WO2020175555A1 - Batterie au lithium-soufre et procédé de production de batterie au lithium-soufre - Google Patents

Batterie au lithium-soufre et procédé de production de batterie au lithium-soufre Download PDF

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Publication number
WO2020175555A1
WO2020175555A1 PCT/JP2020/007760 JP2020007760W WO2020175555A1 WO 2020175555 A1 WO2020175555 A1 WO 2020175555A1 JP 2020007760 W JP2020007760 W JP 2020007760W WO 2020175555 A1 WO2020175555 A1 WO 2020175555A1
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Prior art keywords
positive electrode
lithium
sulfur
battery
electrolyte
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PCT/JP2020/007760
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English (en)
Japanese (ja)
Inventor
渡邉　正義
彩 猿渡
亮多 玉手
和英 上野
獨古　薫
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国立大学法人 横浜国立大学
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Priority to JP2021502318A priority Critical patent/JP7485873B2/ja
Publication of WO2020175555A1 publication Critical patent/WO2020175555A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium-sulfur battery including a positive electrode containing a sulfur-based positive electrode active material, and a method for manufacturing a lithium-sulfur battery including a positive electrode including a sulfur-based positive electrode active material.
  • Lithium-ion secondary batteries are widely used as secondary batteries.
  • a lithium-sulfur battery is drawing attention as a secondary battery having a higher capacity than that of a lithium-ion battery.
  • the theoretical capacity of a lithium-sulfur battery having a sulfur-based positive electrode active material is 1672 mAh/g, and the theoretical capacity of a lithium-ion battery having LiC ⁇ 2 as a positive electrode active material. Very large with a capacity of 1 times 37 mA h/g. In addition, sulfur is low cost and rich in resources.
  • Japanese Patent Laid-Open No. 201 4-4 1 81 1 discloses that a solvated ionic liquid (S L: Solvate Ionic. Liquid) in which an ether compound and a lithium ion form a complex is a fluorine-based compound.
  • S L Solvate Ionic. Liquid
  • a lithium-sulfur secondary battery having an electrolyte solution to which a solvent is added is disclosed.
  • the solvated ionic liquid has a low solubility of lithium polysulfide and a small decrease in charge/discharge capacity and charge/discharge efficiency in the cycle test.
  • the ionic conductivity of the electrolytic solution is improved by adding a fluorine-based solvent that is an auxiliary solvent to the solvated ionic liquid.
  • US Pat. No. 96 1 4252 Japanese Unexamined Patent Publication No. 2016-1221657 discloses that a high-concentration electrolytic solution containing 3 mol or less of a non-aqueous solvent with respect to 1 mol of a lithium salt.
  • a lithium battery including is disclosed.
  • non-protonic organic solvents which are generally used for lithium secondary batteries, such as dimethyethane, acetonitrile, tetrahydrofuran, dimethylsulfoxide, ptyrolactone, and sulfolane, are listed.
  • Patent Document 1 Japanese Patent Laid-Open No. 20 1 4 _ 4 1 8 11
  • Patent Document 2 JP 2 0 1 6-1 2 2 6 5 7
  • Patent Document 3 International Publication No. 2 0 1 3/0 9 6 7 5 1 Summary of Invention
  • An embodiment of the present invention aims to provide a lithium-sulfur battery that is easy to manufacture and has a high capacity and energy density, and a method of easily manufacturing a lithium-sulfur battery that has a high capacity and energy density.
  • the lithium-sulfur secondary battery of the embodiment is a composite positive electrode having a sulfur-based positive electrode active material, carbon particles, a positive electrode electrolyte solution containing a lithium salt and a positive electrode solvent, and a negative electrode having a negative electrode active material. And a spacer provided between the composite positive electrode and the negative electrode, the spacer having a battery electrolyte solution containing a lithium salt and a battery solvent, and 3 mass of sulfur contained in the composite positive electrode. Included in the composite positive electrode ⁇ 2020/175 555 3 (:171? 2020 /007760
  • a method for manufacturing a lithium-sulfur secondary battery includes a positive electrode active material containing a sulfur-based positive electrode active material, carbon particles, a lithium salt and a positive electrode solvent, a dispersion solvent, and a polymer.
