WO2015093580A1 - 非水系電解液及びそれを用いた非水系電解液二次電池 - Google Patents
非水系電解液及びそれを用いた非水系電解液二次電池 Download PDFInfo
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- WO2015093580A1 WO2015093580A1 PCT/JP2014/083622 JP2014083622W WO2015093580A1 WO 2015093580 A1 WO2015093580 A1 WO 2015093580A1 JP 2014083622 W JP2014083622 W JP 2014083622W WO 2015093580 A1 WO2015093580 A1 WO 2015093580A1
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- Prior art keywords
- formula
- carbonate
- aqueous electrolyte
- less
- represented
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- 239000003792 electrolyte Substances 0.000 claims abstract description 23
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- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229960004711 sodium monofluorophosphate Drugs 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 150000005687 symmetric chain carbonates Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- FSZKWHBYBSGMJD-UHFFFAOYSA-N tert-butyl ethyl carbonate Chemical compound CCOC(=O)OC(C)(C)C FSZKWHBYBSGMJD-UHFFFAOYSA-N 0.000 description 1
- QRKULNUXBVSTBL-UHFFFAOYSA-N tert-butyl methyl carbonate Chemical compound COC(=O)OC(C)(C)C QRKULNUXBVSTBL-UHFFFAOYSA-N 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- FCFMKFHUNDYKEG-UHFFFAOYSA-N thietane 1,1-dioxide Chemical class O=S1(=O)CCC1 FCFMKFHUNDYKEG-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/127—Packers; Plugs with inflatable sleeve
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/02—Subsoil filtering
- E21B43/10—Setting of casings, screens, liners or the like in wells
- E21B43/103—Setting of casings, screens, liners or the like in wells of expandable casings, screens, liners, or the like
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B2200/00—Special features related to earth drilling for obtaining oil, gas or water
- E21B2200/01—Sealings characterised by their shape
-
- 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
-
- 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
- H01M2300/0025—Organic electrolyte
-
- 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 non-aqueous electrolyte and a non-aqueous electrolyte secondary battery using the same.
- lithium secondary batteries having higher energy density than nickel / cadmium batteries and nickel / hydrogen batteries have been developed, and up to now, efforts to improve the performance have been repeated.
- Components constituting the lithium secondary battery are mainly classified into a positive electrode, a negative electrode, a separator, and an electrolytic solution.
- electrolytes generally include electrolytes such as LiPF 6 , LiBF 4 , LiClO 4 , LiCF 3 SO 3 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiCF 3 (CF 2 ) 3 SO 3 , Cyclic carbonates such as ethylene carbonate and propylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone; chain esters such as methyl acetate and methyl propionate
- a non-aqueous electrolyte solution dissolved in a non-aqueous solvent such as a liquid is used.
- Patent Documents 1 and 2 introduce a technique of using a hydroxy acid derivative in a non-aqueous electrolyte using a carbon material for a negative electrode.
- Patent Documents 3 and 4 introduce a technique for adding a specific sulfonic acid ester to a nonaqueous electrolyte.
- the present invention has been made in view of the background art, and an object thereof is to provide a non-aqueous electrolyte excellent in cycle capacity retention rate and low-temperature resistance characteristics, and a non-aqueous electrolyte secondary battery using the same.
- the present inventors have included a specific compound in the non-aqueous electrolyte so that the non-aqueous electrolyte secondary battery has a cycle capacity retention rate and low-temperature resistance characteristics.
- the present invention has been improved. That is, the gist of the present invention is as follows.
- a non-aqueous electrolyte solution comprising an electrolyte and a non-aqueous solvent for dissolving the electrolyte, wherein the formula (1): Where X represents an organic group containing a hetero atom, and represents an organic group having at least one oxygen atom as the hetero atom; Y represents a sulfur atom, a phosphorus atom or a carbon atom, n represents an integer of 1 or 2, m represents an integer of 2 to 4, l represents an integer of 1 or 2, Z is a non-aqueous electrolyte containing a compound represented by the formula: Z represents an organic group which may have a hetero atom having 4 to 12 carbon atoms.
- E Any one of (a) to (d), wherein at least one of the compounds represented by the formula (1) is contained in 0.01 to 5% by mass in 100% by mass of the nonaqueous electrolytic solution. Any non-aqueous electrolyte.
- (F) The non-aqueous electrolyte solution according to any one of (a) to (e), wherein the non-aqueous electrolyte solution further contains a cyclic carbonate having an unsaturated bond.
- (G) A non-aqueous electrolyte secondary battery including a negative electrode and a positive electrode capable of inserting and extracting metal ions, and the non-aqueous electrolyte solution of any one of (a) to (f).
- (H) The non-aqueous electrolyte secondary battery according to (g), wherein the positive electrode capable of inserting and extracting metal ions includes at least one layered transition metal oxide.
- a process for producing a sulfonic acid ester comprising: (K) The method for producing a sulfonate ester according to (j), wherein the crystallization is performed by lowering the temperature of the solution containing the sulfonate ester represented by the formula (10). (L) The manufacturing method of the sulfonate ester of (k) whose solution containing the sulfonate ester represented by Formula (10) is a methanol solution. (M) The method for producing a sulfonic acid ester according to any one of (j) to (k), wherein crystallization is performed at a temperature of 20 ° C. or lower.
- a compound having an alcoholic hydroxyl group represented by formula (12) is represented by formula (22): Where R a independently represents an alkyl group having 1 to 4 carbon atoms, The method for producing a sulfonate ester according to any one of (j) to (o), wherein R b independently represents an alkyl group having 1 to 4 carbon atoms. (Q) The method for producing a sulfonic acid ester according to any one of (j) to (p), wherein the compound having an alcoholic hydroxyl group represented by the formula (12) is glycerol carbonate.
- R independently represents an alkyl group having 1 to 4 carbon atoms
- R b independently represents an alkyl group having 1 to 4 carbon atoms
- p is a compound represented by the integer of 4-6.
- S Formula (30): In the formula, p is a compound represented by an integer of 4-6.
- One feature of the present invention is that the compound represented by the formula (1) is used in a non-aqueous electrolyte.
- the metal derived from the compound represented by the formula (1) is electrochemically reduced on the negative electrode surface.
- a salt eg, a lithium salt
- this salt improving the thermal stability of a negative electrode membrane
- the present invention is a non-aqueous electrolyte containing an electrolyte (for example, a lithium salt) and a non-aqueous solvent for dissolving the electrolyte, and contains a compound represented by the formula (1). Is a non-aqueous electrolyte solution.
- an electrolyte for example, a lithium salt
- a non-aqueous solvent for dissolving the electrolyte
- Electrolyte typically includes a lithium salt, but is not limited thereto, and may be a metal salt such as sodium, potassium, calcium, barium and the like.
- the lithium salt is not particularly limited as long as it is known to be used for non-aqueous electrolyte applications. Specific examples include the following.
- lithium salts may be used alone or in combination of two or more.
- a preferable example in the case of using two or more types in combination is a combination of LiPF 6 and LiBF 4 or LiPF 6 and FSO 3 Li, which has an effect of improving load characteristics and cycle characteristics.
- concentration of LiBF 4 or FSO 3 Li in 100% by mass of the non-aqueous electrolyte there is no limitation on the concentration of LiBF 4 or FSO 3 Li in 100% by mass of the non-aqueous electrolyte, and it is optional as long as the effect of the present invention is not significantly impaired. It is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less.
- the concentration of LiPF 6 is not limited and is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.5 mol / L or more, preferably 0.8 mol / L or more, and usually 3 mol / L. Hereinafter, it is preferably 2 mol / L or less.
- Another example is the combined use of an inorganic lithium salt and an organic lithium salt, which has the effect of suppressing deterioration due to high-temperature storage.
- the organic lithium salt CF 3 SO 3 Li, LiN (FSO 2 ) 2 , LiN (FSO 2 ) (CF 3 SO 2 ), LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , Lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropane disulfonylimide, LiC (FSO 2 ) 3 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium tetrafluorooxalatophosphate, lithium difluorobisoxalatophosphate, LiBF 3 CF 3 , LiBF 3 C 2 F 5
- the proportion of the organic lithium salt in 100% by mass of the non-aqueous electrolyte is preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, preferably 30% by mass or less, particularly preferably. It is 20 mass% or less.
- concentration of inorganic lithium salt Although it is arbitrary unless the effect of this invention is impaired remarkably, It is 0.1 mass% or more normally with respect to the nonaqueous electrolyte solution of this invention, Preferably it is 0.2. It is 10 mass% or less normally, Preferably it is 5 mass% or less.
- the concentration of these lithium salts in the nonaqueous electrolytic solution is not particularly limited as long as the effects of the present invention are not impaired.
