging and discharging. That is, in the conventional lithium secondary battery having no buffering function layer, lithium metal is deposited on the surface of the negative electrode by charging, so that the cell volume of the battery after charging expands as compared with the battery before charging.
  • the lithium secondary battery 300 of the present embodiment since the lithium metal is deposited not only on the surface of the negative electrode but also on the pores of the buffer function layer 310, it is possible to suppress the expansion of the cell volume of the battery due to charging. .. Therefore, the lithium secondary battery of the present embodiment is particularly useful as a battery application having a low allowable volume expansion rate such as a battery for a small electronic terminal or the like.
  • the cushioning function layer 310 is not particularly limited as long as it is fibrous or porous and has ionic conductivity and electrical conductivity.
  • a non-limiting example of the buffering functional layer is, for example, a fibrous or porous ion conductive layer in which all or part of the surface is coated with an electric conductive layer; fibrous or porous electric conduction. Examples thereof include those in which all or a part of the surface of the layer is coated with an ion conductive layer; and those in which a fiber-shaped ion conductive layer and a fiber-shaped electric conductive layer are entangled with each other.
  • the ion conductive layer is not limited as long as it can conduct ions, and examples thereof include a solid electrolyte containing an inorganic or organic salt or a pseudo-solid electrolyte (hereinafter, also referred to as “gel electrolyte”). ..
  • the solid electrolyte and the gel electrolyte are not particularly limited as long as they are generally used for lithium secondary batteries, and known materials can be appropriately selected.
  • the resin constituting the solid electrolyte or the gel electrolyte is not particularly limited, and is, for example, a resin having an ethylene oxide unit in the main chain and / or the side chain such as polyethylene oxide (PEO), an acrylic resin, a vinyl resin, and an ester resin.
  • Nylon resin Polyvinylidene flolide (PVDF), Polyacrylonitrile (PAN), Polysiloxane, Polyphosphazene, Polymethylmethacrylate, Polyethylene, Polyimide, Aramid, Polylactic acid, Polyethylene, Polyethylene, Polyurethane, Polypropylene, Polybutylene, Polyacetal, Examples thereof include polysulfone and polytetrafluoroethylene.
  • PVDF Polyvinylidene flolide
  • PAN Polyacrylonitrile
  • Polysiloxane Polyphosphazene
  • Polymethylmethacrylate Polyethylene
  • Polyimide Aramid
  • Polylactic acid Polyethylene
  • Polyethylene Polyethylene
  • Polyurethane Polypropylene
  • Polybutylene Polyacetal
  • Examples thereof include polysulfone and polytetrafluoroethylene.
  • the above resins may be used alone or in combination of two or more.
  • Examples of the salt contained in the solid electrolyte or the gel electrolyte include salts of Li, Na, K, Ca, and Mg.
  • the lithium salt is not particularly limited, but is not particularly limited, for example, LiI, LiCl, LiBr, LiF, LiBF 4 , LiPF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 .
  • the above-mentioned salt or lithium salt may be used alone or in combination of two or more.
  • the content ratio of the resin to the lithium salt in the solid electrolyte or the gel electrolyte may be determined by the ratio of the oxygen atom of the resin to the lithium atom of the lithium salt ([Li] / [O]).
  • the content ratio of the resin and the lithium salt is such that the above ratio ([Li] / [O]) is, for example, 0.02 or more and 0.20 or less, 0.03 or more and 0.15 or less. , Or may be adjusted to be 0.04 or more and 0.12 or less.
  • the solid electrolyte or gel electrolyte may contain an electrolytic solution that can be contained in the lithium secondary battery 300, in addition to the resin and the salt.
  • the electrically conductive layer is not limited as long as it can conduct electrons, and examples thereof include a metal film.
  • metals that can be contained in the electrically conductive layer include, for example, SUS, Si, Sn, Sb, Al, Ni, Cu, Sn, Bi, Ag, Au, Pt, Pb, Zn, In, Bi. -Sn, In-Sn and the like can be mentioned.
  • Si, Sn, Zn, Bi, Ag, In, Pb, Sb, and Al are preferable from the viewpoint of enhancing the affinity with the lithium metal.
