WO2022224572A1 - 電池および電極の製造方法 - Google Patents

電池および電極の製造方法 Download PDF

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WO2022224572A1
WO2022224572A1 PCT/JP2022/006553 JP2022006553W WO2022224572A1 WO 2022224572 A1 WO2022224572 A1 WO 2022224572A1 JP 2022006553 W JP2022006553 W JP 2022006553W WO 2022224572 A1 WO2022224572 A1 WO 2022224572A1
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electrode
active material
solid electrolyte
material layer
current collector
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French (fr)
Japanese (ja)
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貴司 大戸
正久 藤本
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202280027610.3A priority Critical patent/CN117121230A/zh
Priority to JP2023516308A priority patent/JPWO2022224572A1/ja
Publication of WO2022224572A1 publication Critical patent/WO2022224572A1/ja
Priority to US18/479,135 priority patent/US20240030419A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/38—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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to methods for manufacturing batteries and electrodes.
  • lithium secondary batteries have been actively researched and developed, and battery characteristics such as charge/discharge voltage, charge/discharge cycle life characteristics, and storage characteristics are greatly affected by the electrodes used. For this reason, improvements in battery characteristics have been attempted by improving electrode active materials.
  • Patent Literature 1 discloses a lithium secondary battery comprising a negative electrode, a positive electrode, and an electrolyte including a negative electrode material made of an alloy containing silicon, tin, and a transition metal.
  • Patent Document 2 discloses a lithium secondary battery including a negative electrode using a silicon thin film provided on a current collector as an active material, a positive electrode, and an electrolyte.
  • Non-Patent Document 1 discloses a negative electrode containing Bi as a negative electrode active material, which is manufactured using Bi powder.
  • the present disclosure provides batteries with improved cycling characteristics.
  • the battery of the present disclosure is a first electrode; a second electrode; a solid electrolyte layer positioned between the first electrode and the second electrode; with The first electrode is a current collector; an active material layer positioned between the current collector and the solid electrolyte layer; The active material layer contains Bi 3 Ni, The Bi 3 Ni has a crystal structure in which the space group belongs to Pnma.
  • a battery with improved cycle characteristics can be provided.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example of a battery according to an embodiment of the present disclosure.
  • FIG. 2 is a graph showing an example of an X-ray diffraction pattern of an active material layer composed of a Bi 3 Ni-containing thin film formed on a nickel foil.
  • 3 is a graph showing the results of a charge/discharge test of the test cell according to Example 1.
  • FIG. 4 is a graph showing the results of a charge-discharge cycle test of the test cell according to Example 1.
  • FIG. FIG. 5 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Example 1.
  • FIG. 6 is a graph showing the results of a charge/discharge test of the test cell according to Example 2.
  • FIG. 7 is a graph showing the results of a charge-discharge cycle test of the test cell according to Example 2.
  • FIG. 8 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Example 2.
  • FIG. 9 is a graph showing the results of a charge/discharge test of a test cell according to Reference Example 1.
  • FIG. 10 is a graph showing the results of a charge-discharge cycle test of the test cell according to Reference Example 1.
  • FIG. 11 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Reference Example 1.
  • lithium metal When lithium metal is used as the negative electrode active material, a lithium secondary battery having high energy density per weight and per volume can be obtained.
  • lithium deposits in the form of dendrites during charging. Since part of the deposited lithium metal reacts with the electrolytic solution, the charge/discharge efficiency is low and the cycle characteristics are poor.
  • carbon especially graphite
  • a negative electrode using carbon is charged and discharged by intercalation and deintercalation of lithium into and from carbon.
  • lithium metal does not deposit in a dendrite form due to the charge/discharge mechanism.
  • the reaction is topotactic, so the reversibility is very good, and the charge/discharge efficiency is almost 100%.
  • lithium secondary batteries employing negative electrodes using carbon, particularly graphite have been put to practical use.
  • the theoretical capacity density of graphite is 372 mAh/g, which is about 1/10 of the theoretical capacity density of lithium metal, 3884 mAh/g. Therefore, the active material capacity density of the negative electrode using graphite is low. Furthermore, since the actual capacity density of graphite has almost reached the theoretical capacity density, there is a limit to increasing the capacity of negative electrodes using graphite.
  • lithium secondary batteries using electrodes such as aluminum, silicon, and tin that electrochemically alloy with lithium during charging have long been proposed.
  • the capacity density of metals alloyed with lithium is much higher than that of graphite.
  • the theoretical capacity density of silicon is large. Therefore, electrodes using aluminum, silicon, tin, etc., which are alloyed with lithium, are promising as negative electrodes for batteries exhibiting high capacity, and various secondary batteries using these as negative electrodes have been proposed (Patent Documents 1).
  • a negative electrode that uses a metal that alloys with lithium as described above expands when it absorbs lithium and contracts when it releases lithium. If such expansion and contraction are repeated during charging and discharging, the alloy itself, which is the electrode active material, will be pulverized due to charging and discharging, and the current collection characteristics of the negative electrode will deteriorate, so sufficient cycle characteristics have not been obtained.
  • the following attempts have been made to improve such drawbacks. For example, attempts have been made to deposit silicon on a roughened current collector by sputtering or evaporation, or to deposit tin by electroplating (Patent Document 2). In this trial, the active material, that is, the metal that alloys with lithium forms a thin film and adheres to the current collector. not decrease.