- the total molar concentration of lithium in the non-aqueous electrolytic solution is preferably 0.3 mol / L or more, more preferably 0.4 mol from the viewpoint of ensuring the electric conductivity of the electrolytic solution in a good range and ensuring good battery performance.
- / L or more more preferably 0.5 mol / L or more, preferably 3 mol / L or less, more preferably 2.5 mol / L or less, still more preferably 2.0 mol / L or less. If it is this range, since there is not too little lithium which is a charged particle and a viscosity can be made into an appropriate range, it will become easy to ensure favorable electrical conductivity.
- Non-aqueous solvent As the non-aqueous solvent, it is possible to use cyclic carbonates, chain carbonates, cyclic and chain carboxylic acid esters, ether compounds, sulfone compounds, and the like.
- cyclic carbonate examples include those having an alkylene group having 2 to 4 carbon atoms.
- Specific examples of the cyclic carbonate having 2 to 4 carbon atoms include alkylene carbonates having an alkylene group having 2 to 4 carbon atoms such as ethylene carbonate, propylene carbonate, and butylene carbonate.
- ethylene carbonate and propylene carbonate are particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.
- a cyclic carbonate may be used individually by 1 type, and may have 2 or more types by arbitrary combinations and ratios.
- the blending amount of the cyclic carbonate is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired.
- the lower limit of the blending amount when one kind is used alone is 5 volumes in 100 volume% of the non-aqueous solvent. % Or more, more preferably 10% by volume or more. By setting this range, the decrease in electrical conductivity resulting from the decrease in the dielectric constant of the non-aqueous electrolyte is avoided, and the large current discharge characteristics, negative electrode stability, and cycle characteristics of the non-aqueous electrolyte secondary battery are good. It becomes easy to be in a range.
- an upper limit is 95 volume% or less, More preferably, it is 90 volume% or less, More preferably, it is 85 volume% or less.
- the viscosity of the non-aqueous electrolyte solution is set to an appropriate range, a decrease in ionic conductivity is suppressed, and as a result, the load characteristics of the non-aqueous electrolyte secondary battery are easily set in a favorable range.
- One of the preferred combinations when two or more of the cyclic carbonates are used in any combination is a combination of ethylene carbonate and propylene carbonate.
- the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, and particularly preferably 95: 5 to 50:50.
- the amount of propylene carbonate in the entire non-aqueous solvent is 0.1% by volume or more, preferably 1% by volume or more, more preferably 2% by volume or more, and usually 20% by volume or less, preferably 8% by volume or less. More preferably, it is 5 volume% or less.
- propylene carbonate is contained within this range, the low temperature characteristics are further excellent, which is preferable.
- the chain carbonate is preferably one having 3 to 7 carbon atoms.
- the chain carbonate having 3 to 7 carbon atoms dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, Examples thereof include n-butyl methyl carbonate, isobutyl methyl carbonate, t-butyl methyl carbonate, ethyl-n-propyl carbonate, n-butyl ethyl carbonate, isobutyl ethyl carbonate, t-butyl ethyl carbonate and the like.
- dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, ethyl methyl carbonate, and methyl-n-propyl carbonate are preferable, and dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are particularly preferable.
- a chain carbonate having a fluorine atom hereinafter sometimes abbreviated as “fluorinated chain carbonate”.
- the number of fluorine atoms contained in the fluorinated chain carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less.
- the fluorinated chain carbonate When the fluorinated chain carbonate has a plurality of fluorine atoms, they may be bonded to the same carbon or may be bonded to different carbons.
- the fluorinated chain carbonate include a fluorinated dimethyl carbonate derivative, a fluorinated ethyl methyl carbonate derivative, and a fluorinated diethyl carbonate derivative.
- fluorinated dimethyl carbonate derivative examples include fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, trifluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, bis (difluoro) methyl carbonate, bis (trifluoromethyl) carbonate, and the like.
- Fluorinated ethyl methyl carbonate derivatives include 2-fluoroethyl methyl carbonate, ethyl fluoromethyl carbonate, 2,2-difluoroethyl methyl carbonate, 2-fluoroethyl fluoromethyl carbonate, ethyl difluoromethyl carbonate, 2,2,2-trimethyl Examples include fluoroethyl methyl carbonate, 2,2-difluoroethyl fluoromethyl carbonate, 2-fluoroethyl difluoromethyl carbonate, and ethyl trifluoromethyl carbonate.
- Fluorinated diethyl carbonate derivatives include ethyl- (2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis (2-fluoroethyl) carbonate, ethyl- (2,2,2-trifluoro).
- Ethyl) carbonate 2,2-difluoroethyl-2′-fluoroethyl carbonate, bis (2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl-2′-fluoroethyl carbonate, 2,2, Examples include 2-trifluoroethyl-2 ′, 2′-difluoroethyl carbonate, bis (2,2,2-trifluoroethyl) carbonate, and the like.
- a chain carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the blending amount of the chain carbonate is preferably 5% by volume or more, more preferably 10% by volume or more, and still more preferably 15% by volume or more in 100% by volume of the non-aqueous solvent.
- the chain carbonate is preferably 90% by volume or less, more preferably 85% by volume or less, in 100% by volume of the non-aqueous solvent.
- ⁇ Cyclic carboxylic acid ester examples include those having 3 to 12 total carbon atoms in the structural formula. Specific examples include gamma butyrolactone, gamma valerolactone, gamma caprolactone, epsilon caprolactone, and the like. Among these, gamma butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.
- the compounding amount of the cyclic carboxylic acid ester is preferably 5% by volume or more, more preferably 10% by volume or more, in 100% by volume of the non-aqueous solvent. If it is this range, it will become easy to improve the electrical conductivity of a non-aqueous electrolyte solution, and to improve the large current discharge characteristic of a non-aqueous electrolyte secondary battery. Moreover, the compounding quantity of cyclic carboxylic acid ester becomes like this. Preferably it is 50 volume% or less, More preferably, it is 40 volume% or less.
- the viscosity of the non-aqueous electrolyte solution is set to an appropriate range, a decrease in electrical conductivity is avoided, an increase in negative electrode resistance is suppressed, and a large current discharge of the non-aqueous electrolyte secondary battery is performed. It becomes easy to make a characteristic into a favorable range.
- chain carboxylic acid esters include those having 3 to 7 carbon atoms in the structural formula. Specifically, methyl acetate, ethyl acetate, acetate n-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, Isopropyl propionate, n-butyl propionate, isobutyl propionate, t-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid-n- Examples include propyl and isopropyl isobutyrate.
- the amount of the chain carboxylic acid ester is preferably 10% by volume or more, more preferably 15% by volume or more, in 100% by volume of the non-aqueous solvent.
- strand-shaped carboxylic acid ester is preferably 60 volume% or less in 100 volume% of non-aqueous solvents, More preferably, it is 50 volume% or less.
- ether compound a chain ether having 3 to 10 carbon atoms in which part of hydrogen may be substituted with fluorine and a cyclic ether having 3 to 6 carbon atoms are preferable.
- chain ether having 3 to 10 carbon atoms include diethyl ether, di (2-fluoroethyl) ether, di (2,2-difluoroethyl) ether, di (2,2,2-trifluoroethyl) ether, ethyl (2-fluoroethyl) ether, ethyl (2,2,2-trifluoroethyl) ether, ethyl (1,1,2,2-tetrafluoroethyl) ether, (2-fluoroethyl) (2,2,2 -Trifluoroethyl) ether, (2-fluoroethyl) (1,1,2,2-tetrafluoroethyl) ether, (2,2,2-trifluoroethyl) ether,
- Examples of the cyclic ether having 3 to 6 carbon atoms include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 1 , 4-dioxane and the like, and fluorinated compounds thereof.
- dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether have high solvating ability to lithium ions and improve ion dissociation.
- dimethoxymethane, diethoxymethane, and ethoxymethoxymethane are preferable because they have low viscosity and give high ionic conductivity.
- the compounding amount of the ether compound is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more, and preferably 70% by volume or less, in 100% by volume of the non-aqueous solvent. Is 60% by volume or less, more preferably 50% by volume or less. If it is this range, it is easy to ensure the improvement effect of the lithium ion dissociation degree of chain ether, and the improvement of the ionic conductivity derived from a viscosity fall, and when a negative electrode active material is a carbonaceous material, a chain ether with lithium ion It is easy to avoid a situation where the capacity is reduced due to co-insertion.
- a cyclic sulfone having 3 to 6 carbon atoms and a chain sulfone having 2 to 6 carbon atoms are preferable.
- the number of sulfonyl groups in one molecule is preferably 1 or 2.
- Examples of the cyclic sulfone having 3 to 6 carbon atoms include trimethylene sulfones, tetramethylene sulfones, hexamethylene sulfones as monosulfone compounds; trimethylene disulfones, tetramethylene disulfones, hexamethylene disulfones as disulfone compounds, etc. Is mentioned.