  • FIG. 4A shows a schematic cross-sectional view of the fiber-shaped cushioning function layer.
  • the buffer function layer 310 shown in FIG. 4 (A) is made of an ionic electric conductive fiber 410, which is a fiber having ionic conductivity and electric conductivity. That is, in the present embodiment, "the buffer function layer is in the form of a fiber” means that the buffer function layer contains a fiber or is composed of a fiber, and the gap between the solid portion and the solid portion causes the buffer function layer to be in the form of a fiber. It means that it has a formed pore portion.
  • lithium metal is deposited on the surface of the solid portion of the buffer function layer, that is, on the surface of the ion electric conduction fiber 410. Therefore, according to such an embodiment, as shown in the schematic cross-sectional view in FIG. 4B, a hole portion of the buffer function layer is formed on the surface of the ion electric conduction fiber 410 which is a solid portion of the buffer function layer. Lithium metal 420 precipitates to fill.
  • the ion electric conduction fiber 410 includes a fiber-like ion conduction layer 430 and an electric conduction layer 440 that covers the surface of the ion conduction layer 430.
  • the ionic conductive layer 430 may have, for example, the above-mentioned structure as an ionic conductive layer
  • the electric conductive layer 440 may have, for example, the above-mentioned structure as an electric conductive layer.
  • the fiber average diameter of the fibrous ion conductive layer 430 is preferably 30 nm or more and 5000 nm or less, more preferably 50 nm or more and 2000 nm or less, still more preferably 70 nm or more and 1000 nm or less, and further preferably 80 nm or more and 500 nm or less. Is.
  • the surface area of the reaction field where the lithium metal can be deposited becomes a more appropriate range, so that the cycle characteristics tend to be further improved.
  • the average thickness of the electrical conductive layer 440 is preferably 1 nm or more and 300 nm or less, more preferably 5 nm or more and 200 nm or less, and further preferably 10 nm or more and 150 nm or less.
  • the electric conductivity of the ion electric conductive fiber 410 can be more appropriately maintained, so that the cycle characteristics tend to be further improved.
  • the buffer function layer 310 of the lithium secondary battery 300 shown in FIG. 3 may be porous.
  • the porous buffer function layer may include, for example, a porous ionic conductive layer having communication holes, and an electric conductive layer covering the surface of the ionic conductive layer.
  • the cushioning function layer is fibrous or porous, it has pores.
  • the porosity of the buffer function layer is not particularly limited, but is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more in volume%. When the porosity of the buffer function layer is within the above range, the surface area of the reaction field where the lithium metal can be deposited is further increased, so that the cycle characteristics tend to be further improved. Further, according to such an aspect, the effect of suppressing the cell volume expansion tends to be more effectively and surely exerted.
  • the porosity of the buffer function layer is not particularly limited, but may be 99% or less, 95% or less, or 90% or less in volume%.
  • the average thickness of the buffer function layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 30 ⁇ m or less. When the average thickness of the buffer function layer is within the above range, the volume occupied by the buffer function layer 310 in the lithium secondary battery 300 is reduced, so that the energy density of the battery is further improved.
  • the average thickness of the buffer function layer is preferably 1 ⁇ m or more, more preferably 4 ⁇ m or more, and further preferably 7 ⁇ m or more. When the average thickness of the buffer function layer is within the above range, the surface area of the reaction field where the lithium metal can be deposited is further increased, so that the cycle characteristics tend to be further improved. Further, according to such an aspect, the effect of suppressing the cell volume expansion tends to be more effectively and surely exerted.
  • the fiber diameter of the fibrous ion conductive layer, the thickness of the electric conductive layer, the porosity of the buffer functional layer, and the thickness of the buffer functional layer can be measured by a known measuring method.
  • the thickness of the buffer function layer is determined by etching the surface of the buffer function layer with a focused ion beam (FIB) to expose its cross section, and observing the thickness of the buffer function layer on the exposed cut surface by SEM or TEM. It can be measured by FIB.
  • the fiber diameter of the fibrous ion conductive layer, the thickness of the electric conductive layer, and the porosity of the buffer functional layer can be measured by observing the surface of the buffer functional layer with a transmission electron microscope.