  • the active material is formed by sputtering or vapor deposition as described above, the manufacturing cost is high and it is not practical. Although it is practical to form the active material by electroplating, which is inexpensive to manufacture, silicon is very difficult to electroplate. In addition, tin, which is easily electroplated, has poor discharge flatness and is difficult to use as a battery electrode.
  • Bi bismuth
  • LiBi lithium
  • LiBi lithium
  • Li 3 Bi Li 3 Bi
  • the potential of LiBi and the potential of Li 3 Bi are almost the same.
  • tin which has poor discharge flatness
  • Bi does not have the property that different types of compounds formed with lithium have different potentials, unlike tin. Therefore, an electrode containing Bi as an active material has a flat electric potential, and is therefore excellent in discharge flatness. Therefore, an electrode containing Bi as an active material is considered suitable as a battery electrode.
  • Bi has poor malleability and ductility, and is difficult to produce in the form of a metal plate or metal foil, and the obtained form is globules or powder. Therefore, as an electrode containing Bi as an active material, an electrode manufactured by coating a current collector with Bi powder has been studied. However, an electrode manufactured using such a Bi powder is pulverized by repeated charging and discharging, resulting in deterioration of current collection characteristics, and sufficient cycle characteristics have not been obtained. For example, in Non-Patent Document 1, an electrode containing Bi as an active material is produced using Bi powder and PVdF (polyvinylidene fluoride) or PI (polyimide) as a binder.
  • PVdF polyvinylidene fluoride
  • PI polyimide
  • Non-Patent Document 1 charging and discharging of a battery produced using this electrode are performed. However, both the initial charge/discharge curve and cycle characteristics of the fabricated electrode are very poor. Although it is measured at a very low rate equivalent to 0.042C, the initial charge/discharge efficiency is low and the cycle deterioration is severe, making it unusable. Regarding this cycle deterioration, in Non-Patent Document 1, as the Bi active material expands when Li is inserted and the Bi active material contracts when Li is desorbed, the active material becomes finer and an electron conduction path cannot be taken, resulting in a decrease in capacity. is believed to occur.
  • the present inventors have focused on Bi, which does not have the property that the potential differs greatly between the multiple types of compounds formed with Li, and has excellent discharge flatness, and can improve cycle characteristics.
  • the inventors of the present invention have found a new idea that when Bi 3 Ni having a specific crystal structure, specifically a crystal structure in which the space group belongs to Pnma, is used as an active material, the cycle characteristics of the battery are improved. arrived at a technical idea.
  • the inventors of the present invention conducted more detailed studies on batteries in which Bi 3 Ni is used as an active material.
  • a battery using Bi 3 Ni having the specific crystal structure as an active material can maintain a discharge capacity exceeding 10% of the initial discharge capacity if, for example, about 20 cycles of charge and discharge are performed. possible and the cycling characteristics are improved.
  • the discharge capacity retention rate decreases to about 30% of the initial discharge capacity. There was a problem that the discharge capacity retention rate decreased to 5% or less of the initial discharge capacity after about 100 cycles of charging and discharging.
  • the inventors of the present invention conducted further investigations and found that the large decrease in capacity from the initial capacity in about 100 charge-discharge cycles was caused by the following causes.
  • an electrode containing Bi 3 Ni having the above-mentioned specific crystal structure as an active material uses, as an electrolyte layer, a solid electrolyte that does not flow in the battery during the charging and discharging cycles of the battery.
  • the inventors have found that the cycle characteristics can be improved, and have completed the present disclosure.
  • the battery according to the first aspect of the present disclosure includes a first electrode; a second electrode; a solid electrolyte layer positioned between the first electrode and the second electrode; with The first electrode is a current collector; an active material layer positioned between the current collector and the solid electrolyte layer; The active material layer contains Bi 3 Ni, The Bi 3 Ni has a crystal structure in which the space group belongs to Pnma.
  • the battery according to the first aspect includes an electrode containing, as an active material, Bi 3 Ni having a crystal structure in which the space group belongs to Pnma. Therefore, the cycle characteristics of the battery can be improved. Furthermore, in the battery according to the first aspect, the electrolyte layer is a solid electrolyte layer. Therefore, even if the active material layer containing Bi 3 Ni expands and shrinks repeatedly due to charging and discharging, the electrolyte does not enter the active material layer, so that the reduction of electron conduction paths in the active material layer can be suppressed. Therefore, the battery according to the first aspect has improved cycling characteristics.
  • the active material layer may contain at least one selected from the group consisting of LiBi and Li 3 Bi.
  • the battery according to the second aspect has improved capacity and improved cycle characteristics.
  • the active material layer may not contain an electrolyte.
  • a battery having higher capacity per volume and improved cycle characteristics is obtained.
  • the active material layer may contain the Bi 3 Ni as a main component of the active material.
  • the current collector may contain Ni.
  • the battery according to the fifth aspect has improved capacity and improved cycle characteristics.
  • the active material layer may be a heat-treated plated layer.
  • a battery having higher capacity per volume and improved cycle characteristics is obtained.
  • the solid electrolyte layer may contain a halide solid electrolyte, and the halide solid electrolyte contains sulfur. It does not have to be substantially included.
  • the battery according to the seventh aspect has improved capacity and improved cycle characteristics.
  • the solid electrolyte layer may contain a sulfide solid electrolyte.
  • the battery according to the eighth aspect has improved capacity and improved cycle characteristics.
  • the first electrode may be a negative electrode and the second electrode may be a positive electrode.