- tetramethylene sulfones from the viewpoint of dielectric constant and viscosity, tetramethylene sulfones, tetramethylene disulfones, hexamethylene sulfones, and hexamethylene disulfones are more preferable, and tetramethylene sulfones (sulfolanes) are particularly preferable.
- the sulfolane is preferably sulfolane and / or a sulfolane derivative (hereinafter sometimes abbreviated as “sulfolane” including sulfolane).
- sulfolane derivative one in which one or more hydrogen atoms bonded to the carbon atom constituting the sulfolane ring are substituted with a fluorine atom or an alkyl group is preferable.
- Examples of the chain sulfone having 2 to 6 carbon atoms include dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, n-propyl methyl sulfone, n-propyl ethyl sulfone, di-n-propyl sulfone, isopropyl methyl sulfone, isopropyl ethyl sulfone, and diisopropyl.
- the blending amount of the sulfone compound is preferably 0.3% by volume or more, more preferably 1% by volume or more, still more preferably 5% by volume or more, and preferably 40% by volume in 100% by volume of the non-aqueous solvent.
- it is more preferably 35% by volume or less, still more preferably 30% by volume or less.
- durability improvement effects such as cycle characteristics and storage characteristics can be easily obtained, and the viscosity of the non-aqueous electrolyte can be set to an appropriate range to avoid a decrease in electrical conductivity.
- a high dielectric constant solvent such as a cyclic carbonate, a cyclic carbonate having a fluorine atom, or a cyclic carboxylate
- a low viscosity solvent such as a chain carbonate or a chain carboxylate
- One preferred combination of non-aqueous solvents is a combination mainly composed of cyclic carbonate and chain carbonate.
- the total of the cyclic carbonate and the chain carbonate in the non-aqueous solvent is preferably 70% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and the cyclic carbonate and the chain carbonate.
- the ratio of the cyclic carbonate with respect to the total is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more, preferably 50% by volume or less, more preferably 35% by volume or less, It is preferably 30% by volume or less, particularly preferably 25% by volume or less.
- the balance between the cycle characteristics and high-temperature storage characteristics (particularly, the remaining capacity and high-load discharge capacity after high-temperature storage) of a battery produced using the non-aqueous solvent may be improved.
- Cyclic carbonates include ethylene carbonate, propylene carbonate, monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, and 4,5-difluoro-4,5-dimethylethylene carbonate. From the viewpoint of improving high-temperature storage characteristics.
- ethylene carbonate and chain carbonate examples include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethyl Examples thereof include methyl carbonate, ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
- a combination in which propylene carbonate is further added to the combination of these ethylene carbonate and chain carbonate is also mentioned as a preferable combination.
- the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, particularly preferably 95: 5 to 50:50.
- the proportion of propylene carbonate in the entire non-aqueous solvent is preferably 0.1% by volume or more, more preferably 1% by volume or more, still more preferably 2% by volume or more, and preferably 20% by volume or less, more preferably Is 8% by volume or less, more preferably 5% by volume or less. It is preferable to contain propylene carbonate in this concentration range because the low temperature characteristics may be further improved while maintaining the combination characteristics of ethylene carbonate and dialkyl carbonate.
- those containing asymmetric chain alkyl carbonates as chain carbonates are more preferable, especially ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl.
- Those containing ethylene carbonate, symmetric chain carbonates, and asymmetric chain carbonates such as methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferred because of a good balance between cycle characteristics and large current discharge characteristics.
- the asymmetric chain carbonate is preferably ethyl methyl carbonate, and the alkyl group of the chain carbonate preferably has 1 to 2 carbon atoms.
- monofluoroethylene carbonate and chain carbonate examples include monofluoroethylene carbonate and dimethyl carbonate, monofluoroethylene carbonate and diethyl carbonate, monofluoroethylene carbonate and ethyl methyl carbonate, monofluoroethylene carbonate and dimethyl carbonate, Examples include diethyl carbonate, monofluoroethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, monofluoroethylene carbonate, diethyl carbonate and ethyl methyl carbonate, monofluoroethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
- a combination obtained by further adding ethylene carbonate and / or propylene carbonate to the combination of these monofluoroethylene carbonate and chain carbonate is also mentioned as a preferable combination.
- the volume ratio of monofluoroethylene carbonate to ethylene carbonate and / or propylene carbonate when ethylene carbonate and / or propylene carbonate is added is preferably 1: 3 to 3: 1, particularly preferably 1: 2 to 2: 1. .
- ethylene carbonate and / or propylene carbonate is contained in this concentration range, the electrical conductivity of the electrolytic solution can be ensured while forming a stable protective film on the negative electrode.
- the proportion of diethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, still more preferably 25% by volume or more, particularly Preferably it is 30% by volume or more, preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 75% by volume or less, and particularly preferably 70% by volume or less. Gas generation during high temperature storage may be suppressed.
- the proportion of dimethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, still more preferably 25% by volume or more, particularly Preferably it is 30% by volume or more, preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 75% by volume or less, and particularly preferably 70% by volume or less.
- the load characteristics of the battery may be improved.
- the volume ratio of dimethyl carbonate to ethyl methyl carbonate in all non-aqueous solvents is 1.1 or more in terms of improving the electric conductivity of the electrolyte and improving the battery characteristics after storage. Is preferably 1.5 or more, more preferably 2.5 or more.
- the volume ratio (dimethyl carbonate / ethyl methyl carbonate) is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 8 or less, from the viewpoint of improving battery characteristics at low temperatures.
- Other solvents such as cyclic ethers, chain ethers, sulfur-containing organic solvents, phosphorus-containing organic solvents, and aromatic fluorine-containing solvents may be mixed.
- a preferable non-aqueous solvent is that one organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, or a mixed solvent consisting of two or more organic solvents selected from the group is used as the whole. It occupies 60% by volume or more.
- a non-aqueous electrolyte using this mixed solvent may reduce solvent evaporation and liquid leakage even when used at high temperatures.
- the total of ethylene carbonate and propylene carbonate in the non-aqueous solvent is preferably 70% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and the volume of ethylene carbonate and propylene carbonate.
- the ratio is preferably 30:70 to 60:40, the balance between cycle characteristics and high temperature storage characteristics may be improved.
- the volume of the non-aqueous solvent is a measured value at 25 ° C., but a measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.
- the non-aqueous electrolyte solution of the present invention contains a compound represented by formula (1).
- the compound represented by Formula (1) is a compound having a carboxylic acid ester structure, a sulfonic acid ester structure, and / or a phosphoric acid ester structure.
- a polyvalent metal salt suitable for enhancing the thermal stability of the negative electrode film when the compound represented by formula (1) is electrochemically reduced on the negative electrode surface It is considered that the effect of promoting the production of (for example, lithium salt) is expressed.
- these structures can be efficiently formed with high yield, it can be said that the structure represented by the formula (1) is easily synthesized and plays a role of suppressing manufacturing costs.
- the carbon number of Z in the formula (1) is 4 to 12. It is considered that when the carbon number of Z is 4 to 12, the size of the molecule increases, and the solubility of the above-described polyvalent metal salt (for example, lithium salt) in the electrolytic solution is suppressed. This effect is more effective when Z is nonpolar, for example, when Z is a chain alkylene group. It is considered that the negative electrode film is further stabilized and side reactions are suppressed by suppressing the solubility of the polyvalent metal salt (for example, lithium salt) in the electrolytic solution. As a result, it is considered that the cycle capacity retention rate and the low-temperature resistance characteristics are improved.
- X represents an organic group containing a hetero atom, and represents an organic group having at least one oxygen atom as the hetero atom
- Y represents a sulfur atom, a phosphorus atom or a carbon atom
- n represents an integer of 1 or 2
- m represents an integer of 2 to 4
- l represents an integer of 1 or 2
- Z represents an organic group which may have a hetero atom having 4 to 12 carbon atoms.
- the hetero atom represents an atom other than a carbon atom and a hydrogen atom.
- the organic group containing a hetero atom is, for example, a structure containing an atom selected from the group consisting of a nitrogen atom, a phosphorus atom, a boron atom, a sulfur atom, a silicon atom, an oxygen atom and a halogen atom, but at least one oxygen atom It shall have.
- the organic group containing a heteroatom may have a structure not containing a carbon atom, but preferably contains a carbon atom.
- the carbon number of the organic group containing a hetero atom is preferably 1 or more, more preferably 2 or more, preferably 15 or less, more preferably 10 or less.
- the organic group containing a heteroatom may have a structure not containing a carbon atom, but has at least one oxygen atom.
- X is an organic group containing a hetero atom, and has at least one oxygen atom as a hetero atom.