  • the porosity of the buffer function layer is calculated by binary analysis of the observed image of the surface of the buffer function layer using image analysis software and obtaining the ratio of the buffer function layer to the total area of the image. do it.
  • Each of the above measured values is calculated by calculating the average of the measured values measured 3 times or more, preferably 10 times or more.
  • the buffer function layer contains a metal capable of reacting with lithium
  • the total capacity of the negative electrode 140 and the buffer function layer 310 is sufficiently smaller than the capacity of the positive electrode 110, for example, 20% or less, 15% or less, 10 It may be% or less, or 5% or less.
  • the capacities of the positive electrode 110, the negative electrode 140, and the buffer function layer 310 can be measured by a conventionally known method.
  • the SEI layer may be formed on the surface of the negative electrode 140, and in FIG. 4, the SEI layer may be formed on the surface of the ion electric conduction fiber 410.
  • the lithium secondary battery 300 as shown in FIG. 3 has the lithium secondary according to the first embodiment shown in FIG. 1, except that the buffer function layer 310 is formed instead of forming the metal layer 130.
  • the battery 100 can be manufactured in the same manner as described above.
  • the method for producing the buffer function layer 310 is not particularly limited as long as a fibrous or porous layer having ionic conductivity and electrical conductivity can be obtained, but for example, it may be as follows.
  • the fiber-shaped buffer function layer having the ion-electric conduction fiber 410 including the fiber-like ion conduction layer 430 and the electric conduction layer 440 covering the surface of the ion conduction layer 430 is as follows.
  • an appropriate organic solvent for example, N-methylpyrrolidone
  • the separator 120 coated with the resin solution is immersed in a water bath and then sufficiently dried at room temperature to form a fibrous ion conductive layer on the separator 120 (note that the ion conductive layer is, for example, assembled into a battery). Occasionally, the electrolytic solution may be injected to exert the ionic conduction function). Subsequently, a fiber-shaped buffer functional layer can be obtained by depositing an appropriate metal (for example, Ni) on the separator on which the fiber-shaped ion conductive layer is formed under vacuum conditions.
  • Ni an appropriate metal
  • the porous buffer function layer including the porous ion conductive layer and the electric conductive layer covering the surface of the ion conductive layer can be manufactured as follows. First, using a solution in which the above-mentioned resin (for example, PVDF) is dissolved in an appropriate solvent (for example, N-methylpyrrolidone), a method using a conventionally known method (for example, a method using phase separation with a solvent, and foaming). A porous ionic conduction layer having communication holes is formed on the surface of the separator 120 (in addition, the ionic conduction layer is ionic conduction by injecting an electrolytic solution, for example, at the time of assembling a battery). It may be functional). Subsequently, a porous buffer function layer can be obtained by depositing an appropriate metal (for example, Ni) on the separator on which the porous ion conductive layer is formed under vacuum conditions.
  • an appropriate metal for example, Ni
  • a laminated body can be obtained by laminating the positive electrode 110, the separator 120 on which the buffer function layer 310 is formed, and the negative electrode 140 so that the buffer function layer 310 faces the negative electrode 140 in this order.
  • the lithium secondary battery 300 can be obtained by enclosing the obtained laminate together with the electrolytic solution in a closed container.
  • FIG. 5 is a schematic cross-sectional view of the lithium secondary battery according to the third embodiment.
  • the lithium secondary battery 500 of the third embodiment has a positive electrode 110, a negative electrode 140 having no negative electrode active material, and a separator 120 arranged between the positive electrode 110 and the negative electrode 140.
  • the metal layer 130 formed on the surface of the negative electrode 140 facing the separator 120, and the fibrous or porous ionic conductivity and electrical conductivity formed on the surface of the separator 120 facing the negative electrode 140.
  • the buffer function layer 310 is provided.
  • the positive electrode 110 has a positive electrode current collector 150 on a surface opposite to the surface facing the separator 120.
  • the configurations of the positive electrode current collector 150, the positive electrode 110, the separator 120, the metal layer 130, the buffer function layer 310, and the negative electrode 140 and the preferred embodiment thereof are the lithium secondary battery 100 of the first embodiment and the second book. It is the same as the lithium secondary battery 300 of the embodiment, and with respect to these configurations, the lithium secondary battery 500 has the same effect as the lithium secondary battery 100 and the lithium secondary battery 300. Further, the lithium secondary battery 500 may contain the electrolytic solution as described above, similarly to the lithium secondary battery 100.
  • the lithium secondary battery 500 provided with both the metal layer 130 and the buffer function layer 310 is the lithium secondary battery 100 having only one of the metal layer 130 and the buffer function layer 310, and the lithium secondary battery 300.
  • the growth of the lithium metal in the form of dendrite is further suppressed, and the cycle characteristics are further improved.
  • FIG. 6 is a schematic cross-sectional view of the lithium secondary battery according to the fourth embodiment.
  • the lithium secondary battery 600 of the fourth embodiment has a positive electrode 110, a negative electrode 140 having no negative electrode active material, and a solid electrolyte arranged between the positive electrode 110 and the negative electrode 140.
  • a cushioning functional layer 310 having conductivity is provided.
  • the positive electrode 110 has a positive electrode current collector 150 on a surface opposite to the surface facing the solid electrolyte 610.
  • the configurations and preferred embodiments of the positive electrode current collector 150, the positive electrode 110, the metal layer 130, the buffer function layer 310, and the negative electrode 140 are the lithium secondary battery 100 of the first embodiment and the lithium of the second embodiment.
  • the secondary battery 300 and the lithium secondary battery 500 of the third embodiment are the same.
  • the lithium secondary battery 600 includes a lithium secondary battery 100, a lithium secondary battery 300, and a lithium 2. It has the same effect as the next battery 500.
  • Solid electrolyte In general, a battery provided with a liquid electrolyte tends to have a different physical pressure from the electrolyte to the surface of the negative electrode depending on the location due to the fluctuation of the liquid.
  • the lithium secondary battery 600 includes the solid electrolyte 610, the pressure applied from the solid electrolyte 610 to the surface of the negative electrode 140 becomes more uniform, and the shape of the lithium metal deposited on the surface of the negative electrode 140 becomes more uniform. be able to. That is, according to such an embodiment, the carrier metal deposited on the surface of the negative electrode 140 is further suppressed from growing in a dendrite shape, so that the cycle characteristics of the lithium secondary battery 600 are further improved.
  • the solid electrolyte 610 is not particularly limited as long as it is generally used for a lithium solid secondary battery, but a known material can be appropriately selected depending on the use of the lithium secondary battery 600.
  • the solid electrolyte 610 preferably has ionic conductivity and no electrical conductivity. Since the solid electrolyte 610 has ionic conductivity and no electrical conductivity, the internal resistance of the lithium secondary battery 600 is further reduced, and short-circuiting inside the lithium secondary battery 600 is further suppressed. can do. As a result, the energy density, capacity, and cycle characteristics of the lithium secondary battery 600 are further improved.
  • the solid electrolyte 610 is not particularly limited, and examples thereof include those containing a resin and a lithium salt.
  • a resin is not particularly limited, and examples thereof include a resin exemplified as a resin that can be contained in the ion conductive layer of the buffer function layer 310.
  • the lithium salt is not particularly limited, and examples thereof include resins exemplified as lithium salts that can be contained in the ionic conduction layer of the buffer function layer 310.
  • one type may be used alone or two or more types may be used in combination.
  • the content ratio of the resin to the lithium salt is such that the above ratio ([Li] / [O]) is preferably 0.02 or more and 0.20 or less, more preferably 0.03 or more and 0.15.
  • the adjustment is made so as to be more preferably 0.04 or more and 0.12 or less.
  • the solid electrolyte 610 may contain components other than the above resin and lithium salt. Such components are not particularly limited, and examples thereof include salts other than solvents and lithium salts.
  • the salt other than the lithium salt is not particularly limited, and examples thereof include salts of Li, Na, K, Ca, and Mg.
  • the solvent is not particularly limited, and examples thereof include those exemplified in the electrolytic solution that can be contained in the lithium secondary battery 100.
  • the average thickness of the solid electrolyte 610 is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, and further preferably 15 ⁇ m or less. According to such an embodiment, the volume occupied by the solid electrolyte 610 in the lithium secondary battery 600 is reduced, so that the energy density of the lithium secondary battery 600 is further improved.
  • the average thickness of the solid electrolyte 610 is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more. According to such an aspect, the positive electrode 110 and the negative electrode 140 can be more reliably isolated, and the short circuit of the battery can be further suppressed.
  • the solid electrolyte 610 shall contain a gel electrolyte.
  • the gel electrolyte is not particularly limited, and examples thereof include those containing a polymer, an organic solvent, and a lithium salt.
  • the polymer in the gel electrolyte is not particularly limited, and examples thereof include a copolymer of polyethylene and / or polyethylene oxide, polyvinylidene fluoride, and a copolymer of polyvinylidene fluoride and hexafluoropropylene.
  • the lithium secondary battery 600 can be manufactured in the same manner as the manufacturing method of the lithium secondary battery 100 according to the third embodiment described above, except that a solid electrolyte is used instead of the separator.
  • the method for producing the solid electrolyte 610 is not particularly limited as long as it is a method for obtaining the above-mentioned solid electrolyte 610, but for example, the following may be used.
  • a resin conventionally used for a solid electrolyte and a lithium salt (for example, the above-mentioned resin and a lithium salt as a resin that can be contained in the solid electrolyte 610) are dissolved in an organic solvent (for example, N-methylpyrrolidone, acetonitrile).
  • the solid electrolyte 610 is obtained by casting the obtained solution onto a molding substrate so as to have a predetermined thickness.
  • the compounding ratio of the resin and the lithium salt may be determined by the ratio ([Li] / [O]) of the oxygen atom of the resin and the lithium atom of the lithium salt, as described above.
  • the above ratio ([Li] / [O]) is, for example, 0.02 or more and 0.20 or less.
  • the molding substrate is not particularly limited, but for example, a PET film or a glass substrate may be used.
  • the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
  • the present invention can be modified in various ways as long as it does not deviate from the gist thereof. ..
  • either the metal layer 130 or the buffer function layer 310 may be omitted.
  • the metal layers 130 may be formed on both sides of the negative electrode 140.
  • each configuration of the lithium secondary battery is laminated in the following order: positive electrode / separator / metal layer / negative electrode / metal layer / separator / positive electrode.
  • the capacity of the lithium secondary battery can be further improved.
  • the lithium secondary battery 300 of the second embodiment, the lithium secondary battery 500 of the third embodiment, and the lithium secondary battery 600 of the fourth embodiment have the same laminated structure. be able to.
  • the lithium secondary battery of this embodiment may be a lithium solid secondary battery. According to such an embodiment, since it is not necessary to use the electrolytic solution, the problem of electrolytic solution leakage does not occur, and the safety of the battery is further improved.
  • a lithium foil may or may not be formed between the separator or the solid electrolyte and the negative electrode before the initial charge.
  • the lithium secondary battery of the present embodiment does not use a highly flammable lithium metal during manufacturing when a lithium foil is not formed between the separator or the solid electrolyte and the negative electrode before the initial charge. Therefore, it becomes a lithium secondary battery having further excellent safety and productivity.
  • the lithium secondary battery of the present embodiment may or may not have a current collector arranged so as to be in contact with the negative electrode or the positive electrode on the surface of the negative electrode and / or the positive electrode.
  • the current collector is not particularly limited, and examples thereof include those that can be used as a negative electrode material.
  • the lithium secondary battery does not have a positive electrode current collector and a negative electrode current collector, the positive electrode and the negative electrode themselves act as current collectors, respectively.
  • terminals for connecting to an external circuit may be attached to the positive electrode and / or the negative electrode.
  • metal terminals of 10 ⁇ m or more and 1 mm or less for example, Al, Ni, etc.
  • the joining method a conventionally known method may be used, and for example, ultrasonic welding may be used.
  • high energy density or “high energy density” means that the total volume of the battery or the capacity per total mass is high, but preferably 800 Wh / L or more or 350 Wh. It is / kg or more, more preferably 900 Wh / L or more or 400 Wh / kg or more, and further preferably 1000 Wh / L or more or 450 Wh / kg or more.
  • excellent in cycle characteristics means that the rate of decrease in battery capacity is low before and after the number of charge / discharge cycles that can be expected in normal use. That is, when comparing the first discharge capacity after the initial charge / discharge with the capacity after the charge / discharge cycle of the number of times that can be expected in normal use, the capacity after the charge / discharge cycle is the capacity after the initial charge / discharge. It means that there is almost no decrease with respect to the first discharge capacity of.
  • the "number of times that can be assumed in normal use” depends on the application in which the lithium secondary battery is used, but is, for example, 30 times, 50 times, 70 times, 100 times, 300 times, or 500 times. be.
  • the capacity after the charge / discharge cycle is hardly reduced with respect to the first discharge capacity after the initial charge / discharge", depending on the application in which the lithium secondary battery is used, for example, charge.
  • the capacity after the discharge cycle is 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, or 85% or more with respect to the first discharge capacity after the initial charge / discharge. means.
  • a separator having a predetermined size was prepared in which both sides of a 12 ⁇ m polyethylene microporous membrane were coated with 2 ⁇ m polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • Li 2 O 3 and Li 3 N commercially available Li 2 O 3 and Li 3 N were used. Further, those containing Li 2S were produced by the method described in JP-A - 2019-145299. That is, Li 2 S and P 2 S 5 , LiCl, LiBr, or LiI are mixed in a mortar so as to have a molar ratio of 80:20, and a solid phase reaction is carried out in an argon atmosphere using a planetary ball mill device. Then, a lithium sulfide-based solid solution was obtained. Next, the obtained lithium sulfide-based solid solution and activated carbon were mixed at a mass ratio of 90:10 by a ball mill to obtain a sacrificial positive electrode agent.
  • Li 5 FeO 4 was produced by the method described in Chem. Mater. 2010, 22, 1263-1270 1263. That is, a sacrificial positive electrode agent was obtained by pulverizing and mixing LiOH ⁇ H 2 O and Fe 2 O 3 and firing them in a nitrogen atmosphere at 800 ° C. for 72 hours.
  • the mixing ratio of the positive electrode active material and the sacrificial positive electrode agent is the charge capacity density (mAh / g) of the positive electrode active material and the sacrificial positive electrode agent measured as follows, and the irreversible volume density A (mAh / g) of the sacrificial positive electrode agent.
  • the ratio of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the battery was each value described as "addition rate (cell capacity ratio%)" in Table 1.
  • the total amount of the positive electrode active material and the sacrificial positive electrode agent was adjusted so that the cell capacity of the lithium secondary battery was 60 mAh.
  • the content of the sacrificial positive electrode agent with respect to the entire positive electrode is shown in Table 1 as "addition amount (mass%)".
  • a positive electrode active material or a sacrificial positive electrode agent, PVDF, a conductive auxiliary agent, and N-methylpyrrolidone (NMP) were mixed to prepare a slurry, which was applied, dried, and pressed on an aluminum foil.
  • a test cell using lithium metal as the counter electrode is prepared, charged with a current of 0.2 mAh / cm 2 until the voltage reaches 4.2 V, and then discharged until the voltage reaches 3.0 V.
  • mAh / g) and / or the irreversible capacitance density A (mAh / g) were determined.
  • the obtained negative electrode was degreased, washed with pure water, and then immersed in a plating bath containing Sn ions. Tin was plated on the surface of the negative electrode by electrolytically plating the surface of the negative electrode while the negative electrode was left horizontally. The negative electrode was taken out from the plating bath, washed with ethanol, and washed with pure water. As described above, a metal layer was formed on one side of the negative electrode. The electrolysis time was adjusted so that the metal layer had a thickness of 100 nm.
  • Ni was vapor-deposited under vacuum conditions on the separator on which the fibrous ion conductive layer was formed.
  • the ion conduction layer after Ni vapor deposition was observed using an SEM with an energy dispersive X-ray analyzer (EDX), it was confirmed that Ni was distributed so as to cover the fiber-like ion conduction layer. It was confirmed that a fibrous cushioning functional layer was obtained in which the surface of the ionic conductive layer was covered with an electric conductive layer.
  • the cross section of the buffer function layer was prepared by FIB and observed by SEM, the average thickness of the buffer function layer was 10 ⁇ m.
  • the average thickness of the Ni thin film as the electrical conduction layer and the porosity of the buffer function layer were 20 nm and 90%, respectively.
  • a dimethoxyethane (DME) solution of 4M LiN (SO 2 F) 2 (LFSI) was prepared.
  • the positive electrode, the separator, and the negative electrode were laminated in this order to obtain a laminated body.
  • the buffer function layer is formed on the separator, the buffer function layer is laminated so as to face the negative electrode, and when the metal layer is formed on the negative electrode, the metal layer is laminated so as to face the separator.
  • 100 ⁇ m Al terminal and 100 ⁇ m Ni terminal were bonded to the positive electrode and the negative electrode by ultrasonic welding, respectively, and then inserted into the outer body of the laminate.
  • the above electrolytic solution was injected into the above exterior body.
  • a lithium secondary battery was obtained by sealing the exterior body.
  • Examples 1 to 10 Using the sacrificial positive electrode agent shown in Table 1, a lithium secondary battery including a positive electrode, a separator having a buffering function layer formed therein, and a negative electrode having a metal layer formed therein was produced.
  • the mixing ratio of the positive electrode active material and the sacrificial positive electrode agent the ratio of the irreversible capacity of the sacrificial positive electrode agent to the cell capacity of the battery is each value described as "addition rate (cell capacity ratio%)" in Table 1.
  • the content of the sacrificial positive electrode agent with respect to the entire positive electrode was adjusted to be each value described as "addition amount (mass%)" in Table 1.
  • Example 11 A lithium secondary battery was obtained in the same manner as in Example 2 except that a separator having no buffering function layer was used instead of the separator having the cushioning function layer formed therein.
  • Example 12 A lithium secondary battery was obtained in the same manner as in Example 2 except that the negative electrode on which the metal layer was formed was used instead of the negative electrode on which the metal layer was not formed.
  • the prepared lithium secondary battery was charged at 0.2 mAh / cm 2 until the voltage reached 4.2 V (initial charge), and then discharged at 0.2 mAh / cm 2 until the voltage reached 3.0 V. (Initial discharge).
  • a charge / discharge cycle of charging at 1.0 mAh / cm 2 until the voltage reaches 4.2 V and then discharging at 1.0 mAh / cm 2 until the voltage reaches 3.0 V is performed in an environment at a temperature of 25 ° C. Then, 99 cycles were repeated.
  • the capacity (initial capacity) obtained from the initial charge was 60 mAh.
  • the ratio of the discharge capacity obtained from the discharge in the 100th cycle of the charge / discharge cycle to the discharge capacity obtained from the discharge in the second cycle of the charge / discharge cycle is maintained. It was calculated as a rate (%) and used as an index of cycle characteristics. The higher the capacity retention rate, the better the cycle characteristics. Table 1 shows the capacity retention rate in each example.
  • Examples 1 to 12 provided with at least one of a metal layer and a buffer function layer and to which a sacrificial positive electrode agent was added had a higher capacity retention rate and a cycle as compared with Comparative Examples 2 and 2 which did not. It can be seen that the characteristics are excellent.
  • the lithium secondary battery of the present invention has a high energy density and excellent cycle characteristics, it has industrial applicability as a power storage device used for various purposes.

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WO2024079848A1 (ja) * 2022-10-13 2024-04-18 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 リチウム２次電池及びその製造方法
JPWO2024089460A1 (https=) * 2022-10-27 2024-05-02
CN119786716A (zh) * 2025-01-06 2025-04-08 浙江锋锂新能源科技有限公司 一种固态电池用多层电解质膜及其制备方法
WO2025079665A1 (ja) * 2023-10-11 2025-04-17 日本特殊陶業株式会社 蓄電デバイス及びその製造方法
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