  • the battery according to the ninth aspect has improved capacity and improved cycle characteristics.
  • a method for manufacturing an electrode according to a tenth aspect of the present disclosure includes forming a Bi-plated layer on a current collector containing Ni by an electroplating method, heating the current collector and the Bi-plated layer, and obtaining an electrode having an active material layer containing Bi 3 Ni formed on the current collector by diffusing Ni contained in the current collector into the Bi plating layer.
  • the manufacturing method according to the tenth aspect it is possible to manufacture an electrode capable of realizing a battery with improved cycle characteristics.
  • the Bi 3 Ni may have a crystal structure in which the space group belongs to Pnma.
  • the manufacturing method according to the eleventh aspect it is possible to manufacture an electrode capable of realizing a battery with improved cycle characteristics.
  • the temperature for heating the current collector and the Bi plating layer may be 200°C or higher and 350°C or lower.
  • an electrode containing, for example, Bi 3 Ni as a main component of the active material can be produced, so that an electrode that can realize a battery with improved cycle characteristics can be produced.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example of a battery 1000 according to an embodiment of the present disclosure.
  • Battery 1000 includes first electrode 101 , second electrode 103 , and solid electrolyte layer 102 positioned between first electrode 101 and second electrode 103 .
  • the first electrode 101 has a current collector 100 and an active material layer 104 located between the current collector 100 and the solid electrolyte layer 102 .
  • Active material layer 104 contains Bi 3 Ni. This Bi 3 Ni has an orthorhombic crystal structure in which the space group belongs to Pnma.
  • the electrolyte layer is solid electrolyte layer 102 . Therefore, even if the active material layer 104 containing Bi 3 Ni as an active material repeatedly expands and contracts due to charging and discharging, the electrolyte does not enter the active material layer 104 . Therefore, reduction in electron conduction paths in the active material layer 104 due to repeated charging and discharging is suppressed. Accordingly, battery 1000 has improved cycling characteristics.
  • the battery 1000 is, for example, a lithium secondary battery.
  • a case in which lithium ions are intercalated and deintercalated in the active material layer 104 of the first electrode 101 and the second electrode 103 during charging and discharging of the battery 1000 will be described as an example.
  • the active material layer 104 may contain Bi 3 Ni as a main component.
  • the active material layer 104 contains Bi 3 Ni as a main component is defined as "the content of Bi 3 Ni in the active material layer 104 is 50% by mass or more”.
  • the content ratio of Bi 3 Ni in the active material layer 104 is determined by confirming that Bi and Ni are contained in the active material layer 104 by, for example, elemental analysis using EDX (energy dispersive X-ray analysis). It can be obtained by calculating the ratio of the compounds contained by Rietveld analysis of the X-ray diffraction result of 104.
  • the active material layer 104 containing Bi 3 Ni as a main component may be composed of, for example, a thin film containing Bi 3 Ni (hereinafter referred to as "Bi 3 Ni containing thin film").
  • the active material layer 104 has an orthorhombic crystal structure belonging to the space group Pnma[62]. may be
  • the active material layer 104 contains Bi 3 Ni having a crystal structure belonging to the above space group, good cycle characteristics can be obtained.
  • the active material layer 104 composed of a Bi 3 Ni-containing thin film containing Bi 3 Ni as a main component can be produced, for example, by electroplating.
  • a method of manufacturing the first electrode 101 by forming the active material layer 104 by electroplating is, for example, as follows.
  • the current collector 100 serves as a base material, for example.
  • a current collector containing Ni is prepared as the current collector 100 .
  • the method for manufacturing the first electrode 101 includes, for example, forming a Bi-plated layer on a current collector containing Ni by an electroplating method, heating the current collector and the Bi-plated layer, and heating the current collector. diffusing Ni contained in the body into the Bi plating layer to obtain an electrode having an active material layer containing Bi 3 Ni formed on the current collector.
  • the manufacturing method of the first electrode 101 will be explained more specifically.
  • the current collector 100 serves as a base material, for example.
  • a nickel foil is prepared as the current collector 100 .
  • the nickel foil is preliminarily degreased with an organic solvent, one side is masked and immersed in an acid solvent for degreasing, thereby activating the surface of the nickel foil.
  • the activated nickel foil is connected to a power source so that current can be applied.
  • a nickel foil connected to a power supply is immersed in a bismuth plating bath.
  • the bismuth plating bath for example, an organic acid bath containing Bi 3+ ions and an organic acid is used.
  • the unmasked nickel foil surface is electroplated with Bi.
  • the nickel foil is recovered from the plating bath, removed from the masking, washed with pure water, and dried.
  • a Bi plating layer is produced on the surface of the nickel foil.
  • the bismuth plating bath used for producing the Bi plating layer is not particularly limited, and can be appropriately selected from known bismuth plating baths capable of depositing a simple Bi thin film.
  • organic sulfonic acid baths In bismuth plating baths, organic sulfonic acid baths, gluconic acid and ethylenediaminetetraacetic acid (EDTA) baths, or citric acid and EDTA baths can be used as organic acid baths.
  • EDTA ethylenediaminetetraacetic acid
  • a sulfuric acid bath for example, may be used as the bismuth plating bath.
  • Additives may also be added to the bismuth plating bath.
  • Table 1 shows the target thickness of the Bi plating layer produced by electroplating Bi and the thickness of the actually produced Bi plating layer.