- a hetero atom at least one is an oxygen atom
- a more suitable polyvalent metal salt for example, lithium salt
- Specific examples of X include the following.
- R 1 to R 4 independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
- Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group. Of these, an alkyl group is preferred. As an alkyl group, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
- the specific examples of X the following structure containing a sulfonyl group or a carbonyl group is more preferable. These structures are easy to bond and cleave on the negative electrode surface, and by having a plurality of these, the thermal stability of the negative electrode film can be extremely enhanced.
- R 1 to R 3 are as defined above.
- the following structure is more preferable.
- R 1 to R 3 are as defined above.
- the following structure containing a carbonyl group is more preferable.
- R 1 to R 3 are as defined above.
- Y is a sulfur atom, a phosphorus atom or a carbon atom, but a sulfur atom or a carbon atom is more preferable from the viewpoint of improving battery characteristics, and a sulfur atom is most preferable.
- N and l are integers of 1 or 2, but when Y is a sulfur atom, n and l represent 1 and 2, or 1 and 1, respectively, and n and l represent 2 and 1, respectively. The case is preferred.
- n and l both represent 1.
- m is an integer of 2 to 4, and is particularly preferably 2 from the viewpoint of the thermal stability of the negative electrode film.
- Z is an organic group that may have a heteroatom having 4 to 12 carbon atoms.
- the organic group which may have a hetero atom includes, for example, an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, a phosphorus atom, a boron atom, a sulfur atom, a silicon atom, an oxygen atom and a halogen atom.
- the carbon number is preferably 4 to 10, and more preferably 4 to 6.
- the carbon atom may be linear or branched, but is preferably linear.
- the organic group for Z is preferably an alkylene group, an ether group or an ester group, more preferably an alkylene group or an ether group, still more preferably an alkylene group, and particularly preferably a linear alkylene group having 4 to 6 carbon atoms.
- Z is a linking group that connects Y to each other, and a plurality of Ys may be bonded to any atom in Z, and even if they are bonded to the same atom in Z, they may be bonded to different atoms. It may be bonded. Preferably, they are bonded to different atoms in Z.
- Preferred examples of the compound represented by the formula (1) include the following.
- R a independently represents an alkyl group having 1 to 4 carbon atoms
- R b independently represents an alkyl group having 1 to 4 carbon atoms
- p is a compound represented by the integer of 4-6.
- formula (30) In addition to the compound represented by formula (2), formula (30): In addition to the compound represented by formula (2), formula (30): In the formula, p is preferably a compound represented by an integer of 4 to 6.
- W represents an organic group containing a hetero atom, and represents an organic group having at least one oxygen atom as the hetero atom
- m represents an integer of 2 to 4
- Z will be described by taking as an example a sulfonate ester represented by an organic group which may have a heteroatom having 4 to 12 carbon atoms.
- W is an alcoholic hydroxyl group when the part bonded to W is replaced with a hydroxyl group.
- the sulfonic acid ester represented by the formula (10) can be obtained by reacting a corresponding sulfonic acid chloride with a compound having an alcohol skeleton.
- S-based compounds represented by monosulfonic acid esters are used in a wide range of technical fields ranging from pharmaceutical uses to secondary battery material uses, and there are many reports on their production. However, with regard to polysulfonic acid esters, only the following two reports can be said to specifically describe production methods for some sulfonic acid esters included in formula (10) (Reference 1: US Pat. No. 3,748,132A, Literature 2: Chemistry “of Materials” (2004), 16 (9), 1770-1774).
- Document 1 describes a method for producing a disulfonic acid ester by a reaction between a disulfonic acid chloride and an alcohol compound.
- the disulfonic acid ester of this document is synthesized as an intermediate and is subjected to the next reaction without special purification. Therefore, it is impossible to deny the possibility that disulfonic acid chloride and alcohol form remain, and it is also impossible to deny the mixture of monosulfonic acid ester that has reacted only in one of the two reaction points, but these were removed.
- a method for isolating high purity products is not shown.
- disulfonic acid ester is synthesized by reaction of butanedisulfonic acid chloride with 2-hydroxyethyl methacrylate, but there is no description about purification, and it cannot be denied that impurities are mixed.
- a method for purifying the obtained sulfonic acid ester is not specifically shown.
- chemicals used as raw materials, reaction accelerators such as bases, and compounds that have reacted only at a part of the reaction points may also be present, so the target product must be purified with high purity.
- the setting of a specific purification method is indispensable.
- the purity of the compound becomes important, and establishment of a purification method is essential.
- the present invention also provides a method for producing a sulfonic acid ester represented by the formula (10) with high purity.
- the target product can be obtained with high purity by this method.
- the present invention relates to formula (10): Where W represents an organic group containing a hetero atom, and represents an organic group having at least one oxygen atom as the hetero atom, m represents an integer of 2 to 4, Z represents a method for producing a sulfonic acid ester represented by an organic group which may have a hetero atom having 4 to 12 carbon atoms, Formula (11): Where m and Z are synonymous with the formula (10), and a sulfonic acid chloride represented by the formula (12): W-OH
- W is synonymous with formula (10), a step of reacting a compound having an alcoholic hydroxyl group represented by: and a step of taking out the sulfonate ester represented by formula (10) as a solid by crystallization
- the present invention relates to a method for producing a sulfonic acid ester.
- W, Z, and m apply the description regarding X, Z, and m in the compound represented by the formula (1).
- the hydroxyl group is an alcoholic hydroxyl group.
- W include an organic group having an aliphatic moiety.
- sulfonic acid esters can be synthesized from the corresponding sulfonic acid chloride and a compound having an alcoholic hydroxyl group, respectively.
- the compound represented by p represents an integer of 4 to 6, is represented by the formula (21):
- p represents a sulfonic acid chloride represented by an integer of 4 to 6, represented by formula (22):
- R a independently represents an alkyl group having 1 to 4 carbon atoms R b can be obtained independently by reacting a compound having an alcoholic hydroxyl group represented by an alkyl group having 1 to 4 carbon atoms.
- the reaction between the sulfonic acid chloride and the compound having an alcoholic hydroxyl group can be carried out without solvent or in a solvent.
- the reaction is preferably performed in a non-aqueous solvent at a low temperature by adding a base as a reaction accelerator.
- a non-aqueous solvent can be used, and it is preferable to use a solvent that does not react with sulfonic acid chloride.
- aliphatic hydrocarbons such as pentane, hexane, heptane, octane, petroleum ether; ethers such as diethyl ether, diisopropyl ether, t-butyl methyl ether, anisole, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether; Halogenated hydrocarbons such as methylene, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, bromopropane, chlorobenzene, dichlorobenzene; cyanohydrocarbons such as acetonitrile, propionitrile, butyronitrile, benz
- solvents may be used alone or in combination of two or more. Further, water may be mixed and used as long as the sulfonic acid chloride is not decomposed. From the viewpoint of cost, aliphatic hydrocarbons, ethers, cyano hydrocarbons, esters, aromatic hydrocarbons, and ketones are preferable, and aliphatic hydrocarbons, ethers, esters, aromatic hydrocarbons, and ketones are more preferable. It is.
- the amount of the solvent used is usually in the range of 1 to 50 times the weight of the corresponding sulfonic acid chloride, and preferably in the range of 1 to 20 times the weight.
- examples of the base include carbonates such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; hydroxide salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride; hydrogen Inorganic bases such as sodium hydride, potassium hydride, metallic sodium and metallic potassium; metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide and sodium-t-butoxide; amines such as triethylamine and trimethylamine; pyridine, Examples thereof include pyridines such as picoline; anilines such as N, N-dimethylaniline; alkyl metal compounds such as methyl lithium, ethyl lithium, propyl lithium and butyl lithium; aryl metal compounds such as phenyl lithium.
- the base can be appropriately selected depending on the type of solvent used. From the viewpoint of solubility in a reaction solvent and ease of handling, amines, pyridine
- the amount of the base used is preferably in the range of 1 to 10 equivalents, more preferably in the range of 1 to 3 equivalents, based on the alcoholic hydroxyl group in the compound having an alcoholic hydroxyl group.
- the upper limit temperature of the esterification reaction is preferably 80 ° C. or less, more preferably 60 ° C. or less, and further preferably 50 ° C. or less. Since this reaction is an exothermic reaction, by setting the upper limit temperature in this way, reaction runaway can be suppressed, and thermal decomposition of the produced sulfonic acid ester can also be suppressed. Further, the minimum temperature of the esterification reaction is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 25 ° C. or higher, and further preferably ⁇ 20 ° C. or higher. By setting the lower limit temperature in this way, it is possible to avoid the risk of reaction stoppage or reaction accumulation.
- the time for the esterification reaction is preferably 30 minutes or longer, more preferably 1 hour or longer. Since sulfonic acid chloride has multiple reaction points, if the reaction time is short, there may be a mixture of products that have reacted only at some reaction points, but such a situation can be easily avoided. be able to.
- the upper limit of the reaction is not particularly limited, but the reaction time can be 48 hours or less, preferably 24 hours or less, in order to avoid degradation of productivity due to decomposition of the produced sulfonic acid ester or prolonged time. It is not longer than time, more preferably not longer than 10 hours.
- the esterification reaction can be performed under normal pressure, increased pressure, or reduced pressure. From the viewpoint of productivity and safety, it is preferably carried out under normal pressure conditions.
- the reaction apparatus for the esterification reaction is not particularly limited, and a known metal or those whose inner surfaces are lined with glass, resin, or the like, or a glass or resin apparatus can be used. From the viewpoint of strength and safety, an apparatus made of metal or glass lining on the inner surface thereof is preferable.
- the metal material known materials can be used, for example, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic stainless steel such as SUS310, SUS304, SUS316, clad steel, Examples thereof include cast iron, copper, copper alloy, aluminum, inconel, hastelloy, titanium, and the like.
- the reagent used for the reaction of the present invention may be a commercially available one, or may be used after purification. You may manufacture and use from another compound. Although there is no particular limitation on the purity, a high-purity reagent with few impurities derived from the raw material is preferable because the reaction has a plurality of reaction points, and it is preferably 90% by mass or more.
- the sulfonic acid chloride may be a commercially available product or may be used after purification. If there is no commercial product, it may be manufactured and used separately. When manufacturing separately, the following method is mentioned, for example. a) Preparation by oxidative chlorination of the corresponding alkylthioronium salt: eg) Synlett (2013), 24 (16), 2165-2169 .; Journal of the Chemical Society (1952), 3334-40. b) Production method by oxidative chlorination of the corresponding thiol: Example) Inorganica Chimica Acta (2011), 369 (1), 45-48 .; Industrial & Engineering Chemistry Process Design and Development (1964), 3 (2) , 164-9.
- the method of a) via an alkylthioronium salt is preferable because the reaction rate is high, the desired sulfonic acid chloride can be obtained in a short time, and post-treatment is easy.
- the counter ion of the alkylthioronium salt is bromide ion or iodide ion
- sulfonic acid chloride, sulfonic acid bromide, and sulfonic acid iodide may be mixed from the oxidative chlorination reaction. It can be converted to the desired sulfonic acid ester by reaction with the compound having it. Therefore, these acid halides may be mixed.
- the reagent used for the oxidative chlorination of alkylthioronium salt is not particularly limited as long as it is a reagent that generates a chlorine cation, but chlorine gas, sodium hypochlorite aqueous solution, sodium chlorite, NCS, and trichloroisocyanuric acid are available. It is preferable because the reaction rate and reaction efficiency are high.
- hypochlorous acid aqueous solution and sodium chlorite are more preferable from the viewpoint of easiness of post-treatment of the reaction, cost of the oxidant reagent, and environmental load, and hypochlorous acid aqueous solution is most preferable from the viewpoint of easy handling.
- These oxidative chlorinating agents may be used as they are, or may be used after purification, or may be produced from other compounds and used.
- the aqueous sodium hypochlorite solution is available in various concentrations. However, the higher the concentration of sodium hypochlorite, the higher the pot efficiency and the higher the productivity. % Or more, more preferably 10% by mass or more, and most preferably 12% by mass or more.
- the counter ion of the alkylthioronium salt is not particularly limited, but halide ions, sulfate ions and the like have been reported, and chloride ions, bromide ions, and iodide ions are preferred from the viewpoint that they can be easily synthesized from the corresponding haloalkanes. These counter ions may be used alone or as a mixture of two or more kinds of counter ions.
- crystallization refers to an operation of taking out the sulfonic acid ester as a solid from a solution containing the sulfonic acid ester represented by the formula (10).
- the reaction product of the corresponding sulfonic acid chloride and the compound having an alcoholic hydroxyl group is optionally filtered and concentrated, and then mixed with a solvent, which can be subjected to a crystallization step.
- the sulfonic acid ester may be completely dissolved or partially precipitated in the solvent. Since the ability to remove impurities is remarkably improved by performing the crystallization operation after completely dissolving, it is preferable to completely dissolve it once.
- the operation for removing the sulfonic acid ester from the solution includes a method of precipitating a solid by increasing the concentration by volatilizing and concentrating the solvent under normal pressure or reduced pressure, and another solvent having a lower solubility of the target product as a poor solvent.
- a precipitation method a method in which a solvent and a poor solvent are combined, a method in which the temperature of the solution is lowered from the melting temperature, and the target product is precipitated are exemplified.
- a method of adding a poor solvent and a method of lowering the temperature are preferable because the target product can be precipitated efficiently in a short time.
- a method of lowering the temperature is more preferable because it can suppress an increase in the size of the reaction kettle, reduce a work load such as a filtration operation, and obtain good productivity.
- the target product can be obtained with high purity by performing crystallization at least once, preferably 1 to 3 times.
- the upper limit temperature for adjusting the solution containing the sulfonic acid ester is the upper limit of the boiling point of the solvent used, but is preferably 80 ° C. or less, more preferably 60 ° C. or less, and still more preferably 50 ° C. It is as follows. If it is this upper limit temperature range, it is anticipated that a sulfonate ester can exist stably in a solution. Since the target sulfonic acid ester can be precipitated as a solid by lowering the temperature, the temperature setting on the low temperature side is not limited as long as it is lower than the upper limit temperature, but is preferably 40 ° C. or lower, more preferably 30 ° C or lower, more preferably 20 ° C or lower. By setting the temperature on the low temperature side, the solubility of the sulfonate ester decreases, and the target product can be obtained in good yield.
- the solvent is not particularly limited as long as it is a non-aqueous solvent capable of dissolving the target sulfonic acid ester, but is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, 1- Pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-2-butanol, cyclohexanol, ethylene glycol, trimethylene glycol, etc.
- Alcohols such as diethyl ether, diisopropyl ether, t-butyl methyl ether, anisole, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether; methylene chloride, chloroform , Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, trichloroethane, bromopropane, chlorobenzene, dichlorobenzene; cyanohydrocarbons such as acetonitrile, propionitrile, butyronitrile, benzonitrile; ethyl acetate, butyl acetate And esters such as acetone and methyl ethyl ketone. These solvents may be used alone or in combination of two or more. Of these, low boiling alcohols such as methanol and ethanol are preferred because of the solubility of the base used in the reaction and salts thereof and the ease
- the poor solvent is not particularly limited as long as the solubility of the target sulfonic acid ester is lower than that of the solvent and is miscible with the solvent, but from the viewpoint of solubility, aliphatic such as pentane, hexane, heptane, octane, petroleum ether Hydrocarbons: aromatic hydrocarbons such as benzene, toluene and nitrobenzene. These solvents may be used alone or in combination of two or more. Further, either the volume of the solvent or the poor solvent may be large. Moreover, as long as it mixes with a solvent, if it is a small amount, you may use water.
- the solvent used in the crystallization step may remain in the sulfonic acid ester solid represented by the formula (10) obtained by crystallization, it is preferably removed by drying.
- the removal method is not particularly limited, but a method of removing the solvent under reduced pressure is preferable.
- the temperature condition is preferably 80 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 50 ° C. or lower, preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 10 ° C. or higher. Within such a range, the solvent can be sufficiently removed while avoiding thermal decomposition of the target sulfonic acid ester.
- the removal time is preferably 30 minutes or more, more preferably 1 hour or more, still more preferably 2 hours or more, and preferably 48 hours or less, more preferably from the viewpoint of both sufficient removal and production efficiency. Is 36 hours or less, more preferably 24 hours or less.
- the compound represented by Formula (1) may be used individually by 1 type, and may have 2 or more types by arbitrary combinations and ratios. There is no restriction
- the blending amount can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and 5% by mass or less, preferably 4% by mass. % Or less, more preferably 2% by mass or less.
- effects such as output characteristics, load characteristics, low temperature characteristics, cycle characteristics, and high temperature storage characteristics are further improved.
- it is preferable that the compound represented by the formula (1) is purified in advance within a range in which the productivity is not significantly reduced and a compound having as few impurities as possible is used.
- an auxiliary agent may be appropriately used depending on the purpose in addition to the compound represented by the formula (1).
- auxiliary agents the following cyclic carbonates having a carbon-carbon unsaturated bond, unsaturated cyclic carbonates having a fluorine atom, monofluorophosphates and difluorophosphates, overcharge inhibitors, and other auxiliary agents Etc.
- the unsaturated cyclic carbonate is not particularly limited as long as it is a cyclic carbonate having a carbon-carbon double bond, and any unsaturated carbonate can be used.
- the cyclic carbonate having a substituent having an aromatic ring is also included in the unsaturated cyclic carbonate.
- the unsaturated cyclic carbonate include vinylene carbonates, ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond, phenyl carbonates, vinyl carbonates, and allyl carbonates.
- vinylene carbonates examples include vinylene carbonate (hereinafter sometimes abbreviated as “VC”), methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, Examples include 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, 4,5-diallyl vinylene carbonate, and the like.
- VC vinylene carbonate
- methyl vinylene carbonate methyl vinylene carbonate
- phenyl vinylene carbonate 4,5-diphenyl vinylene carbonate
- vinyl vinylene carbonate examples include 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, 4,5-diallyl vinylene carbonate, and the like.
- Examples of ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond include vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, 4-allyl-5. -Vinyl ethylene carbonate, phenyl ethylene carbonate, 4,5-diphenyl ethylene carbonate, 4-phenyl-5-vinyl ethylene carbonate, 4-allyl-5-phenyl ethylene carbonate, allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, 4 -Methyl-5-allylethylene carbonate and the like.
- preferable unsaturated cyclic carbonates for use in combination with the compound represented by the formula (1) are vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl vinylene carbonate, 4,5-vinyl vinylene.
- Carbonate, allyl vinylene carbonate, 4,5-diallyl vinylene carbonate, vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, 4- Methyl-5-allylethylene carbonate and 4-allyl-5-vinylethylene carbonate are more preferably used because they form a stable interface protective film.
- the molecular weight of the unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
- the molecular weight is preferably 86 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the unsaturated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will fully be expressed easily.
- the molecular weight of the unsaturated cyclic carbonate is more preferably 150 or less.
- the production method of the unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method.
- the unsaturated cyclic carbonate may be used alone or in combination of two or more in any combination and ratio. Moreover, the compounding quantity of unsaturated cyclic carbonate is not restrict
- the amount of the unsaturated cyclic carbonate is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, in 100% by mass of the non-aqueous electrolyte. , Preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.
- the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exerted. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
- a cyclic carbonate having an unsaturated bond and a fluorine atom (hereinafter sometimes abbreviated as “fluorinated unsaturated cyclic carbonate”) is also preferably used.
- the number of fluorine atoms contained in the fluorinated unsaturated cyclic carbonate is not particularly limited as long as it is 1 or more. Especially, a fluorine atom is 6 or less normally, Preferably it is 4 or less, and the thing of 1 piece or 2 pieces is the most preferable.
- fluorinated unsaturated cyclic carbonate examples include a fluorinated vinylene carbonate derivative, a fluorinated ethylene carbonate derivative substituted with an aromatic ring or a substituent having a carbon-carbon double bond.
- Fluorinated vinylene carbonate derivatives include 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-phenyl vinylene carbonate, 4-allyl-5-fluoro vinylene carbonate, 4-fluoro-5- And vinyl vinylene carbonate.
- fluorinated ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon double bond examples include 4-fluoro-4-vinylethylene carbonate, 4-fluoro-4-allylethylene carbonate, 4-fluoro-5 -Vinylethylene carbonate, 4-fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate, 4,4-difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate 4,5-difluoro-4-allylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4-fluoro-4,5-diallylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate , 4,5-Diff Oro-4,5-diallylethylene carbonate, 4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylene carbonate, 4,4-difluoro-5-phenyl
- fluorinated unsaturated cyclic carbonates particularly preferred for use in combination with the compound represented by formula (1) include 4-fluorovinylene carbonate, 4-fluoro-5-methylvinylene carbonate, 4-fluoro-5-vinyl.
- the molecular weight of the fluorinated unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
- the molecular weight is preferably 86 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the fluorinated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed.
- the production method of the fluorinated unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method.
- the molecular weight is more preferably 150 or less.
- Fluorinated unsaturated cyclic carbonates may be used alone or in combination of two or more in any combination and ratio. Moreover, the compounding quantity of a fluorinated unsaturated cyclic carbonate is not restrict
- the blending amount of the fluorinated unsaturated cyclic carbonate is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more, in 100% by mass of the non-aqueous electrolyte solution. Moreover, it is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.
- the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exerted. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
- the counter cations of monofluorophosphate and difluorophosphate are not particularly limited, but lithium, sodium, potassium, magnesium, calcium, and NR 5 R 6 R 7 R 8 (wherein R 5 to R 8 Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms).
- the organic group having 1 to 12 carbon atoms represented by R 5 to R 8 of ammonium is not particularly limited, and examples thereof include an alkyl group which may be substituted with a halogen atom, a halogen atom or an alkyl group. And an optionally substituted cycloalkyl group, an aryl group optionally substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group optionally having a substituent, and the like.
- R 5 to R 8 are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrogen atom-containing heterocyclic group, or the like.
- monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium difluorophosphate, sodium difluorophosphate, and potassium difluorophosphate. And lithium monofluorophosphate and lithium difluorophosphate are preferable, and lithium difluorophosphate is more preferable.
- Monofluorophosphate and difluorophosphate may be used alone or in combination of two or more in any combination and ratio.
- the compounding quantity of a monofluoro phosphate and a difluoro phosphate is not restrict
- the blending amount of the monofluorophosphate and the difluorophosphate is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% in 100% by mass of the nonaqueous electrolytic solution. It is at least 5% by mass, preferably at most 5% by mass, more preferably at most 4% by mass, still more preferably at most 3% by mass. Within this range, the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high temperature storage characteristics are reduced, the amount of gas generation is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid the situation.
- an overcharge inhibitor can be used in order to effectively suppress battery explosion / ignition when the non-aqueous electrolyte secondary battery is in an overcharged state or the like.
- aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; 2-fluorobiphenyl, Partially fluorinated products of the above aromatic compounds such as o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5-difluoroanisole and the like And a fluorine-containing anisole compound.
- aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene
- aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, terphenyl partially hydrogenated, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran are preferable. These may be used alone or in combination of two or more.
- a combination of cyclohexylbenzene and t-butylbenzene or t-amylbenzene biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene,
- aromatic compounds not containing oxygen such as t-amylbenzene
- oxygen-containing aromatic compounds such as diphenyl ether, dibenzofuran, etc.
- the blending amount of the overcharge inhibitor is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired.
- the overcharge inhibitor is preferably 0.1% by mass or more and 5% by mass or less in 100% by mass of the non-aqueous electrolyte solution. If it is this range, it will be easy to fully express the effect of an overcharge inhibiting agent, and it will be easy to avoid the situation where the battery characteristics, such as a high temperature storage characteristic, fall.
- the overcharge inhibitor is more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more, and more preferably 3% by mass or less, still more preferably. Is 2% by mass or less.
- auxiliaries include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, anhydrous Carboxylic anhydrides such as itaconic acid, diglycolic anhydride, cyclohexanedicarboxylic anhydride, and phenylsuccinic anhydride; 2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-divinyl Spiro compounds such as -2,4,8,10-tetraoxaspiro [5.5] undecane; ethylene sulfite, 1,3-propane sultone, 1-fluoro-1,3-propane
- the compounding amount of other auxiliary agents is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
- the other auxiliary agent is preferably 0.01% by mass or more and 5% by mass or less in 100% by mass of the non-aqueous electrolyte solution. Within this range, the effects of other auxiliaries can be sufficiently exhibited, and it is easy to avoid a situation in which battery characteristics such as high-load discharge characteristics deteriorate.
- the blending amount of other auxiliaries is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, more preferably 3% by mass or less, still more preferably 1% by mass or less. .
- the non-aqueous electrolyte solution of the present invention includes a non-aqueous electrolyte solution existing inside the non-aqueous electrolyte secondary battery.
- components of the non-aqueous electrolyte such as an electrolyte (for example, lithium salt), a non-aqueous solvent, a compound represented by the formula (1), and an optional auxiliary agent are separately synthesized and substantially isolated.
- non-aqueous electrolyte solution in a non-aqueous electrolyte secondary battery obtained by preparing a non-aqueous electrolyte solution from these and pouring it into a separately assembled battery
- the components of the non-aqueous electrolyte solution of the present invention are obtained separately in the battery and mixed in the battery to obtain the same composition as the non-aqueous electrolyte solution of the present invention, and further, the components constituting the non-aqueous electrolyte solution of the present invention are further added to the non-aqueous electrolyte solution.
- the same composition as that of the nonaqueous electrolytic solution of the present invention is obtained by generating in the electrolytic solution secondary battery is also included.
- the non-aqueous electrolyte solution of the present invention is suitable as an electrolyte solution for a secondary battery, for example, a lithium secondary battery among non-aqueous electrolyte secondary batteries.
- the non-aqueous electrolyte secondary battery of the present invention can adopt a known structure.
- the negative electrode and the positive electrode capable of inserting and extracting metal ions (for example, lithium ions), and the non-aqueous system of the present invention.
- An electrolyte solution is an electrolyte solution for a secondary battery, for example, a lithium secondary battery among non-aqueous electrolyte secondary batteries.
- the negative electrode active material used for the negative electrode is not particularly limited as long as it can electrochemically occlude and release metal in (eg, lithium ions). Specific examples include carbonaceous materials, alloy materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily.
- the negative electrode active material examples include carbonaceous materials, alloy materials, lithium-containing metal composite oxide materials, and the like.
- a carbonaceous material used as a negative electrode active material (1) natural graphite, (2) a carbonaceous material obtained by heat-treating an artificial carbonaceous material and an artificial graphite material at least once in the range of 400 to 3200 ° C; (3) a carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different crystallinities and / or has an interface in contact with the different crystalline carbonaceous materials, (4) A material selected from a carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different orientations and / or has an interface in contact with the carbonaceous materials having different orientations.
- a good balance between initial irreversible capacity and high current density charge / discharge characteristics is preferable.
- the carbonaceous materials (1) to (4) may be used alone or in combination of two or more in any combination and ratio.
- the artificial carbonaceous material and artificial graphite material of (2) above include natural graphite, coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, those obtained by oxidizing these pitches, needle coke, pitch coke and Carbon materials that are partially graphitized, furnace black, acetylene black, organic pyrolysis products such as pitch-based carbon fibers, carbonizable organic materials and their carbides, or carbonizable organic materials are benzene, toluene, xylene, quinoline And a solution dissolved in a low-molecular organic solvent such as n-hexane, and carbides thereof.
- the single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements (that is, excluding carbon), more preferably aluminum, silicon and tin (hereinafter referred to as “ Simple metals) and alloys or compounds containing these atoms (sometimes abbreviated as “specific metal elements”). These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- a negative electrode active material having at least one kind of atom selected from a specific metal element, a metal simple substance of any one specific metal element, an alloy composed of two or more specific metal elements, one type or two or more specific types Alloys comprising metal elements and one or more other metal elements, as well as compounds containing one or more specific metal elements, and oxides, carbides, nitrides and silicides of the compounds And composite compounds such as sulfides or phosphides.
- these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.
- compounds in which these complex compounds are complexly bonded to several elements such as simple metals, alloys or non-metallic elements are also included.
- silicon and tin an alloy of these elements and a metal that does not operate as a negative electrode can be used.
- tin a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not operate as a negative electrode, and a nonmetallic element may be used. it can.
- any one simple metal of a specific metal element, an alloy of two or more specific metal elements, oxidation of a specific metal element In particular, silicon and / or tin metal simple substance, alloy, oxide, carbide, nitride and the like are preferable from the viewpoint of capacity per unit mass and environmental load.
- the lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium, but a material containing titanium and lithium is preferable from the viewpoint of high current density charge / discharge characteristics, A lithium-containing composite metal oxide material containing titanium is more preferable, and a composite oxide of lithium and titanium (hereinafter sometimes abbreviated as “lithium titanium composite oxide”). That is, it is particularly preferable to use a lithium titanium composite oxide having a spinel structure in a negative electrode active material for a non-aqueous electrolyte secondary battery because the output resistance is greatly reduced.
- lithium or titanium of the lithium titanium composite oxide is at least selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. Those substituted with one element are also preferred.
- the metal oxide is a lithium titanium composite oxide represented by the general formula (A). In the general formula (A), 0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3, It is preferable that 0 ⁇ z ⁇ 1.6 because the structure upon doping and dedoping of lithium ions is stable.
- M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
- M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
- (A) 1.2 ⁇ x ⁇ 1.4, 1.5 ⁇ y ⁇ 1.7, z 0
- This structure is particularly preferable because of a good balance of battery performance.
- Particularly preferred representative compositions of the above compounds are Li 4/3 Ti 5/3 O 4 in (a), Li 1 Ti 2 O 4 in (b), and Li 4/5 Ti 11/5 O in (c). 4 .
- the d value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction by the Gakushin method of carbonaceous materials is preferably 0.335 nm or more, and is usually 0.360 nm or less. 350 nm or less is preferable, and 0.345 nm or less is more preferable. Further, the crystallite size (Lc) of the carbonaceous material obtained by X-ray diffraction by the Gakushin method is preferably 1.0 nm or more, and more preferably 1.5 nm or more.
- the volume-based average particle diameter of the carbonaceous material is a volume-based average particle diameter (median diameter) determined by a laser diffraction / scattering method, and is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and 7 ⁇ m.
- the above is particularly preferable, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
- the volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. This is carried out using a total (LA-700 manufactured by Horiba Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material of the present invention.
- the Raman R value of the carbonaceous material is a value measured using an argon ion laser Raman spectrum method, and is usually 0.01 or more, preferably 0.03 or more, more preferably 0.1 or more, and usually 1.5 or less, preferably 1.2 or less, more preferably 1 or less, and particularly preferably 0.5 or less.
- the Raman half-width in the vicinity of 1580 cm ⁇ 1 of the carbonaceous material is not particularly limited, but is usually 10 cm ⁇ 1 or more, preferably 15 cm ⁇ 1 or more, and usually 100 cm ⁇ 1 or less, and 80 cm ⁇ 1 or less. 60 cm ⁇ 1 or less is more preferable, and 40 cm ⁇ 1 or less is particularly preferable.
- the Raman R value and the Raman half width are indices indicating the crystallinity of the surface of the carbonaceous material, but the carbonaceous material has appropriate crystallinity from the viewpoint of chemical stability, and Li enters through charge and discharge. It is preferable that the crystallinity is such that the sites between the layers are not lost, that is, the charge acceptability is not lowered. In the case where the density of the negative electrode is increased by press after applying to the current collector, it is preferable to take account of this because crystals tend to be oriented in a direction parallel to the electrode plate.
- the Raman R value or the Raman half width is in the above range, a suitable film can be formed on the negative electrode surface to improve the storage characteristics, cycle characteristics, and load characteristics, and the efficiency associated with the reaction with the non-aqueous electrolyte solution Reduction and gas generation can be suppressed.
- the measurement of the Raman spectrum using a Raman spectrometer (manufactured by JASCO Corporation Raman spectrometer), the sample is naturally dropped into the measurement cell and filled, and while irradiating the sample surface in the cell with argon ion laser light, This is done by rotating the cell in a plane perpendicular to the laser beam.
- the Raman R value calculated by the measurement is defined as the Raman R value of the carbonaceous material of the present invention.
- the half width of the peak PA near 1580 cm ⁇ 1 of the obtained Raman spectrum is measured, and this is defined as the Raman half width of the carbonaceous material of the present invention.
- said Raman measurement conditions are as follows. Argon ion laser wavelength: 514.5nm ⁇ Laser power on the sample: 15-25mW ⁇ Resolution: 10-20cm -1 Measurement range: 1100 cm ⁇ 1 to 1730 cm ⁇ 1 ⁇ Raman R value, Raman half width analysis: Background processing ⁇ Smoothing processing: Simple average, 5 points of convolution
- BET specific surface area of the carbonaceous material is a value of the measured specific surface area using the BET method is usually 0.1 m 2 ⁇ g -1 or more, 0.7 m 2 ⁇ g -1 or more, 1. 0 m 2 ⁇ g -1 or more, and particularly preferably 1.5 m 2 ⁇ g -1 or more, generally not more than 100 m 2 ⁇ g -1, preferably 25 m 2 ⁇ g -1 or less, 15 m 2 ⁇ More preferably, g ⁇ 1 or less is preferable, and 10 m 2 ⁇ g ⁇ 1 or less is particularly preferable.
- the specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately prepared so that the value of the relative pressure is 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used.
- the specific surface area determined by the measurement is defined as the BET specific surface area of the carbonaceous material of the present invention.
- the circularity is measured as the degree of the sphere of the carbonaceous material, it is preferably within the following range.
- the degree of circularity of the particles having a carbonaceous material particle size in the range of 3 to 40 ⁇ m is desirably close to 1, and is preferably 0.1 or more, more preferably 0.5 or more, and more preferably 0.8 or more, 0.85 or more is more preferable, and 0.9 or more is particularly preferable.
- the filling property is improved and the resistance between the particles can be suppressed as the circularity is larger, so that the high current density charge / discharge characteristics are improved. Therefore, it is preferable that the circularity is as high as the above range.
- the circularity is measured using a flow type particle image analyzer (FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute.
- the detection range is specified as 0.6 to 400 ⁇ m, and the particle size is measured in the range of 3 to 40 ⁇ m.
- the circularity determined by the measurement is defined as the circularity of the carbonaceous material of the present invention.
- the method for improving the degree of circularity is not particularly limited, but a spheroidized sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable.
- spheroidizing treatment include a method of mechanically approaching a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by the binder or the adhesive force of the particles themselves, etc. Is mentioned.
- the tap density of the carbonaceous material is usually 0.1 g ⁇ cm ⁇ 3 or more, preferably 0.5 g ⁇ cm ⁇ 3 or more, more preferably 0.7 g ⁇ cm ⁇ 3 or more, and 1 g ⁇ cm ⁇ 3 or more. particularly preferred, and is preferably 2 g ⁇ cm -3 or less, more preferably 1.8 g ⁇ cm -3 or less, 1.6 g ⁇ cm -3 or less are particularly preferred.
- the tap density is in the above range, battery capacity can be ensured and increase in resistance between particles can be suppressed.
- the tap density is measured by passing through a sieve having an opening of 300 ⁇ m, dropping the sample onto a 20 cm 3 tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated from the volume at that time and the mass of the sample. The tap density calculated by the measurement is defined as the tap density of the carbonaceous material of the present invention.
- the orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less. When the orientation ratio is in the above range, excellent high-density charge / discharge characteristics can be ensured.
- the upper limit of the above range is the theoretical upper limit value of the orientation ratio of the carbonaceous material.
- the orientation ratio is measured by X-ray diffraction after pressure molding the sample.
- Set the molded body obtained by filling 0.47g of the sample into a molding machine with a diameter of 17mm and compressing it with 58.8MN ⁇ m-2 so that it is flush with the surface of the sample holder for measurement.
- X-ray diffraction is measured.
- From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.
- the orientation ratio calculated by the measurement is defined as the orientation ratio of the carbonaceous material of the present invention.
- the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
- ⁇ Target Cu (K ⁇ ray) graphite monochromator
- Light receiving slit 0.15
- Scattering slit 0.5 degree / measurement range and step angle / measurement time: (110) plane: 75 degrees ⁇ 2 ⁇ ⁇ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ⁇ 2 ⁇ ⁇ 57 degrees 1 degree / 60 seconds
- the aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. Within the above range, streaking during electrode plate formation is suppressed, and more uniform coating is possible, so that excellent high current density charge / discharge characteristics can be ensured.
- the lower limit of the above range is the theoretical lower limit value of the aspect ratio of the carbonaceous material.
- the aspect ratio by magnifying the carbonaceous material particles with a scanning electron microscope. Carbonaceous material particles when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 ⁇ m or less and rotating and tilting the stage on which the sample is fixed. The longest diameter A and the shortest diameter B orthogonal thereto are measured, and the average value of A / B is obtained. The aspect ratio (A / B) obtained by the measurement is defined as the aspect ratio of the carbonaceous material of the present invention.
- Rhombohedral crystal ratio The rhombohedral crystal ratio defined in the present invention is expressed by the following formula based on the ratio of rhombohedral structure graphite layer (ABC stacking layer) and hexagonal structure graphite layer (AB stacking layer) by X-ray wide angle diffraction (XRD). Can be obtained.
- Rhombohedral crystal ratio (%) integrated intensity of ABC (101) peak of XRD ⁇ XRD AB (101) peak integrated intensity ⁇ 100
- the rhombohedral crystal ratio is usually 0% or more, preferably greater than 0%, more preferably 3% or more, still more preferably 5% or more, particularly preferably 12% or more, and usually 35% or less, preferably Is 27% or less, more preferably 24% or less, and particularly preferably 20% or less.
- the rhombohedral crystal ratio of 0% indicates that no XRD peak derived from the ABC stacking layer is detected.
- “greater than 0%” means that even a slight XRD peak derived from the ABC stacking layer is detected.
- the rhombohedral crystal ratio is too large, since there are many defects in the crystal structure of the negative electrode active material, the amount of Li insertion tends to decrease and it is difficult to obtain a high capacity. In addition, since the electrolyte is decomposed during the cycle due to the defects, the cycle characteristics tend to deteriorate. On the other hand, if the rhombohedral crystal ratio is within the range of the present invention, for example, there are few defects in the crystal structure of the negative electrode active material, the reactivity with the electrolyte is small, and the electrolyte is not consumed during the cycle. It is preferable because of its excellent characteristics.
- the XRD measurement method for determining the rhombohedral crystal ratio is as follows. A 0.2 mm sample plate is filled so that the negative electrode active material powder is not oriented, and measured with an X-ray diffraction apparatus (for example, X'Pert Pro MPD manufactured by PANalytical, with CuK ⁇ ray, output 45 kV, 40 mA). Using the obtained diffraction pattern, the peak integrated intensity is calculated by profile fitting using the asymmetric Pearson VII function using analysis software JADE5.0, and the rhombohedral crystal ratio is obtained from the above formula.
- an X-ray diffraction apparatus for example, X'Pert Pro MPD manufactured by PANalytical, with CuK ⁇ ray, output 45 kV, 40 mA.
- the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
- ⁇ Target Cu (K ⁇ ray) graphite monochromator
- ⁇ Slit Solar slit 0.04 degree divergence slit 0.5 degree side divergence mask 15mm Anti-scattering slit 1 degree
- Measurement range and step angle / measurement time (101) plane: 41 ° ⁇ 2 ⁇ ⁇ 47.5 ° 0.3 ° / 60 sec. Background correction: A line between 42.7 and 45.5 ° is connected by a straight line and subtracted as background.
- -Peak of rhombohedral-structure graphite particle layer refers to a peak around 43.4 degrees.
- -Peak of hexagonal structure graphite particle layer It indicates a peak around 44.5 degrees.
- any known method can be used for producing the electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.
- a method of forming a thin film layer (negative electrode active material layer) containing the above-described negative electrode active material by a technique such as vapor deposition, sputtering, or plating is also used.
- the current collector for holding the negative electrode active material As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable from the viewpoint of ease of processing and cost.
- the shape of the current collector may be, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, or the like when the current collector is a metal material.
- a metal thin film is preferable, and a copper foil is more preferable, and a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method are more preferable, and both can be used as a current collector.
- the thickness of the current collector is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, and usually 100 ⁇ m or less, preferably 50 ⁇ m or less, from the viewpoint of securing battery capacity and handling properties.
- the ratio of the thickness of the current collector to the negative electrode active material layer is not particularly limited, but the value of “(the thickness of the negative electrode active material layer on one side immediately before the nonaqueous electrolyte injection) / (thickness of the current collector)”
- 150 or less is preferable, 20 or less is more preferable, 10 or less is particularly preferable, 0.1 or more is preferable, 0.4 or more is further preferable, and 1 or more is particularly preferable.
- the ratio of the thickness of the current collector to the negative electrode active material layer is in the above range, battery capacity can be secured and heat generation of the current collector during high current density charge / discharge can be suppressed.
- the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used in manufacturing the electrode.
- resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose
- SBR styrene-butadiene rubber
- isoprene rubber butadiene rubber, fluorine rubber
- Rubber polymers such as NBR (acrylonitrile / butadiene rubber) and ethylene / propylene rubber
- EPDM ethylene / propylene / diene terpolymer
- styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / styrene cop
- the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less, 15% by mass. The following is more preferable, 10 mass% or less is still more preferable, and 8 mass% or less is especially preferable. When the ratio of the binder to the negative electrode active material is within the above range, the battery capacity and the strength of the negative electrode can be sufficiently secured.
- the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, and 0 .6% by mass or more is more preferable, and is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.
- the main component contains a fluorine-based polymer typified by polyvinylidene fluoride
- the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. Preferably, it is usually 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.
- the solvent for forming the slurry is not particularly limited as long as it is a solvent capable of dissolving or dispersing the negative electrode active material, the binder, and the thickener and conductive material used as necessary.
- aqueous solvent or an organic solvent may be used.
- the aqueous solvent include water and alcohol.
- organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N- Examples include dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, and the like.
- NMP N-methylpyrrolidone
- dimethylformamide dimethylacetamide
- methyl ethyl ketone cyclohexanone
- methyl acetate methyl acrylate
- diethyltriamine N
- N- Examples include dimethylaminopropylamine, tetrahydr
- aqueous solvent when used, it is preferable to add a dispersant or the like in addition to the thickener and make a slurry using a latex such as SBR.
- these solvents may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.
- a thickener is usually used to adjust the viscosity of the slurry.
- the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
- the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Moreover, it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is still more preferable.
- the ratio of the thickener to the negative electrode active material is in the above range, it is possible to suppress a decrease in battery capacity and an increase in resistance, and it is possible to ensure good coatability.
- the electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g ⁇ cm ⁇ 3 or more, and 1.2 g ⁇ cm ⁇ 3 or more. but more preferably, particularly preferably 1.3 g ