WO2015072577A1 - Batterie sodium-ion - Google Patents

Batterie sodium-ion Download PDF

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Publication number
WO2015072577A1
WO2015072577A1 PCT/JP2014/080564 JP2014080564W WO2015072577A1 WO 2015072577 A1 WO2015072577 A1 WO 2015072577A1 JP 2014080564 W JP2014080564 W JP 2014080564W WO 2015072577 A1 WO2015072577 A1 WO 2015072577A1
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WIPO (PCT)
Prior art keywords
sodium
aqueous electrolyte
secondary battery
positive electrode
aqueous
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PCT/JP2014/080564
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English (en)
Japanese (ja)
Inventor
淳一 影浦
山口　滝太郎
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住友化学株式会社
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Priority to JP2015547819A priority Critical patent/JP6420252B2/ja
Publication of WO2015072577A1 publication Critical patent/WO2015072577A1/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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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 invention relates to a sodium secondary battery.
  • a sodium secondary battery using a non-aqueous electrolyte is suitable as a battery having a high energy density because it can generate a higher voltage than a battery of an aqueous electrolyte. Moreover, since sodium is an abundant and inexpensive material, it is expected that large-scale power can be supplied in large quantities by putting it into practical use.
  • a sodium secondary battery usually includes at least a pair of electrodes, a positive electrode including a positive electrode active material capable of doping and dedoping sodium ions, and a negative electrode including a negative electrode active material capable of doping and dedoping sodium ions. And an electrolyte.
  • Non-aqueous electrolyte is mentioned as an electrolyte used for a sodium secondary battery.
  • a non-aqueous electrolyte a sodium secondary battery using a non-aqueous electrolyte in which an electrolyte salt composed of sodium hexafluorophosphate is dissolved in a non-aqueous solvent composed of a saturated cyclic carbonate such as propylene carbonate is known. (JP 2007-35283 A).
  • an object of the present invention is to provide a sodium secondary battery excellent in charge / discharge cycle characteristics when charged at a relatively high speed.
  • a positive electrode having a positive electrode active material that can be doped and dedoped with sodium ions, a negative electrode having a negative electrode active material that can be doped and dedoped with sodium ions, a nonaqueous solvent, and saturation to the nonaqueous solvent A sodium secondary battery having a non-aqueous electrolyte containing a sodium salt in an amount exceeding the solubility is provided.
  • a sodium secondary battery excellent in charge / discharge cycle characteristics when charged at a relatively high speed that is, at a relatively large current value.
  • a sodium secondary battery excellent in output characteristics can be provided.
  • the sodium secondary battery of the present invention has a positive electrode having a positive electrode active material that can be doped and dedoped with sodium ions, a negative electrode having a negative electrode active material that can be doped and dedoped with sodium ions, and a non-aqueous electrolyte. Usually, it further has a separator.
  • a sodium secondary battery usually contains a laminate in which a negative electrode, a separator and a positive electrode are stacked, and an electrode group obtained by winding or folding the laminate in a battery can or an aluminum laminate pack, and a non-aqueous electrolyte. Can be manufactured by impregnating the electrode group.
  • a cross section when the electrode group is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, a rectangle with rounded corners, or the like.
  • the shape can be raised.
  • examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
  • the non-aqueous electrolyte used in the sodium secondary battery of the present invention is a non-aqueous electrolyte containing a non-aqueous solvent and a sodium salt, and the amount of sodium salt exceeds the saturation solubility at 25 ° C. in the non-aqueous solvent. It is included.
  • Sodium salts used in the non-aqueous electrolyte include NaPF 6 , NaBF 4 , NaClO 4 , NaN (SO 2 CF 3 ) 2 , NaN (SO 2 C 2 F 5 ) 2 , NaCF 3 SO 3 , NaAsF 6 , NaSbF 6 , NaBC 4 O 8 , lower aliphatic carboxylic acid sodium salt, NaAlCl 4 NaPO 2 F 2 , Na 2 PO 3 F and the like, and two or more of these may be used in combination.
  • the sodium salt in the non-aqueous electrolyte is present in the non-aqueous solvent beyond the saturation solubility of 25 ° C. in the non-aqueous solvent, and the sodium salt dissolves to the saturation solubility of 25 ° C. Salt is insoluble.
  • the sodium salt is preferably in a proportion of 1.0 mol or more, more preferably 1.1 mol or more, and even more preferably 1.2 mol or more with respect to 1 L of the non-aqueous electrolyte. A ratio of 1.3 mol or more is particularly preferable.
  • the sodium salt has a ratio of 3.0 mol or less with respect to 1 L of the non-aqueous electrolyte.
  • the ratio is preferably 2.5 mol or less, more preferably 2.3 mol or less, and particularly preferably 2.1 mol or less.
  • the sodium salt in the non-aqueous electrolyte is present in excess of the saturation solubility of 25 ° C. in the non-aqueous solvent.