  • a sample of the Bi plating layer was produced in the same manner as in Example 1, which will be described later. However, the sample was prepared by adjusting the current application time to the nickel foil, which is the plating substrate, aiming at a plating thickness of 5 ⁇ m.
  • the thickness of the obtained Bi plating layer was measured using a fluorescent X-ray device SEA6000VX manufactured by Seiko Instruments Inc. The average thickness of the Bi layer in the five samples was 5.7 ⁇ m, 5.1 ⁇ m, 5.1 ⁇ m, 5.7 ⁇ m and 5.8 ⁇ m.
  • the nickel foil and the Bi plating layer formed on the nickel foil are heated.
  • Ni is allowed to diffuse in the solid phase from the nickel foil to the Bi plating layer, and an active material layer composed of a Bi 3 Ni-containing thin film containing Bi 3 Ni can be produced.
  • a sample obtained by electroplating Bi on a nickel foil is subjected to heat treatment, for example, at a temperature of 200 ° C. or more and 350 ° C. or less in a non-oxidizing atmosphere for 30 minutes or more and less than 100 hours.
  • Ni diffuses into the Bi plating layer in the solid phase, and an active material layer composed of a thin film containing Bi 3 Ni can be produced.
  • the sample obtained by electroplating Bi on the nickel foil with a thickness of 5 ⁇ m was subjected to heat treatment at 250° C. for 30 minutes in an argon atmosphere to prepare an active material layer composed of a thin film containing Bi 3 Ni. rice field.
  • structural analysis of the surface of the active material layer composed of the manufactured Bi 3 Ni-containing thin film was also performed by surface X-ray diffraction measurement.
  • FIG. 2 is a graph showing an example of an X-ray diffraction pattern of an active material layer composed of a Bi 3 Ni-containing thin film formed on a nickel foil.
  • the X-ray diffraction pattern was obtained from the surface of the active material layer, that is, from the thickness direction of the active material layer 104 using an X-ray diffractometer (MiNi Flex manufactured by RIGAKU) using Cu-K ⁇ rays with wavelengths of 1.5405 ⁇ and 1.5444 ⁇ . is measured by the ⁇ -2 ⁇ method using X-rays.
  • Bi 3 Ni with a space group belonging to Pnma as a crystal structure BiNi with a space group belonging to C2/m as a crystal structure, nickel foil as a current collector and A phase of Ni contained within the active material layer was identified.
  • first electrode 101 has current collector 100 and active material layer 104 .
  • the configuration of the active material layer 104 is as described above.
  • the first electrode 101 functions as a negative electrode. Therefore, the active material layer 104 includes a negative electrode active material that has the property of intercalating and deintercalating lithium ions.
  • the active material layer 104 contains Bi 3 Ni having a crystal structure in which the space group belongs to Pnma, and this Bi 3 Ni functions as a negative electrode active material.
  • the active material layer 104 contains Bi 3 Ni as an active material.
  • Bi is a metal element that alloys with lithium.
  • an alloy containing Ni reduces the load on the crystal structure of the negative electrode active material when lithium atoms are desorbed and inserted during charge and discharge, and the capacity retention rate of the battery is reduced. It is presumed that the decrease in When Bi 3 Ni functions as a negative electrode active material, lithium is occluded by forming an alloy with lithium during charging. That is, a lithium-bismuth alloy is generated in the active material layer 104 when the battery 1000 is charged.
  • the produced lithium-bismuth alloy contains, for example, at least one selected from the group consisting of LiBi and Li 3 Bi.
  • the active material layer 104 contains at least one selected from the group consisting of LiBi and Li 3 Bi, for example. Upon discharge of battery 1000, lithium is released from the lithium bismuth alloy and the lithium bismuth alloy reverts to Bi3Ni .
  • Active material layer 104 may not contain an electrolyte.
  • the active material layer 104 may be a layer of an intermetallic compound of Ni and Bi, such as Bi 3 Ni, and/or a lithium-bismuth alloy and nickel produced during charging.
  • the active material layer 104 may be arranged in direct contact with the surface of the current collector 100 .
  • the active material layer 104 may be in the form of a thin film.
  • the active material layer 104 may be a heat-treated plated layer.
  • the active material layer 104 may be a heat-treated plated layer provided in direct contact with the surface of the current collector 100 . That is, as described above, the active material layer 104 may be a layer formed by heat-treating a Bi-plated layer formed on the Ni-containing current collector 100 .
  • the active material layer 104 When the active material layer 104 is a heat-treated plated layer provided in direct contact with the surface of the current collector 100 , the active material layer 104 firmly adheres to the current collector 100 . This makes it possible to further suppress the deterioration of the current collection characteristics of the first electrode 101 that occurs when the active material layer 104 repeatedly expands and contracts. Therefore, the cycle characteristics of battery 1000 are further improved. Furthermore, when the active material layer 104 is a heat-treated plated layer, the active material layer 104 contains Bi alloying with lithium at a high density, so that the capacity can be further increased.
  • the active material layer 104 may contain materials other than Bi 3 Ni.
  • the active material layer 104 may further contain a conductive material.
  • Conductive materials include carbon materials, metals, inorganic compounds, and conductive polymers.
  • Carbon materials include graphite, acetylene black, carbon black, ketjen black, carbon whiskers, needle coke, and carbon fibers.
  • Graphite includes natural graphite and artificial graphite.
  • Natural graphite includes massive graphite and flake graphite.
  • Metals include copper, nickel, aluminum, silver, and gold.
  • Inorganic compounds include tungsten carbide, titanium carbide, tantalum carbide, molybdenum carbide, titanium boride, and titanium nitride. These materials may be used alone, or a mixture of multiple types may be used.
  • the active material layer 104 may further contain a binder.
  • Binders include fluorine-containing resins, thermoplastic resins, ethylene propylene diene monomer (EPDM) rubber, sulfonated EPDM rubber, and natural butyl rubber (NBR).
  • Fluorine-containing resins include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluororubber.
  • Thermoplastic resins include polypropylene and polyethylene. These materials may be used alone, or a mixture of multiple types may be used.
  • the thickness of the active material layer 104 is not particularly limited, and may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the material of the current collector 100 is, for example, a single metal or alloy. More specifically, it may be a single metal or alloy containing at least one selected from the group consisting of copper, chromium, nickel, titanium, platinum, gold, aluminum, tungsten, iron, and molybdenum. Current collector 100 may be stainless steel.
  • the current collector 100 may contain nickel (Ni).
  • the current collector 100 may be plate-shaped or foil-shaped. From the viewpoint of easily ensuring high conductivity, the negative electrode current collector may be a metal foil or a metal foil containing nickel. Metal foils containing nickel include, for example, nickel foils and nickel alloy foils. The content of nickel in the metal foil may be 50% by mass or more, or may be 80% by mass or more. In particular, the metal foil may be a nickel foil containing substantially only nickel as metal.
  • the current collector 100 may be formed by forming a Ni layer such as a Ni plating layer on the surface of a metal foil made of a metal or alloy other than nickel.
  • the current collector 100 may be a laminated film.
  • Solid electrolyte layer As the solid electrolyte contained in the solid electrolyte layer 102, a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used.
  • a halide solid electrolyte means a solid electrolyte containing a halogen element.
  • the halide solid electrolyte may contain not only halogen elements but also oxygen.
  • Halide solid electrolytes do not contain sulfur (S).
  • the halide solid electrolyte may be, for example, a material represented by the following compositional formula (1).
  • Li ⁇ M ⁇ X ⁇ Formula (1) where, ⁇ , ⁇ , and ⁇ are values greater than 0, M is at least one selected from the group consisting of metal elements other than Li and metalloid elements, and X is F, Cl, Br , and at least one selected from the group consisting of I.
  • Simetallic elements are B, Si, Ge, As, Sb, and Te.
  • Metallic element means all elements contained in Groups 1 to 12 of the periodic table except hydrogen, and B, Si, Ge, As, Sb, Te, C, N, P, O, S, and It is an element contained in all Groups 13 to 16 except Se. In other words, it is a group of elements that can become cations when a halogen compound and an inorganic compound are formed.
  • M may contain Y, and X may contain Cl and Br.
  • halide solid electrolytes include Li 3 (Ca, Y, Gd) X 6 , Li 2 MgX 4 , Li 2 FeX 4 , Li (Al, Ga, In) X 4 , Li 3 (Al, Ga, In ) X 6 , LiI, etc. may be used.
  • the element X is at least one selected from the group consisting of F, Cl, Br and I.
  • this notation indicates at least one element selected from the parenthesized element group. That is, "(Al, Ga, In)” is synonymous with "at least one selected from the group consisting of Al, Ga and In". The same is true for other elements.
  • halide solid electrolyte is the compound represented by LiaMebYcX6 .
  • Me is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • m represents the valence of Me.
  • Simetallic elements are B, Si, Ge, As, Sb, and Te.
  • Metallic element means all elements contained in Groups 1 to 12 of the periodic table (excluding hydrogen), and all elements contained in Groups 13 to 16 of the periodic table (however, B , Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Me is the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb to enhance the ionic conductivity of the halide solid electrolyte material. It may be at least one more selected.
  • the halide solid electrolyte may be Li3YCl6 , Li3YBr6 , or Li3YBrpCl6 - p . Note that p satisfies 0 ⁇ p ⁇ 6.
  • a sulfide solid electrolyte means a solid electrolyte containing sulfur (S).
  • the sulfide solid electrolyte may contain not only sulfur but also halogen elements.
  • Examples of sulfide solid electrolytes include Li 2 SP 2 S 5 , Li 2 S—SiS 2 , Li 2 S—B 2 S 3 , Li 2 S—GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , Alternatively, Li 10 GeP 2 S 12 or the like may be used.
  • oxide solid electrolytes examples include NASICON solid electrolytes typified by LiTi 2 (PO 4 ) 3 and element-substituted products thereof, (LaLi)TiO 3 -based perovskite solid electrolytes, Li 14 ZnGe 4 O 16 , Li LISICON solid electrolytes typified by 4 SiO 4 , LiGeO 4 and elemental substitutions thereof, garnet type solid electrolytes typified by Li 7 La 3 Zr 2 O 12 and elemental substitutions thereof, Li 3 PO 4 and its N substitutions glass or glass-ceramics based on Li—BO compounds such as LiBO 2 and Li 3 BO 3 , with additions of Li 2 SO 4 , Li 2 CO 3 , etc., and the like can be used.
  • NASICON solid electrolytes typified by LiTi 2 (PO 4 ) 3 and element-substituted products thereof
  • (LaLi)TiO 3 -based perovskite solid electrolytes Li 14 ZnG
  • a compound of a polymer compound and a lithium salt can be used.
  • the polymer compound may have an ethylene oxide structure.
  • a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt. Therefore, the ionic conductivity can be further increased.