  • the embodiments of the present invention it is possible to provide a lithium-sulfur battery that is easy to manufacture and has a high capacity and energy density, and an easy manufacturing method of a lithium-sulfur battery that has a high capacity and energy density. ..
  • Fig. 1 is a cross-sectional view showing a configuration of a lithium-sulfur battery of a first embodiment.
  • FIG. 2 A diagram showing discharge characteristics of the lithium-sulfur battery of the first embodiment.
  • FIG. 3 Lithium-sulfur battery It is a figure which shows the relationship between and energy density.
  • FIG. 4 A diagram showing tensile properties of a sheet.
  • FIG. 5 is a diagram showing charge/discharge characteristics of a lithium-sulfur battery of Modification 1 of the first embodiment.
  • FIG. 6 is a diagram showing charge/discharge characteristics of a lithium-sulfur battery of Modification 2 of the first embodiment.
  • FIG. 7 is a diagram showing charge/discharge characteristics of a lithium-sulfur battery of Modification 3 of the first embodiment.
  • FIG. 8 is a diagram showing charge/discharge characteristics of the lithium-sulfur battery of the second embodiment.
  • FIG. 9 A diagram showing charge/discharge characteristics of a lithium-sulfur battery according to a modification of the second embodiment.
  • FIG. 10 is a diagram showing discharge characteristics of the lithium-sulfur battery of the third embodiment. ⁇ 2020/175 555 4 (:171? 2020/007760
  • FIG. 11 is a diagram showing charge/discharge characteristics of the lithium-sulfur battery of the fourth embodiment.
  • FIG. 12 is a diagram showing cycle characteristics of the lithium-sulfur battery of the fourth embodiment.
  • FIG. 13 is a diagram showing charge/discharge characteristics of the lithium-sulfur battery of the fifth embodiment.
  • the lithium-sulfur battery (hereinafter, also referred to as “battery”) 10 of the present embodiment is a spacer including a composite positive electrode 11, a negative electrode (anode) 12 and a battery electrolyte solution 14. 1 3 and are provided.
  • a composite positive electrode 11 and a negative electrode 12 are stacked in a coin cell case 15 with a spacer 13 interposed therebetween.
  • a spring 16 is arranged on the negative electrode 12, and a coin cell case 15 is sealed with a lid 17.
  • a gasket 18 is provided on the side wall of the coin cell case 15.
  • composite positive electrode 1 1 has a elemental sulfur is a sulfur-based positive electrode active material (3 8), a force over carbon nanotubes are carbon particles (Rei_1 ⁇ 1 chome), a polymer, a positive electrode electrolyte 1 9 , With.
  • the composite positive electrode 11 containing the polymer is a self-supporting positive electrode sheet. "Free-standing” means that it can be handled as a separate sheet without the aid of a substrate or carrier. That is, “independence” has the same meaning as “self-support”.
  • the positive electrode electrolytic solution 19 is [!_ ⁇ (3 !_) 2 ] [Die 38] containing a lithium salt and a positive electrode solvent. That is, the lithium salt is lithium bis(trifluoromethanesulfonyl)amide (!_ ⁇ [Ding 38]), and the positive electrode solvent is sulfolane (3 !_).
  • the polymer is ⁇ -1 to 1 which is a copolymer of vinylidene fluoride ( ⁇ ) and hexafluoropropylene (1 to 1?).
  • Composite positive electrode 1 Is. Also included in composite positive electrode 11 ⁇ 2020/175 555 5 (: 171-1? 2020 /007760
  • the ratio of the volumetric capacity of the positive electrode electrolyte 19 contained in the composite positive electrode 11 to the mass of sulfur 3 is 3/3. . 9 1 1-/ ⁇ 19, extremely small. This is because, as described later, the composite positive electrode 11 is produced by forming a sheet of the kneaded positive electrode slurry.
  • the negative electrode 12 is metallic lithium that is a negative electrode active material that absorbs and desorbs lithium.
  • the spacer 13 is a separator having a function of absorbing and retaining the battery electrolyte solution 14, and is a glass filter having a thickness of 200 (manufactured by Toyo Roshi Kaisha, Ltd.: 0881-55).
  • the battery electrolyte 14 contained in the spacer 13 is the same as the cathode electrolyte 19 [I-(3
  • 1 to 1 is 1 to 1 2 0 2 0 1 to 1 2 0 1 0 1 0 2 0 2 1 to 1 (1, 1,2, 2 -tetrafluoroethyl (2, 2, 3, 3-tetrafluoropropyl)ether) (manufactured by Daikin Industries Co., Ltd.).
  • the molar ratio of the composition of the battery electrolyte is ([!- ⁇ (31_) 2 ][ D3 8]
  • Figure 2 shows the discharge characteristics of battery 10 (30 ° ⁇ : 13 cycles).
  • the current density is ⁇ /100 rate.
  • ⁇ / 1 00 rate corresponds to the current density per unit area 40 eight / ⁇ second electrode.
  • the discharge capacity of the battery 10 was 1 500 8 (1/9-3 or more. Further, the energy density was 1 76 ⁇ //1 ⁇ 9.
  • FIG. 3 shows an example of the relationship between the value of the value of the value of the value of the value of the value of /3 (1-/ 9 ) and the energy density.
  • the value of Mami/3 is preferably 71-/ ⁇ 19 or less, and particularly preferably 5/9 or less. If the value of Mami/3 is equal to or less than the upper limit, the energy density can be increased.
  • the amount of sulfur in the composite positive electrode 11 is ⁇ 2020/175 555 6 ⁇ (:171? 2020 /007760
  • the upper limit of the amount of sulfur in the composite positive electrode 11 is set to, for example, 30% in order to ensure electron conductivity and ionic conductivity. Is 2 .
  • the sulfur content of the composite positive electrode 11 is at least the lower limit of the above range, the energy density can be increased.
  • the manufacturing method of the battery 10 is as follows: a positive electrode slurry manufacturing process (step 310), a positive electrode sheet manufacturing process (step 320), a laminated sheet manufacturing process (step 330), and an assembly process (step 3 40).
  • elemental sulfur 3 8 is a sulfur-based positive electrode active material, and force over carbon nanotube, a polymer one, the positive electrode electrolyte 1 9 containing a lithium salt and a positive electrode solvent, a dispersion solvent, a positive electrode slurry containing is produced.
  • the sulfur-based positive electrode active material is not limited to elemental sulfur, but a sulfur-based positive electrode containing at least one selected from the group consisting of metal sulfides, metal polysulfides, and organic sulfur compounds. It only needs to have an active material.
  • the metal sulfide include lithium sulfide and lithium polysulfide.
  • the organic sulfur compounds include organic disulphide compounds and carbon sulfide compounds. You may mix and use a different kind of positive electrode active material.
  • the sulfur-based positive electrode active material is at least one of elemental sulfur, lithium polysulfide, and lithium sulfide.
  • Force-bon nanotubes have a diameter of 1 Length ⁇ ⁇ ! ⁇ 600
  • multi-walled carbon nanotubes with diameters of 10 nm to 100 001 and lengths of 0.4 111 to 15
  • ⁇ 1 ⁇ 1 is a bundle structure in which many tubes are intertwined. However, as described below, the solvated ionic liquid cathode electrolyte 19
  • the force-bon nanotubes preferably have an aspect ratio of 500 or more.
  • a value of 0 0 0 or higher is particularly preferable. If it is at least the lower limit of the above range, the electron conductivity can be ensured even if the composite positive electrode becomes thick.
  • the upper limit of the aspect ratio is, for example, 2,000 because manufacturing is difficult.
  • the polymer is ⁇ -!? , Vinylidene fluoride (V 0 ), which is a homopolymer ⁇ , poly 1 ⁇ 1 _ isopropyl acrylate, poly (styrene-methyl methacrylate-styrene) triblock copolymer, poly (styrene-butyl acrylate) -Styrene) triblock copolymer, poly(styrene-ethylene oxide-styrene) triblock copolymer, and/or polyvinylpyrrolidone.
  • V 0 Vinylidene fluoride
  • the polymer content of the composite positive electrode is preferably 5% by mass or more and 30% by mass or less, and particularly preferably 8% by mass or more and 20% by mass or less. If it is at least the lower limit of the above range, sheeting is easy. If it is at most the upper limit of the above range, the energy density will not decrease.
  • lithium salt (1_ ⁇ 4 ), (1_ ⁇ [3 8]: lithium bis(fluorosulfonyl) amide), or (1- ⁇ ⁇ ⁇ ⁇ 4 ) may be used.
  • the positive electrode solvent it is preferable to use a sulfonyl group-containing compound in which the viscosity increases exponentially even if the concentration is increased, but the ion conductivity decreases only in a linear function (straight line). it can.
  • the positive electrode solvent is preferably at least one of sulfolane (3!_), 3-methylsulfolane, ethylmethylsulfone (Mimi 1 ⁇ /13), and ethylisopropyl sulfone.
  • the amount of the positive electrode solvent relative to 1 mol of the lithium salt is preferably 1.3 mol or more and 5 mol or less.
  • the dispersion solvent is methyl isoptyl ketone (IV!: 4-methyl-2-pentanone).
  • the 10% weight reduction temperature of [!_ ⁇ (3 !_) 2 ] [Ding 3 8], which is the positive electrode electrolyte 19 is about 220 ° ⁇ , while!
  • the 10% weight loss temperature of ⁇ /1 is ⁇ 2020/175 555 8 ⁇ (:171? 2020 /007760
  • the 10% weight loss temperature is the temperature at which the weight decreases by 10% when the temperature is raised from room temperature at a heating rate of 10 ° ⁇ /min in a nitrogen atmosphere and atmospheric pressure.
  • the dispersion solvent it is preferable to select an organic solvent having a 10% weight loss temperature lower than that of the positive electrode electrolyte 19 by 180 ° C or more because it can be easily removed by evaporation.
  • Acetone, methyl ethyl ketone, tetrahydrofuran, 1 ⁇ 1-methylpyrrolidone, or the like can also be used as the dispersion solvent.
  • the dispersion solvent contained in the positive electrode slurry is preferably 100% by mass or more and 100% by mass or less with respect to the composite positive electrode, and 200% by mass or more and 500% by mass or more. % Or less is particularly preferable. If it is at least the lower limit of the above range, the slurry will have good coating properties, and if it is at most the upper limit of the above range, non-uniformity after coating can be prevented.
  • the bundle structure is reduced by being kneaded with the positive electrode electrolyte solution 19 and then diluted with the dispersion solvent.
  • the positive electrode slurry is subjected to a mechanical dispersion step in a state where it contains the positive electrode electrolyte solution 19 and a dispersion solvent.
  • the positive electrode slurry preparation step 310 composite particles containing a sulfur-based positive electrode active material and carbon nanotubes are prepared, and the positive electrode electrolyte is added to the composite particles and kneaded. After that, the dispersion solvent is preferably added. ⁇ 2020/175 555 9 boxes (:171? 2020 /007760
  • kneading does not simply mean “mixing”, but an operation (1 ⁇ 6301) of kneading the composite particles together with the positive electrode electrolyte.
  • the polymer may be added after kneading with the dispersion solvent, or may be added and kneaded with the positive electrode electrolyte solution.
  • a positive electrode sheet is produced by evaporating the dispersion solvent of the positive electrode slurry.
  • a vacuum drying method may be used to evaporate the dispersion solvent in a short time.
  • the dispersion solvent evaporates. can get.
  • the thickness of the positive electrode sheet is 50 to 100.
  • the dispersion solvent is ⁇ -1 to 1? 400 mass% was added to the composite positive electrode containing.
  • Fig. 4 shows, as a reference, the tensile properties of a positive electrode sheet containing an ionic liquid described below as a solvent and containing no sulfur.
  • sample width 500 1 01.
  • the mass ratio of the positive electrode sheet is ( ⁇ 1 ⁇ 1 pcs: [!_ ⁇ (0 4 )] [Ds 3 8]:
  • the sheet is easy to handle when the breaking elongation is 5% or more.
  • a sheet with a breaking elongation of 100% or more and 200% or less rarely breaks or stretches greatly even if wound, so for example, wind it in a roll shape. It is also possible and easy to handle.
  • the force-carbon nanotube is preferably 1% by mass or more and 30% by mass or less of the composite positive electrode, and particularly preferably 5% by mass or more and 20% by mass or less.
  • the electron conductivity is secured, and if it is at most the upper limit of the above range, the breaking elongation is large.
  • the tensile properties of the positive electrode sheet containing sulfur and the tensile properties of the positive electrode sheet prepared in step 320 were substantially the same as those of the positive electrode sheet containing no sulfur shown in FIG. ..
  • a laminated sheet is produced by laminating a positive electrode sheet, a spacer sheet containing a battery electrolyte solution, and a negative electrode sheet containing a negative electrode active material.
  • the spacer sheet is a glass filter that is a separator.
  • a battery electrolyte is added to the spacer sheet.
  • the battery electrolytic solution is substantially the same as the positive electrode electrolytic solution 19, but it is preferable that the diluent solvent 1 to 1 is added.
  • the separator may be a porous sheet or non-woven fabric made of glass fiber, ceramic or polymer that absorbs and holds the battery electrolyte.
  • the porous sheet is made of, for example, a microporous polymer or the like.
  • the polymer that constitutes such a porous sheet include polyolefins such as polyethylene (Mitsumi) and polypropylene (); laminates having a three-layer structure of 9/9o/9, polyimido, and aramid. ..
  • the polyolefin microporous separator and the glass fiber separator are preferable because they have the property of being chemically stable with respect to the organic solvent and can suppress the reactivity with the electrolytic solution to a low level.
  • the thickness of the separator is not limited, but in the secondary battery for automobile, it is preferable that the thickness of the separator is a single layer or a multilayer and the total thickness is 41 to 60. Further, the separator preferably has a pore diameter of 10 or less (for example, 1 O nm to 1 O O nm) and a porosity of 20% to 95%.
  • a fluorinated solvent is preferable.
  • Examples include rofluoroethers (1 to 1), perfluoropolyethers (M), or hydrofluoropolyethers (1 to 1?M), and preferred are hydrofluorocarbons (1 to 10) or high. Drofluoroether (1 to 1°), more preferably hydrofluoroether (1 to 1°).
  • the dilution solvent is preferably 0.3 mol or more and 10 mol or less, and particularly preferably 0.5 mol or more and 5 mol or less, relative to 1 mol of the lithium salt. If it is at least the lower limit of the above range, sufficient viscosity reduction occurs, and if it is at most the upper limit of the above range, a sufficient lithium ion concentration can be secured.
  • the negative electrode 12 is a lithium metal sheet having a thickness of 200.
  • the negative electrode 12 may include a negative electrode active material that absorbs and desorbs lithium ions.
  • the negative electrode active material a conventionally known negative electrode material such as a metal material or a carbon material can be used.
  • the metal material includes lithium titanate, lithium metal, sodium metal, lithium aluminum alloy, lithium tin alloy, lithium silicon alloy, sodium silicon alloy, lithium antimony alloy and the like.
  • Carbon materials include natural graphite, artificial graphite, carbon black, acetylene black, graphite, graphene, activated carbon, carbon fiber, coke, soft carbon, hard carbon, etc., which may be crystalline or amorphous.
  • a carbon material, lithium, or a lithium-transition metal composite oxide is preferable because it can form a battery having excellent capacity and input/output characteristics.
  • a laminated sheet is sealed in a coin cell case 15 (3 II 3304, thickness 3.2 ⁇ ⁇ ) of 2 032 type, and a spring is placed on the negative electrode 12 2. 16 was placed, and the coin cell case 15 was sealed from the top of the spring 16 with the lid 17.
  • the composite positive electrode 11 is an electrolyte-containing positive electrode that already contains the electrolyte solution (positive electrode electrolyte solution 19) before being laminated with the spacer containing the electrolyte solution.
  • the electrolyte solution positive electrode electrolyte solution 19
  • the composite positive electrode 11 contains 1 ⁇ 1, a positive electrode electrolyte solution 19, a positive electrode active material and a polymer.
  • the concentration of the lithium salt in the positive electrode electrolyte solution 19 is higher than the concentration of the lithium salt in the battery electrolyte solution containing the diluting solvent.
  • a laminated sheet can be produced by laminating a self-supporting positive electrode sheet, a spacer, and a negative electrode sheet, and therefore the production is easy.
  • the lithium-sulfur battery 108, etc. of the modified example of the first embodiment is similar to the lithium-sulfur battery 10 and has the same effect. Therefore, constituent elements having the same function are designated by the same reference numerals, and a description thereof will be omitted. Omit it.
  • Fig. 5 shows the discharge characteristics of the battery 108 (30° ⁇ .
  • the current density is ⁇ /50%.
  • the ⁇ /50 rate is 120 8/per unit area of the electrode.
  • the volumetric capacity of the positive electrode electrolyte solution 19 contained in 18 is 9/3, which is 7 1-/19.
  • Fig. 6 shows the discharge characteristics of the battery 108-1 (30° ⁇ .
  • the current density is 0/20 rate.
  • the discharge capacity (second cycle) of the battery 108-1 is 10000 ⁇ . It was 1/8 11/9_3.
  • the composite positive electrode 1 1 18 2 of the battery 10 8 2 of this modified example has not only carbon nanotubes as carbon particles but also Ketjen black ( ⁇ M) which is a porous graphite.
  • the sulfur content of the composite positive electrode 1 1 8 2 is 1 1 1 019/001 2 .
  • the volumetric capacity of the positive electrode electrolyte 19 contained in the composite positive electrode 1 18 2 with respect to the mass 3 of sulfur contained in the composite positive electrode 1 1 18 2 is £/3. Is.
  • ⁇ Mitsu has a better dispersibility than that of 0 1 ⁇ 1, so that a composite positive electrode 1 1 18 2 containing only a small amount of the positive electrode electrolyte 19 can be prepared.
  • the lower limit is, for example, 0. 1 1-/9 due to technical problems, and the upper limit is energy density guarantee. Is.
  • Fig. 7 shows the discharge characteristics (30° ⁇ ) of the battery 108. 2
  • the current density is 0/48 rate.
  • the discharge capacity of the battery 1082 is 10 I II cycle, It was 1 1 00 0 18 11/9-3.
  • the positive electrode sheet that does not include 1 ⁇ 1 unit is self-supporting because it contains a polymer, but has a low breaking strength. For this reason, it is preferable that 1% of the composite positive electrode 1 1 8 2 is contained in an amount of 1% by mass or more. However, even if the positive electrode sheet contains a small amount of 0,1%, or even if the positive electrode sheet does not contain 0,1%, for example, a positive electrode sheet is prepared using a holding sheet made of aluminum as a substrate. Prevents breakage of the positive electrode sheet by peeling the holding sheet after stacking with the spacer sheet ⁇ 2020/175 555 14 ⁇ (:171? 2020 /007760
  • the lithium-sulfur battery 10 according to the second embodiment is similar to the lithium-sulfur battery 10, the components having the same functions are designated by the same reference numerals and the description thereof will be omitted.
  • the battery 10m differs from the battery 108 only in the spacer 13m. Mass ratio of the composition of the composite positive electrode of the battery 1 0 1 0 1 battery ( ⁇ 1 ⁇ 1 pcs: [!_ ⁇ (3 !_) 2 ] [D 3 8
  • Spacer 13 of battery 10 is a sheet (electrolyte sheet) made of polymer gel electrolyte containing battery electrolyte.
  • a spacer slurry is prepared by mixing the positive electrode electrolyte solution 19 [!_ ⁇ (3 !_) 2 ] [Ding 38] and acetone, which is a dispersion solvent. Spacer 13 was made by coating the spacer slurry and then evaporating the acetone. A vacuum drying method may be used to evaporate the acetone in a short time. Tetrahydrofuran, 1 ⁇ 1-methylpyrrolidone, or the like can also be used as the dispersion solvent.
  • the mass ratio ([!_ ⁇ (31_) 2 ] [Ding 38]: ⁇ -1 to 1?) of the composition of spacers 13 and 13 of thickness 86 is (80: 20).
  • the battery electrolyte is not diluted with a fluorine solvent.
  • the positive electrode sheet and the electrolyte sheet may be produced by continuously coating the current collector with the positive electrode slurry and the spacer slurry.
  • Fig. 8 shows the discharge characteristics of battery 10 (30° ⁇ . Current density is ⁇ /20 layers. ⁇ /20 rate is 76 8/ ⁇ per unit area of electrode. Corresponding to the current density of.
  • the lithium-sulfur battery 10M 1 of the modified example of the second embodiment is similar to the lithium-sulfur battery 10M and has the same effect, so that the components having the same functions are designated by the same reference numerals. The description is omitted.
  • the composite positive electrode 1 1 _ 1 of the battery 10_ 1 of the present modification is the same as the composite positive electrode 1 1 8 2. Also, the spacer is the same as the spacer 13 of the battery 10.
  • Fig. 9 shows the discharge characteristics (30° ⁇ of Battery 10M 1).
  • the current density is 0/48 rate.
  • the discharge capacity of Battery 10M 1 is 41:11 cycles, Eight 1"!/9—3 or more.
  • the lithium-sulfur battery 100 according to the third embodiment is similar to the lithium-sulfur battery 10, the components having the same functions are designated by the same reference numerals and the description thereof will be omitted.
  • the composite positive electrode 1100 of the battery 100 does not contain a polymer.
  • the spacer 13 (3 is a separator made of a porous metal containing a battery electrolyte, a porous ceramic or a porous resin.
  • the composite positive electrode 11 (3 of the battery 10 (3 is manufactured by a method similar to that of the composite positive electrode 11 of the battery 10. However, the composite positive electrode 1 1 1 0 containing no polymer is self-supporting. Therefore, the positive electrode slurry was coated on a foamed aluminum foil, which was a current collector, and the mass ratio of the composition of the composite positive electrode 1 10 (0: :[!_ I (3! _) 2 ] [Ding 3 8] :3 8 ) is (15: 63: 22) The sulfur content of the composite positive electrode 1 10 is 9. 9 9/001 2 . Is ...! .8 1-/ ⁇ 19, and the energy density of battery 100 is
  • the battery electrolyte is diluted by the addition of 1 to 1 mil.
  • the composition of the battery electrolyte is (( [1_ ⁇ (31_) 2 ] [Ding 38]) +41 ⁇ 1 ⁇ ).
  • Fig. 10 shows the discharge characteristics of the battery 100 (30°).
  • the current density is 0/16.
  • ⁇ / 1 65 rate corresponds to 1 00 eight / ⁇ 01 2 of current density per unit area of the electrode.
  • ⁇ 02020/175555 16 ⁇ (: 17 2020/007760
  • the discharge capacity (13 cycles) of the battery 100 is 1 000 8 11/9 _3 or more. Also, the energy density of battery 100 is
  • the lithium-sulfur battery 100 of the fourth embodiment is similar to the lithium-sulfur battery 10 etc., components having the same functions are designated by the same reference numerals, and the description thereof will be omitted.
  • the positive electrode electrolytic solution 190 and the battery electrolytic solution are glyme solvated ionic liquids in which an ether compound and a lithium ion form a complex.
  • tetraglyme (04) which is an ether compound, is a solvated ionic liquid of the lime type that forms a complex with lithium salt 38. !_ ⁇ (04) ][ Ding 3 8] ).
  • the composite positive electrode 11 containing polymer has a total of 4.2/3-/19 for Mimi/3, which is a self-supporting positive electrode sheet.
  • Fig. 11 and Fig. 12 show discharge characteristics (30° ⁇ ) of 10 batteries. Current density is ⁇ /8 rate. ⁇ /8 rate is 1 per unit area of electrode. 70 corresponds to a current density of eight / ⁇ 01 2.
  • Battery 100 had a discharge capacity of 730.1818/11/ 9 and a coulombic efficiency of 98.4% even after 90 cycles.
  • ether compound constituting the glyme-based solvated ionic liquid monoglyme, diglyme, triglyme, tetraglyme, methyl monoglyme, ethyl monoglyme, ethyl diglyme or pentyl diglyme may be used. ⁇ 2020/175 555 17 ⁇ (:171? 2020/007760
  • Glyme solvated ionic liquids are particularly preferable as the positive electrode solvent and the battery solvent, because they are excellent in dispersibility of 0 1 ⁇ 1.
  • the lithium-sulfur battery 10M of the fifth embodiment is similar to the lithium-sulfur battery 10M, the components having the same functions are designated by the same reference numerals and description thereof will be omitted.
  • Battery 10M differs from battery 100 only in that spacer 13M is an electrolyte sheet.
  • spacer 13M is an electrolyte sheet.
  • the composite positive electrode 11 11 of battery 10 0 is the same as the composite positive electrode 11 10 of battery 100.
  • FIG. 3 the battery 1 0 Snake discharge characteristics (30 ° ⁇ shown. Cell 1 0 only discharge capacity is 600 eight / 9 or more even after 3 cycles.
  • the batteries 10 and 108 to 10 are not limited to the coin type, and may have various known structures such as a wound type and a laminated type. Further, the battery 10 or the like may have a plurality of unit cells (positive electrode/electrolyte/negative electrode), or may have a plurality of units composed of a plurality of unit cells.

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Abstract

L'invention concerne une batterie au lithium-soufre 10 comportant : une électrode positive composite 11 qui contient du soufre, des particules de carbone et un électrolyte d'électrode positive 19 comprenant un sel de lithium et un solvant d'électrode positive ; une électrode négative 12 qui contient un matériau actif d'électrode négative ; et un espaceur 13 qui est disposé entre l'électrode positive composite 11 et l'électrode négative 12, et contient un électrolyte de batterie 14 comprenant un sel de lithium et un solvant de batterie. Le rapport E/S du volume E de l'électrolyte d'électrode positive 19 contenu dans l'électrode positive composite 11 à la masse S de soufre contenu dans l'électrode positive composite 11 est inférieur ou égal à 7 μL/mg.
PCT/JP2020/007760 2019-02-27 2020-02-26 Batterie au lithium-soufre et procédé de production de batterie au lithium-soufre WO2020175555A1 (fr)

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CN113131001A (zh) * 2021-04-21 2021-07-16 郑州航空工业管理学院 一种结构可调的溶剂化离子液体电解液及其制备方法、锂硫电池
WO2023074213A1 (fr) * 2021-10-29 2023-05-04 株式会社Abri Électrode positive pour batteries au lithium-soufre et batterie au lithium-soufre

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JP2014041811A (ja) * 2012-03-19 2014-03-06 Yokohama National Univ アルカリ金属−硫黄系二次電池
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JP2017168435A (ja) * 2016-03-11 2017-09-21 東京電力ホールディングス株式会社 固体電池用正極材およびその製造方法、ならびに、固体電池用正極材を用いた全固体リチウム硫黄電池およびその製造方法
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JP2012109223A (ja) * 2010-10-29 2012-06-07 Yokohama National Univ アルカリ金属−硫黄系二次電池
JP2015506899A (ja) * 2011-12-22 2015-03-05 ボード・オブ・リージエンツ，ザ・ユニバーシテイ・オブ・テキサス・システム 再充電可能リチウム−硫黄電池のための結合剤を含まない硫黄−カーボンナノチューブ複合体カソードおよびその作製方法
JP2014041811A (ja) * 2012-03-19 2014-03-06 Yokohama National Univ アルカリ金属−硫黄系二次電池
JP2016122657A (ja) * 2012-03-26 2016-07-07 国立大学法人 東京大学 リチウム二次電池用電解液、及び当該電解液を含む二次電池
JP2017168435A (ja) * 2016-03-11 2017-09-21 東京電力ホールディングス株式会社 固体電池用正極材およびその製造方法、ならびに、固体電池用正極材を用いた全固体リチウム硫黄電池およびその製造方法
WO2019049826A1 (fr) * 2017-09-07 2019-03-14 国立大学法人 横浜国立大学 Batterie au lithium-soufre

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113131001A (zh) * 2021-04-21 2021-07-16 郑州航空工业管理学院 一种结构可调的溶剂化离子液体电解液及其制备方法、锂硫电池
WO2023074213A1 (fr) * 2021-10-29 2023-05-04 株式会社Abri Électrode positive pour batteries au lithium-soufre et batterie au lithium-soufre

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