  • a screw tube model No. 7, capacity 50 mL, bottom diameter 35 mm, height 78 mm
  • heat at 50 ° C. or higher using a polytetrafluoroethylene rotator with a total length of 20 mm.
  • the region was in the range of 10 nm to 200 nm. If the particles are counted, it can be determined that the sodium salt in the non-aqueous electrolyte exceeds the saturation solubility at 25 ° C. in the non-aqueous solvent.
  • the particle size distribution of the non-aqueous electrolyte can be measured by measuring the particle size using a dynamic scattering method, and can be measured using a Zetasizer Nano particle measuring device (manufactured by Sysmex Corporation). When the amount of the non-aqueous solvent and the sodium salt is less than 25 mL in total, it can be confirmed that the saturated solubility is exceeded by the same operation as above except that the screw tube size and the rotor size are changed. .
  • the sodium salt insoluble portion in the non-aqueous electrolyte is dispersed in the non-aqueous electrolyte and deposited and deposited on other members of the sodium secondary battery such as electrodes and separators. However, it is preferably dispersed in the non-aqueous electrolyte.
  • the non-aqueous electrolyte used in the present invention can be obtained by adding and stirring a sodium salt to a non-aqueous solvent and dissolving the sodium salt to saturation solubility. Alternatively, it can also be obtained by adding and stirring an additional sodium salt to a nonaqueous electrolytic solution in which the sodium salt is dissolved at a saturation solubility or lower. Alternatively, it can also be obtained by adding a nonaqueous solvent to a nonaqueous electrolytic solution containing a sodium salt in excess of the saturation solubility and diluting it. It is preferable to perform the said process in inert gas atmosphere, such as argon and nitrogen.
  • examples of the nonaqueous solvent used in the nonaqueous electrolytic solution include cyclic carbonates such as propylene carbonate and ethylene carbonate; Chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; Ethers such as 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; Esters such as methyl formate and methyl acetate; Lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone; Nitriles such as acetonitrile and butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylace
  • the non-aqueous solvent used for the non-aqueous electrolyte is preferably at least one solvent selected from solvents having a flash point of 70 ° C. or higher, and a solvent having a flash point of 70 ° C. or higher with respect to the non-aqueous electrolyte. It is preferable that 25 volume% or more is included. From the viewpoint of improving the heat resistance of the battery, the solvent having a flash point of 70 ° C. or higher is more preferably contained in an amount of 35% by volume or more, more preferably 45% by volume or more, and more preferably 60% by volume or more. It is particularly preferred.
  • the flash point of non-aqueous solvent you can refer to the published information. It can also be measured by a general flash point measurement test. Examples of the flash point measurement test method include a seta sealing type (JIS K2265-2, ISO 3679, ASTM D3278, D3828).
  • Examples of the solvent having a flash point of 70 ° C. or higher include propylene carbonate, ethylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfate, Dipropyl sulfite, ethylene sulfite, dimethyl sulfone, ethyl methyl sulfone, diphenyl sulfone, sulfolane, methyl methane sulfonate, dimethyl sulfoxide, 1,3-propane sultone, etc. are included, and two or more of these are mixed May be used.
  • surfactants such as trioctyl phosphate, diphenyl ether, polyoxyethylene ethers having a perfluoroalkyl group, and perfluorooctane sulfonate esters are included in the non-aqueous electrolyte. One or more of these may be added.
  • the addition amount of the surfactant is preferably 3% by weight or less, more preferably 0.01 to 1% by weight with respect to the weight of the electrolytic solution.
  • the positive electrode has a positive electrode active material that can be doped and dedoped with sodium ions.
  • a positive electrode may be comprised from a collector and the positive mix containing the said positive electrode active material carry
  • the positive electrode mixture contains a conductive material and a binder as necessary in addition to the positive electrode active material.
  • the positive electrode active material comprises a sodium-containing transition metal compound, and the sodium-containing transition metal compound can be doped and dedoped with sodium ions.
  • sodium-containing transition metal compound examples include the following compounds. That, NaFeO 2, NaMnO 2, NaNiO 2 and NaCoO oxide represented by NaM 3 a1 O 2, such as 2, oxide represented by Na 0.44 Mn 1-a2 M 3 a2 O 2, Na 0.
  • Oxide represented by Mn 1-a2 M 3 a2 O 2.05 (M 3 is one or more transition metal elements, 0 ⁇ a1 ⁇ 1, 0 ⁇ a2 ⁇ 1); Oxides represented by Na b1 M 4 c Si 12 O 30 such as Na 6 Fe 2 Si 12 O 30 and Na 2 Fe 5 Si 12 O 30 (M 4 is one or more transition metal elements, 2 ⁇ b1 ⁇ 6, 2 ⁇ c ⁇ 5); Na 2 Fe 2 Si 6 O 18 and Na 2 MnFeSi 6 O 18 Na d M 5 e Si 6 O 18 oxide represented by such (M 5 is one or more transition metal elements, 2 ⁇ d ⁇ 6, 1 ⁇ e ⁇ 2); Na 2 FeSiO Na f M 6 g Si oxide represented by 2 O 6, such as 6 (M 6 is at least one element selected from the group consisting of transition metal elements, Mg and Al, 1 ⁇ f ⁇ 2, 1 ⁇ g ⁇ 2) NaFePO 4 , NaMnPO 4 , Na 3
  • a composite metal oxide represented by the following formula (A) can be preferably used as the positive electrode active material.
  • the charge / discharge capacity of the battery can be improved.
  • Na a M 1 b M 2 O 2 (A) (Here, M 1 represents one or more elements selected from the group consisting of Mg, Ca, Sr and Ba, and M 2 represents a group consisting of Mn, Fe, Co, Cr, V, Ti and Ni. Represents one or more selected elements, a is 0.5 or more and 1 or less, b is 0 or more and 0.5 or less, and a + b is 0.5 or more and 1 or less.
  • a carbon material can be used as the conductive material.
  • the carbon material include carbon black (for example, acetylene black, ketjen black, furnace black), fibrous carbon material (carbon nanotube, carbon nanofiber, vapor grown carbon fiber, etc.) and the like.
  • the carbon material has a large surface area, and when added in a small amount in the electrode mixture, it is possible to improve the conductivity inside the resulting electrode and improve the charge / discharge efficiency and large current discharge characteristics.
  • the proportion of the conductive material in the positive electrode mixture is 4 to 20 parts by weight with respect to 100 parts by weight of the positive electrode active material, and two or more kinds may be contained.
  • binder used for the electrode examples include a polymer of a fluorine compound and an addition polymer of a monomer containing an ethylenic double bond not containing a fluorine atom.
  • the glass transition temperature of the binder is preferably -50 to 25 ° C. By setting the glass transition temperature within the above range, the flexibility of the obtained electrode can be improved, and a sodium secondary battery that can be sufficiently used even in a low temperature environment can be obtained.
  • binder examples include Polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer Fluororesins such as polymers; Vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-pentafluoropropylene copolymer, fluoride Fluoro rubbers such as vinylidene-pentafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoro fluor
  • Methacrylic polymers such as polymethacrylic acid, polyalkylmethacrylate (the alkyl group has 1 to 20 carbon atoms in the alkyl moiety), methacrylic acid-alkylmethacrylate copolymer; Polyvinyl alcohol (partially or completely saponified), ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-alkyl acrylate (the alkyl group has 1 carbon atom in the alkyl moiety) 20) Olefin such as copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-alkyl methacrylate copolymer, ethylene-alkyl acrylate copolymer, ethylene-acrylonitrile copolymer Based polymers; Examples thereof include styrene-containing polymers such as acrylonitrile-
  • the positive electrode is manufactured, for example, by supporting a positive electrode mixture containing a positive electrode active material that can be doped and dedoped with sodium ions on a positive electrode current collector.
  • a positive electrode active material, a conductive material, a binder and a solvent are kneaded to prepare a positive electrode mixture paste, and the obtained positive electrode mixture paste is collected into a current collector.
  • a method of applying to the body and drying is mentioned.
  • the method for applying the positive electrode mixture paste to the current collector is not particularly limited.
  • drying performed after application may be performed by heat treatment, or may be performed by air drying, vacuum drying, or the like.
  • the temperature is usually about 50 to 150 ° C.
  • the pressing method include a mold press and a roll press.
  • An electrode can be manufactured by the method mentioned above. The thickness of the electrode mixture is usually about 5 to 500 ⁇ m.
  • the ratio of the positive electrode mixture component in the positive electrode mixture paste that is, the total ratio of the positive electrode active material, the conductive material, and the binder in the positive electrode mixture paste is usually 40 to 40 from the viewpoint of the thickness of the obtained electrode and applicability. 70% by weight.
  • examples of the current collector include Al, Ni, stainless steel and the like, and Al is preferable in that it is easy to process into a thin film and is inexpensive.
  • the shape of the current collector is, for example, a foil shape, a flat plate shape, a mesh shape, a net shape, a lath shape, a punching metal shape, an embossed shape, or a combination thereof (for example, a mesh flat plate). Can be given. Concavities and convexities may be formed on the surface of the current collector by etching.
  • the sodium-containing transition metal oxide which is an example of the positive electrode active material, can be produced by firing a mixture of metal-containing compounds having a composition that can be used for the sodium-containing transition metal oxide used in the present invention by firing.
  • the metal-containing compound containing the corresponding metal element can be produced by weighing and mixing so as to have a predetermined composition, and then firing the resulting mixture.
  • a sodium-containing transition metal oxide having a metal element ratio represented by Na: Mn: Fe: Ni 1: 0.3: 0.4: 0.3, which is one of the preferred metal element ratios, is Na 2 CO 3 , MnO 2 , Fe 3 O 4 , and Ni 2 O 3 are weighed so that the molar ratio of Na: Mn: Fe: Ni is 1: 0.3: 0.4: 0.3 And mixing them and firing the resulting mixture.
  • M 1 is one or more elements selected from the group consisting of Mg, Ca, Sr and Ba
  • a raw material containing M 1 is added during mixing. do it.
  • Examples of the metal-containing compound that can be used to produce the sodium-containing transition metal compound used in the present invention include oxides and compounds that can be converted to oxides when decomposed and / or oxidized at high temperatures, such as hydroxides. , Carbonates, nitrates, halides or oxalates can be used.
  • Examples of the sodium compound include one or more compounds selected from the group consisting of sodium hydroxide, sodium chloride, sodium nitrate, sodium peroxide, sodium sulfate, sodium bicarbonate, sodium oxalate, and sodium carbonate. Hydrates can also be given. From the viewpoint of handleability, sodium carbonate is more preferable.
  • the manganese compound is preferably MnO 2
  • the iron compound is preferably Fe 3 O 4
  • the nickel compound is preferably Ni 2 O 3 .
  • the mixture of metal-containing compounds can be obtained, for example, by obtaining a precursor of a metal-containing compound by the following precipitation method, and mixing the obtained precursor of the metal-containing compound and the sodium compound.
  • compounds such as chloride, nitrate, acetate, formate, and oxalate are used as raw materials for M 2 (where M 2 is as defined above), and these are dissolved in water and precipitated.
  • a precipitate containing a precursor of a metal-containing compound can be obtained by contacting with an agent. Of these raw materials, chloride is preferred.
  • these raw materials are added to acids such as hydrochloric acid, sulfuric acid, nitric acid, or aqueous solutions thereof. dissolved, it is also possible to obtain an aqueous solution containing M 2.
  • LiOH lithium hydroxide
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • Li 2 CO 3 lithium carbonate
  • Na 2 CO 3 sodium carbonate
  • K 2 CO Li 2 CO 3
  • hydrates of the compounds can be used. 1 or more types may be used and a compound and a hydrate may be used together.
  • the concentration of the precipitating agent in the aqueous solution is about 0.5 to 10 mol / L, preferably about 1 to 8 mol / L.
  • KOH is the KOH aqueous solution which melt
  • ammonia water can be mention
  • the method of adding an aqueous solution containing M 2 to the aqueous precipitation agent is preferable in terms of easy maintenance of pH and easy control of the particle size.
  • the pH tends to decrease, but the pH is adjusted to 9 or more, preferably 10 or more. while, preferably added an aqueous solution containing M 2.
  • This adjustment can also be performed by adding an aqueous solution of a precipitant.
  • a precipitate can be obtained by the above contact.
  • This precipitate contains a precursor of a metal-containing compound.
  • Solid-liquid separation may be performed by any method, but from the viewpoint of operability, a method by solid-liquid separation such as filtration is preferably used, and a method of volatilizing the liquid by heating such as spray drying may be used. Moreover, you may perform washing
  • the precipitate obtained after the solid-liquid separation may have an excessive component of the precipitant attached thereto, and the component can be reduced by washing.
  • the cleaning liquid used for cleaning is preferably water, and a water-soluble organic solvent such as alcohol or acetone may be used.
  • the drying may be performed by heat drying, and may be performed by air drying, vacuum drying, or the like.
  • heat drying it is usually carried out at 50 to 300 ° C. and preferably at about 100 to 200 ° C.
  • the mixing apparatus include stirring and mixing, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, and a ball mill.
  • the firing may be carried out usually at a temperature of about 400 to 1200 ° C., preferably about 500 to 1000 ° C., although it depends on the type of sodium compound used.
  • the time for holding at the holding temperature is usually 0.1 to 20 hours, preferably 0.5 to 10 hours.
  • the rate of temperature rise to the holding temperature is usually 50 to 400 ° C./hour, and the rate of temperature drop from the holding temperature to room temperature is usually 10 to 400 ° C./hour.
  • baking can be performed in the atmosphere of air
  • the halide may play a role as a reaction accelerator (flux).
  • the flux include NaF, MnF 3 , FeF 2 , NiF 2 , CoF 2 , NaCl, MnCl 2 , FeCl 2 , FeCl 3 , NiCl 2 , CoCl 2 , NH 4 Cl and NH 4 I.
  • These fluxes may be hydrates.
  • other metal-containing compounds that are reaction accelerators include Na 2 CO 3 , NaHCO 3 B 2 O 3, and H 3 BO 3 .
  • the sodium-containing transition metal compound used in the present invention is used as a positive electrode active material for a sodium secondary battery
  • the sodium-containing transition metal compound obtained as described above is usually industrially used, such as a ball mill, a jet mill, and a vibration mill. It is preferable to adjust the particle size by performing pulverization using an apparatus to be used, washing, classification, and the like. Moreover, you may perform baking twice or more. Further, a surface treatment such as coating the particle surface of the sodium-containing transition metal compound with an inorganic substance containing Si, Al, Ti, Y or the like may be performed.
  • a negative electrode that can be used in the sodium secondary battery of the present invention an electrode in which a negative electrode mixture containing a negative electrode active material is carried on a negative electrode current collector, a sodium metal or sodium alloy electrode that can be doped and dedoped with sodium ions, Can be used.
  • a sodium metal or sodium alloy electrode that can be doped and dedoped with sodium ions
  • the negative electrode active material in addition to the above-mentioned sodium metal or sodium alloy, carbon such as coke, carbon black, pyrolytic carbons, carbon fiber, and organic polymer compound fired body that can be doped and dedoped with sodium ions Materials and metals.
  • the shape of the carbon material may be any of a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder.
  • the carbon material may play a role as a conductive material.
  • the carbon material examples include non-graphitized carbon materials (hereinafter sometimes referred to as hard carbon) such as carbon black, pyrolytic carbons, carbon fibers, and fired organic materials.
  • the hard carbon is preferably one having an interlayer distance d (002) by an X-ray diffraction method of 0.360 nm or more and 0.395 nm or less and a crystallite size Lc in the c-axis direction of 1.30 nm or less.
  • the R value (ID / IG) obtained by Raman spectroscopy is preferably 1.07 or more and 3 or less.
  • a Raman spectrum obtained by irradiating a laser having a wavelength of 532 nm and performing Raman spectroscopic measurement (the vertical axis is the scattered light intensity in an arbitrary unit, and the horizontal axis is the Raman shift wave number (cm ⁇ 1 ).
  • the hard carbon for example, carbon micro beads made of non-graphitized carbon material can be mentioned, and specifically, ICB (trade name: Nika beads) manufactured by Nippon Carbon Co., Ltd. can be mentioned.
  • the shape of the particles constituting the carbon material include a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, and an aggregate shape of fine particles.
  • the average particle diameter is preferably 0.01 ⁇ m or more and 30 ⁇ m or less, more preferably 0.1 ⁇ m or more and 20 ⁇ m or less.
  • Examples of the metal used for the negative electrode active material include tin, lead, silicon, germanium, phosphorus, bismuth, and antimony.
  • Examples of the alloy include an alloy composed of two or more metals selected from the group consisting of the above metals, an alloy composed of two or more metals selected from the group consisting of the above metals and transition metals, and Si— Examples of the alloy include Zn, Cu 2 Sb, and La 3 Ni 2 Sn 7 . These metals and alloys are used as an electrode active material by being carried on a current collector in combination with a carbon material.
  • Examples of the oxide used for the negative electrode active material include Li 4 Ti 5 O 12 and the like.
  • Examples of sulfides include TiS 2 , NiS 2 , FeS 2 , Fe 3 S 4 and the like.
  • Examples of nitrides, Na 3 N, Na 2.6 Co 0.4 Na such as N 3-x M x N (where, M is a transition metal element, 0 ⁇ x ⁇ 3), and the like.
  • These carbon materials, metals, oxides, sulfides, and nitrides that are negative electrode active materials may be used in combination, and may be crystalline or amorphous. From the viewpoint of cycle characteristics, it is preferable to use a carbon material as the negative electrode active material, and it is more preferable to use hard carbon.
  • These carbon materials, metals, oxides, sulfides, and nitrides are mainly supported on current collectors and used as electrodes.
  • the negative electrode mixture may contain a binder and a conductive material as necessary.
  • the binder and conductive material include the same binders and conductive materials used for the positive electrode.
  • the binder contained in the negative electrode mixture is preferably polyacrylic acid, sodium polyacrylate, lithium polyacrylate, potassium polyacrylate, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylene-vinyl acetate.
  • the binder contained in the negative electrode mixture includes polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoro. It is preferable to use one or more selected from the group consisting of ethylene copolymers.
  • the ratio of the binder in the negative electrode mixture is usually about 0.5 to 30 parts by weight, preferably about 2 to 20 parts by weight with respect to 100 parts by weight of the carbon material.
  • Examples of the negative electrode current collector include Al, Cu, Ni, and stainless steel, and Al is preferable because it can be easily processed into a thin film and is inexpensive.
  • the shape of the current collector is, for example, a foil shape, a flat plate shape, a mesh shape, a net shape, a lath shape, a punching metal shape, an embossed shape, or a combination thereof (for example, a mesh flat plate). Can be given. Concavities and convexities may be formed by etching on the current collector surface.
  • the thickness of the separator is preferably as thin as possible as long as the mechanical strength is maintained in that the volume energy density of the battery is increased and the internal resistance is reduced. In general, the thickness of the separator is preferably about 5 to 200 ⁇ m, more preferably about 5 to 40 ⁇ m.
  • the separator preferably has a porous film containing a thermoplastic resin.
  • a secondary battery normally, when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode, the current is interrupted to prevent an excessive current from flowing (shut down). is important. Therefore, the separator shuts down at the lowest possible temperature when the normal use temperature is exceeded (when the separator has a porous film containing a thermoplastic resin, the micropores of the porous film are blocked). Even after the shutdown, even if the temperature in the battery rises to a certain high temperature, it is required to maintain the shutdown state without breaking the film due to the temperature, in other words, to have high heat resistance.
  • the thermal breakage of the secondary battery of the present invention It becomes possible to prevent more.
  • the heat-resistant porous layer may be laminated on both surfaces of the porous film.
  • Particle size distribution measurement of non-aqueous electrolyte The particle size distribution measurement of the non-aqueous electrolyte was performed using Zetasizer Nano (Nano ZS (ZEN3600), manufactured by Sysmex Corporation). The measurement was performed at 25 ° C. using a glass cuvette.
  • the mixture was placed in an alumina calcination vessel, then calcined by holding for six hours at 850 ° C. in an air atmosphere using an electric furnace and then cooled to room temperature to obtain a composite metal oxide A 1.
  • a powder X-ray diffraction analysis of the composite metal oxide A 1 was performed, it was found that the composite metal oxide A 1 was assigned to the ⁇ -NaFeO 2 type crystal structure.
  • the composition of the composite metal oxide A 1 is analyzed by ICP-AES, the molar ratio of Na: Ca: Fe: Ni: Mn is 0.99: 0.01: 0.4: 0.3: 0. 3.
  • a positive electrode mixture paste was prepared using Kida Chemical Co., Ltd.).
  • Composite metal oxide A 1 : Conductive material: Binder: Weighed to have a composition of NMP 90: 5: 5: 100 (weight ratio), and 4,000 rpm, 5 using a disperse mat (made by VMA-GETZMANN)
  • a positive electrode mixture paste was obtained by stirring and mixing for a minute.
  • the obtained positive electrode mixture paste was applied to a 20 ⁇ m thick aluminum foil using a doctor blade, dried at 60 ° C. for 2 hours, and then using a roll press (SA-602, manufactured by Tester Sangyo Co., Ltd.)
  • a positive electrode AE 1 was obtained by rolling at a pressure of 200 kN / m.
  • Carbon material C 1 : PVdF: NMP 90: 10: 100 (weight ratio) is weighed so as to have a composition, and is stirred and mixed using a disperse mat (VMA-GETZMANN Co., Ltd.). Obtained. The rotation conditions of the rotating blades were 2,000 rpm for 10 minutes. The obtained electrode mixture paste was applied to a copper foil using a doctor blade, dried at 60 ° C. for 2 hours, and then rolled at 100 kN / m using a roll press to obtain carbon electrode CE 1 . .
  • Example 1> (Production of Sodium Secondary Battery B 1) A propylene carbonate (PC) solution (NaPF 6 PC) containing 1.3 mol of NaPF 6 in 1 L (manufactured by Kishida Chemical Co., Ltd.) and fluoroethylene carbonate (FEC) (manufactured by Kishida Chemical Co., Ltd.) 98: 2 Take the screw tube (manufactured by ASONE, model No. 7) to a total volume ratio of 25 mL and heat at 80 ° C. using a polytetrafluoroethylene rotor with a total length of 20 mm at 250 rpm.
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • non-aqueous electrolyte EL 1 (PC / FEC containing 1.3 mol of NaPF 6 in 1 L).
  • the flash points of PC and FEC are disclosed as 135 ° C. and 122 ° C., respectively, in the product safety data seed issued by Kishida Chemical Co., Ltd.
  • the ratio of PC and FEC to non-aqueous electrolyte EL 1 is 91 vol. %.
  • the electrolyte EL 1 As a result of measuring the particle size distribution of the non-aqueous electrolyte EL 1 , it was confirmed that particles were counted in a region of 10 nm or more and 200 nm or less, and that the sodium salt exceeded the saturation solubility at 25 ° C.
  • a positive electrode AE 1 punched to a diameter of 14.5 mm is placed in a recess in the lower part of a coin cell (manufactured by Hosen Co., Ltd.), and a carbon electrode CE 1 punched to a diameter of 15.0 mm is used as the negative electrode in the electrolyte.
  • the electrolyte EL 1 to produce a sodium secondary battery B 1 with polyethylene porous film (thickness 20 [mu] m) as a separator.
  • the battery was assembled in a glove box in an argon atmosphere.
  • Example 2> (Production of Sodium Secondary Battery B 2) The same as Example 1 except that PC containing 2.0 mol of NaPF 6 in 1 L, PC (manufactured by Kishida Chemical Co., Ltd.), and FEC were in a ratio of 74: 24: 2 (volume ratio).
  • the non-aqueous electrolyte EL 2 (PC / FEC containing 1.5 mol of NaPF 6 in 1 L) was prepared by the operation.
  • the ratio of PC and FEC to the non-aqueous electrolyte EL 2 is 90% by volume.
  • Example 3 (Production of Sodium Secondary Battery B 3) A non-aqueous electrolyte EL 3 (in 1 L) was prepared in the same manner as in Example 1 except that PC containing 2.0 mol of NaPF 6 in 1 L and FEC were in a ratio of 98: 2 (volume ratio). the PC / FEC solution) containing 2.0 mol of NaPF 6 in the adjustment. The ratio of PC and FEC to the non-aqueous electrolyte EL 3 is 86% by volume.
  • Example 4> (Preparation of Sodium Secondary Battery B 4)
  • PC containing 2.0 mol of NaPF 6 in 1 L as non-aqueous electrolyte EL 4 is taken into a screw tube (manufactured by ASONE, model No. 7) so as to be 25 mL, and heated to 80 ° C., with a total length of 20 mm.
  • a polytetrafluoroethylene rotator prepared by stirring at 250 rpm in an argon gas atmosphere for 6 hours. Percentage of PC relative to the non-aqueous electrolyte EL 4 is a 86% by volume.
  • a sodium secondary battery B 4 was produced in the same manner as in Example 1 except that PC (nonaqueous electrolyte EL 4 ) containing 2.0 mol of NaPF 6 in 1 L was used.
  • Example 5 (Production of Sodium Secondary Battery B 5) Example 1 except that NaPF 6 (manufactured by Johnson Matthey) was added to a PC containing 2.0 mol of NaPF 6 in 1 L so as to be a PC containing 2.5 mol of NaPF 6 in 1 L.
  • the non-aqueous electrolyte EL 5 (PC containing 2.5 mol of NaPF 6 in 1 L) was prepared in the same manner as in Example 1. Percentage of PC relative to the non-aqueous electrolyte EL 5 is 82% by volume.
  • Example 6 (Production of Sodium Secondary Battery B 6) A PC containing 1.0 mol of NaN (SO 2 CF 3 ) 2 in 1 L (manufactured by Kishida Chemical Co., Ltd.) becomes a PC containing 2.0 mol of NaN (SO 2 CF 3 ) 2 in 1 L.
  • the non-aqueous electrolyte EL 6 (2.0 mol of NaN in 1 L) was prepared in the same manner as in Example 1 except that NaN (SO 2 CF 3 ) 2 (NaTFSI) (manufactured by Kishida Chemical Co., Ltd.) was added.
  • PC containing (SO 2 CF 3 ) 2 was adjusted.
  • the ratio of PC to non-aqueous electrolyte EL 6 is 68% by volume.
  • a sodium secondary battery B 6 was produced in the same manner as in Example 1 except that the non-aqueous electrolyte EL 6 was used as the electrolyte.
  • Example 7> (Production of Sodium Secondary Battery B 7)
  • PC made by Kishida Chemical Co., Ltd.
  • the non-aqueous electrolyte EL 7 (1.0 mol of NaPF 6 and 0.3 mol in 1 L) was prepared in the same manner as in Example 1 except that NaTFSI (manufactured by Kishida Chemical Co., Ltd.) was added so as to be PC.
  • PC / FEC containing NaTFSI The ratio of PC and FEC to non-aqueous electrolyte EL 7 is 89% by volume.
  • Example 8> (Production of Sodium Secondary Battery B 8) Example 1 except that NaTFSI was added to a PC containing 1.0 mol of NaPF 6 in 1 L so as to be a PC containing 1.0 mol of NaTFSI in 1 L.
  • the non-aqueous electrolyte EL 8 (PC containing 1.0 mol of NaPF 6 and 1.0 mol of NaTFSI in 1 L) was prepared by the above procedure. Percentage of PC relative to the non-aqueous electrolyte EL 8 is 80% by volume.
  • a sodium secondary battery BH 1 was produced in the same manner as in Example 1 except that the non-aqueous electrolyte EH 1 was used as the electrolyte.
  • ⁇ Charge / discharge test> Prior to the charge / discharge test, the sodium secondary batteries B 1 to B 8 and BH 1 to BH 3 were stabilized (stabilized), and then the output test and the charge / discharge cycle test were performed. .
  • CC Constant Current
  • CC charging was performed at a 0.05 C rate until reaching 3.8 V, and then a current-carrying treatment for performing CC discharging until reaching 2.0 V at a 0.1 C rate was performed for one cycle.
  • CC-CV constant voltage
  • CC-CV constant voltage
  • CC-CV constant voltage
  • ⁇ Output test> After the stabilization treatment, an output test was performed under the following conditions. After performing CC-CV charge at a 0.2C rate until reaching 4.0V (charging is completed when the current value reaches 0.02C), a charge / discharge test is performed to perform CC discharge until reaching 2.0V at a 0.2C rate. It was. Thereafter, an output test was performed under the same charging conditions as those described above, with discharge currents of 0.5, 1, 2, 5, 10C. Table 1 shows a ratio of 5C discharge capacity to 0.2C discharge capacity (5C discharge capacity / 0.2C discharge capacity ⁇ 100 (%)). ⁇ Charge / discharge cycle test> After the output test, a charge / discharge cycle test was performed under the following conditions.
  • a sodium secondary battery excellent in charge / discharge cycle characteristics when charged at a relatively high speed that is, at a relatively large current value (1C rate).
  • a sodium secondary battery excellent in output characteristics can be provided.

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Abstract

L'invention concerne une batterie sodium-ion ayant une électrode positive qui comporte une substance active d'électrode active dans laquelle des ions sodium peuvent être dopés et dédopés, une électrode négative qui comporte une substance active d'électrode positive dans laquelle des ions sodium peuvent être dopés et dédopés, un solvant non aqueux et un électrolyte non aqueux comprenant un sel de sodium qui dépasse la solubilité à saturation dans l'électrolyte non aqueux. Il est donc possible de proposer une batterie sodium-ion présentant d'excellentes caractéristiques de cycle de charge/décharge lors d'une charge à vitesse relativement élevée, c'est-à-dire avec un courant relativement important. De plus, il est possible de proposer une batterie sodium-ion présentant d'excellentes caractéristiques de puissance.
PCT/JP2014/080564 2013-11-18 2014-11-12 Batterie sodium-ion WO2015072577A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2016183638A1 (fr) * 2015-05-20 2016-11-24 Deakin University Cellule électrochimique
WO2017149204A3 (fr) * 2016-03-04 2017-12-21 Broadbit Batteries Oy Cellules de sodium rechargeables pour l'utilisation de batterie à haute densité d'énergie
KR20190125471A (ko) * 2017-03-17 2019-11-06 브로드빗 배터리즈 오와이 슈퍼커패시터용 전해질 및 고출력 배터리 용도
US11316191B2 (en) 2015-09-30 2022-04-26 Broadbit Batteries Oy Electrochemical secondary cells for high-energy or high-power battery use
CN117497860A (zh) * 2023-12-28 2024-02-02 深圳博钠新能源科技有限公司 一种阻燃型钠离子电池电解液、制备方法及电池

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JP2010251283A (ja) * 2008-07-30 2010-11-04 Sumitomo Chemical Co Ltd ナトリウム二次電池
JP2013058442A (ja) * 2011-09-09 2013-03-28 Ricoh Co Ltd 非水電解液二次電池
WO2013157187A1 (fr) * 2012-04-16 2013-10-24 パナソニック株式会社 Électrolyte non aqueux pour élément électrochimique, procédé de production associé, et élément électrochimique utilisant cet électrolyte

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Publication number Priority date Publication date Assignee Title
JPH01124970A (ja) * 1987-11-10 1989-05-17 Hitachi Maxell Ltd リチウム二次電池
JP2010251283A (ja) * 2008-07-30 2010-11-04 Sumitomo Chemical Co Ltd ナトリウム二次電池
JP2013058442A (ja) * 2011-09-09 2013-03-28 Ricoh Co Ltd 非水電解液二次電池
WO2013157187A1 (fr) * 2012-04-16 2013-10-24 パナソニック株式会社 Électrolyte non aqueux pour élément électrochimique, procédé de production associé, et élément électrochimique utilisant cet électrolyte

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016183638A1 (fr) * 2015-05-20 2016-11-24 Deakin University Cellule électrochimique
US11961963B2 (en) 2015-05-20 2024-04-16 Deakin University Electrochemical cell
US11316191B2 (en) 2015-09-30 2022-04-26 Broadbit Batteries Oy Electrochemical secondary cells for high-energy or high-power battery use
WO2017149204A3 (fr) * 2016-03-04 2017-12-21 Broadbit Batteries Oy Cellules de sodium rechargeables pour l'utilisation de batterie à haute densité d'énergie
CN108780917A (zh) * 2016-03-04 2018-11-09 博比特电池有限公司 用于高能量密度电池的可再充电钠电池单元
JP2019508856A (ja) * 2016-03-04 2019-03-28 ブロードビット バッテリーズ オーイー 高エネルギー密度電池の使用のための再充電可能なナトリウム電池
KR20190125471A (ko) * 2017-03-17 2019-11-06 브로드빗 배터리즈 오와이 슈퍼커패시터용 전해질 및 고출력 배터리 용도
JP2020512660A (ja) * 2017-03-17 2020-04-23 ブロードビット バッテリーズ オーイー スーパーキャパシタおよび高出力バッテリ用の電解質
JP7483375B2 (ja) 2017-03-17 2024-05-15 ブロードビット バッテリーズ オーイー スーパーキャパシタおよび高出力バッテリ用の電解質
US12113175B2 (en) 2017-03-17 2024-10-08 Broadbit Batteries Oy Electrolyte for supercapacitor and high-power battery use
CN117497860A (zh) * 2023-12-28 2024-02-02 深圳博钠新能源科技有限公司 一种阻燃型钠离子电池电解液、制备方法及电池

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