  • Lithium salts include LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiSO3CF3, LiN(SO2CF3)2 , LiN ( SO2C2F5 ) 2 , LiN ( SO2CF3 ) ( SO2C4F9 ), and LiC ( SO2CF3 ) 3 , etc. may be used.
  • One lithium salt selected from the exemplified lithium salts can be used alone. Alternatively, mixtures of two or more lithium salts selected from the exemplified lithium salts can be used.
  • LiBH 4 --LiI LiBH 4 --P 2 S 5 , etc.
  • LiBH 4 --P 2 S 5 LiBH 4 --P 2 S 5 , etc.
  • the solid electrolyte layer 102 may contain a halide solid electrolyte.
  • Halide solid electrolytes do not contain sulfur.
  • the solid electrolyte layer 102 may consist essentially of a halide solid electrolyte. In this specification, the term “substantially” means that the content of impurities is allowed to be less than 0.1%.
  • the solid electrolyte layer 102 may consist only of a halide solid electrolyte.
  • the ionic conductivity of the solid electrolyte layer 102 can be increased. This can reduce the decrease in the energy density of the battery.
  • the solid electrolyte layer 102 may further contain a binder.
  • a binder the same material as the material that can be used for the active material layer 104 may be used.
  • the solid electrolyte layer 102 may have a thickness of 1 ⁇ m or more and 500 ⁇ m or less. When solid electrolyte layer 102 has a thickness of 1 ⁇ m or more, first electrode 101 and second electrode 103 are less likely to short-circuit. When the solid electrolyte layer 102 has a thickness of 500 ⁇ m or less, the battery can operate at high output.
  • the shape of the solid electrolyte is not particularly limited.
  • its shape may be, for example, acicular, spherical, ellipsoidal, or the like.
  • the shape of the solid electrolyte may be particulate.
  • the median diameter of the solid electrolyte may be 100 ⁇ m or less, or 10 ⁇ m or less.
  • volume diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
  • the solid electrolyte contained in the solid electrolyte layer 102 can be manufactured by the following method.
  • Raw material powder is prepared so that it has the desired composition.
  • Examples of raw powders are oxides, hydroxides, halides or acid halides.
  • the desired composition is Li 3 YBr 4 Cl 2
  • LiBr, YCl, and YBr are mixed in a molar ratio on the order of 3:0.66:0.33.
  • the raw material powders may be mixed in pre-adjusted molar ratios to compensate for possible compositional changes in the synthesis process.
  • the raw material powders are mechanochemically reacted with each other in a mixing device such as a planetary ball mill (that is, using the method of mechanochemical milling) to obtain a reactant.
  • the reactants may be fired in vacuum or in an inert atmosphere.
  • a mixture of raw material powders may be fired in vacuum or in an inert atmosphere to obtain a reactant. Firing is preferably performed at, for example, 100° C. or higher and 300° C. or lower for 1 hour or longer.
  • the raw material powder is desirably fired in a sealed container such as a quartz tube.
  • the solid electrolyte of the solid electrolyte layer 102 is obtained.
  • the second electrode 103 functions as a positive electrode.
  • the second electrode 103 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
  • the material is, for example, a positive electrode active material.
  • the second electrode 103 may have a current collector 105 and an active material layer 106 .
  • Active material layer 106 includes a positive electrode active material.
  • the active material layer 106 is arranged, for example, between the current collector 105 and the solid electrolyte layer 102 .
  • the active material layer 106 may be arranged on the surface of the current collector 105 in direct contact with the current collector 105 .
  • positive electrode active materials examples include lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, or transition metal oxynitrides.
  • lithium-containing transition metal oxides include LiNi1 -xyCoxAlyO2 ( ( x + y ) ⁇ 1), LiNi1 -xyCoxMnyO2 ( ( x + y ) ⁇ 1 ) or LiCoO2, etc.
  • the positive electrode active material may include Li(Ni,Co,Mn) O2 .
  • Materials for the current collector 105 include, for example, metal materials.
  • Metal materials include copper, stainless steel, iron, and aluminum.
  • the second electrode 103 may contain a solid electrolyte.
  • the solid electrolyte the solid electrolyte exemplified as the material forming the solid electrolyte layer 102 may be used.
  • the positive electrode active material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the positive electrode active material and the solid electrolyte can form a good dispersion state. This improves the charge/discharge characteristics of the battery.
  • the positive electrode active material has a median diameter of 100 ⁇ m or less, the lithium diffusion rate is improved. This allows the battery to operate at high output.
  • the positive electrode active material may have a larger median diameter than the solid electrolyte. Thereby, the positive electrode active material and the solid electrolyte can form a good dispersion state.
  • the ratio of the volume of the positive electrode active material to the sum of the volume of the positive electrode active material and the volume of the solid electrolyte is 0.30 or more and 0.95 or less. good too.
  • a coating layer may be formed on the surface of the positive electrode active material in order to prevent the solid electrolyte from reacting with the positive electrode active material. Thereby, an increase in the reaction overvoltage of the battery can be suppressed.
  • coating materials contained in the coating layer are sulfide solid electrolytes, oxide solid electrolytes or halide solid electrolytes.
  • the thickness of the second electrode 103 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the second electrode 103 is 10 ⁇ m or more, a sufficient energy density of the battery can be secured. When the thickness of the second electrode 103 is 500 ⁇ m or less, the battery can operate at high output.
  • the second electrode 103 may contain a conductive material for the purpose of enhancing electronic conductivity.
  • the second electrode 103 may contain a binder.
  • the same materials that can be used for the active material layer 104 may be used as the conductive material and the binder.
  • the second electrode 103 may contain a non-aqueous electrolyte, a gel electrolyte, or an ionic liquid for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery.
  • the non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents are cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • linear carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
  • Examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • Examples of linear ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a linear ester solvent is methyl acetate.
  • Examples of fluorosolvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
  • One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
  • lithium salts are LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiSO3CF3, LiN(SO2CF3)2 , LiN ( SO2C2F5 ) 2 , LiN ( SO2CF3 ). ( SO2C4F9 ) , or LiC ( SO2CF3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • the lithium salt concentration is, for example, in the range of 0.5 mol/liter or more and 2 mol/liter or less.
  • a polymer material impregnated with a non-aqueous electrolyte can be used as the gel electrolyte.
  • examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
  • ionic liquids examples include (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums; or (iii) nitrogen-containing heterogeneous compounds such as pyridiniums or imidazoliums. It is a ring aromatic cation.
  • Examples of anions contained in the ionic liquid are PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SO 3 CF 3 ⁇ , N(SO 2 CF 3 ) 2 ⁇ , N(SO 2 C 2 F 5 ) 2- , N( SO2CF3 ) ( SO2C4F9 ) - , or C ( SO2CF3 ) 3- .
  • the ionic liquid may contain a lithium salt.
  • the configuration example in which the first electrode 101 is the negative electrode and the second electrode 103 is the positive electrode has been described. good too.
  • the active material layer 104 is a positive electrode active material layer. That is, Bi contained in the active material layer 104 functions as a positive electrode active material.
  • the second electrode 103 which is the negative electrode, is made of lithium metal, for example.
  • a battery 1000 has a basic configuration of a first electrode 101, a solid electrolyte layer 102, and a second electrode 103, and is enclosed in a sealed container so as to prevent air and moisture from entering.
  • the shape of the battery 1000 includes a coin shape, a cylindrical shape, a square shape, a sheet shape, a button shape, a flat shape, a laminate shape, and the like.
  • Example 1 ⁇ Production of first electrode>
  • a nickel foil (10 cm ⁇ 10 cm, thickness: 10 ⁇ m) was preliminarily degreased with an organic solvent, masked on one side, and immersed in an acidic solvent for degreasing and activation of the nickel foil surface.
  • a plating bath was prepared by adding bismuth methanesulfonate as a soluble bismuth salt to 1.0 mol/L of methanesulfonic acid so that Bi 3+ ions would be 0.18 mol/L.
  • the activated nickel foil was immersed in the plating bath after being connected to a power source so that current could be applied.
  • Bi was electroplated to a thickness of approximately 5 ⁇ m on the unmasked nickel foil surface.
  • the nickel foil was recovered from the acid bath, removed from the masking, washed with pure water, and dried.
  • the nickel foil electroplated with Bi was heat-treated at 250° C. for 30 minutes in an electric furnace in an argon atmosphere.
  • surface X-ray diffraction measurement was performed on the Bi plating layer on the nickel foil. The X-ray diffraction pattern obtained by this measurement is as shown in FIG. From this X-ray diffraction pattern, it was confirmed that Bi 3 Ni having an orthorhombic crystal structure and belonging to the space group Pnma was produced.
  • a laminate composed of a current collector made of nickel foil and an active material layer containing Bi 3 Ni having a crystal structure belonging to the space group Pnma and arranged in direct contact with the surface of the current collector. was gotten.
  • the first electrode was obtained by punching the obtained laminate into a size of ⁇ 0.92 cm. That is, the first electrode of Example 1 had a structure in which an active material layer containing Bi 3 Ni having a crystal structure belonging to the space group Pnma was provided on a current collector made of nickel foil.
  • An indium-lithium alloy was made by pressing a piece of lithium foil against an indium foil and diffusing the lithium into the indium. A pressure of 360 MPa was applied to this laminate to form a working electrode, a solid electrolyte layer and a counter electrode.
  • the thickness of the first electrode as the working electrode was 6 ⁇ m
  • the thickness of the solid electrolyte layer was 500 ⁇ m
  • the thickness of the counter electrode was 15 ⁇ m.
  • current collectors made of stainless steel were attached to the working electrode and the counter electrode, and current collecting leads were attached to the current collectors.
  • Example 1 a test cell of Example 1 was obtained, in which the first electrode, which was an electrode having an active material layer containing Bi 3 Ni, was used as the working electrode, and the lithium-indium alloy was used as the counter electrode.
  • the test cell produced here is a unipolar test cell using a working electrode and a counter electrode, and is used to test the performance of one of the electrodes in a secondary battery.
  • the working electrode is the electrode under test and the counter electrode is a suitable active material in sufficient quantity to cover the reaction of the working electrode. Since this test cell tests the performance of the first electrode as a negative electrode, a large excess of lithium-indium alloy was used as the counter electrode, as is commonly used.
  • the negative electrode whose performance has been tested using such a test cell is, for example, combined with a positive electrode containing a positive electrode active material, such as a transition metal oxide containing Li, as described in the above-described embodiment. It can be used as a secondary battery.
  • a positive electrode active material such as a transition metal oxide containing Li
  • a charge/discharge test was performed on the prepared test cell under the following conditions. From the weight of electroplated Bi, the theoretical capacity of Bi is set to 384 mAh / g, and the rate is charged to -0.2 V (0.42 V vs Li + / Li) at a constant current value at which the rate is 0.1 IT based on Bi, and then 1.38 V (2.0 V vs Li+/Li) and then charged to -0.2 V (0.42 V vs Li+/Li). A charge/discharge test was performed on the test cells in a constant temperature bath at 25°C. 3 is a graph showing the results of a charge/discharge test of the test cell according to Example 1. FIG. The initial charge capacity was about 352.1 mAh/g. The subsequent discharge capacity and charge capacity were 278.5 mAh/g and 255.7 mAh/g, respectively.
  • FIG. 5 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Example 1.
  • Example 2 ⁇ Preparation of test cell>
  • a solid electrolyte a sulfide solid electrolyte Li6PS5Cl ( manufactured by Ampcera , 80 mg) was used in place of Li3YBr4Cl2 .
  • a test cell of Example 2 was obtained in the same manner as the test cell of Example 1 except for this point.
  • a charge/discharge test was performed on the prepared test cell under the following conditions. Based on the weight of electroplated Bi, the theoretical capacity of Bi is set to 384 mAh / g, and the rate is charged to -0.42 V (0.2 V vs Li + / Li) at a constant current value at which the rate is 0.1 IT based on Bi, and then 1.38 V. (2.0 V vs Li+/Li), and then charged to -0.2 V (0.42 V vs Li+/Li).
  • a charge/discharge test was performed on the test cells in a constant temperature bath at 25°C. 6 is a graph showing the results of a charge/discharge test of the test cell according to Example 2.
  • FIG. The initial charge capacity was about 340.8 mAh/g.
  • the subsequent discharge capacity and charge capacity were 269.9 mAh/g and 245.1 mAh/g.
  • FIG. 7 is a graph showing the results of a charge-discharge cycle test of the test cell according to Example 2.
  • FIG. 8 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Example 2. FIG. From FIG. 8, it can be seen that the discharge capacity of 80% or more of the initial discharge capacity is maintained even after 100 cycles.
  • ⁇ Preparation of test cell> A first electrode was used as the working electrode. Li metal with a thickness of 0.34 ⁇ m was used as the counter electrode. The Li metal was double coated with a microporous separator (Celgard 3401, Asahi Kasei Celgard). As an electrolytic solution, a solution was prepared by dissolving LiPF 6 in vinylene carbonate (VC) at a concentration of 1.0 mol/L. Thus, a test cell of Reference Example 1 was obtained.
  • VC vinylene carbonate
  • a charge/discharge test was performed on the prepared test cell under the following conditions. Based on the weight of the electroplated Bi, the theoretical capacity of Bi is 384 mAh / g, the rate is 0.1 IT based on Bi, and the constant current value is 0.12 mA. A charge/discharge cycle test was performed by repeating up to 100 cycles as one cycle. A charge/discharge test was performed on the test cells in a constant temperature bath at 25°C. 9 is a graph showing the results of a charge/discharge test of a test cell according to Reference Example 1. FIG. 10 is a graph showing the results of a charge-discharge cycle test of the test cell according to Reference Example 1. FIG. FIG. FIG.
  • FIG. 11 is a graph showing the discharge capacity maintenance rate in each charge/discharge cycle with respect to the initial discharge capacity of the test cell according to Reference Example 1.
  • FIG. 11 in the battery according to Reference Example 1, the discharge capacity decreased to 5% or less of the initial discharge capacity after about 100 cycles. This is because when the active material layer containing Bi 3 Ni repeatedly expands and contracts due to repeated charging and discharging, the non-aqueous electrolyte enters into cavities generated in the active material layer containing Bi 3 Ni, thereby This is probably because the electron conduction paths in the active material layer are reduced due to the destruction of the structure of the active material layer.
  • the battery of the present disclosure can be used, for example, as an all-solid lithium secondary battery.

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WO2023145426A1 (ja) * 2022-01-25 2023-08-03 パナソニックＩｐマネジメント株式会社 電池および電極の製造方法

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JPH10241670A (ja) * 1997-02-25 1998-09-11 Sanyo Electric Co Ltd 非水電解質二次電池用電極及びその製造方法
JP2000030703A (ja) * 1997-06-03 2000-01-28 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極材料とそれら負極材料を用いた非水電解質二次電池
WO2000041259A1 (fr) * 1999-01-04 2000-07-13 Toyo Kohan Co., Ltd. Accumulateur alcalin et noyau associe
JP2019164961A (ja) * 2018-03-20 2019-09-26 株式会社Ｇｓユアサ 合金、負極活物質、負極及び非水電解質蓄電素子

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Publication number Priority date Publication date Assignee Title
JPH10241670A (ja) * 1997-02-25 1998-09-11 Sanyo Electric Co Ltd 非水電解質二次電池用電極及びその製造方法
JP2000030703A (ja) * 1997-06-03 2000-01-28 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極材料とそれら負極材料を用いた非水電解質二次電池
WO2000041259A1 (fr) * 1999-01-04 2000-07-13 Toyo Kohan Co., Ltd. Accumulateur alcalin et noyau associe
JP2019164961A (ja) * 2018-03-20 2019-09-26 株式会社Ｇｓユアサ 合金、負極活物質、負極及び非水電解質蓄電素子

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Publication number Priority date Publication date Assignee Title
WO2023145426A1 (ja) * 2022-01-25 2023-08-03 パナソニックＩｐマネジメント株式会社 電池および電極の製造方法

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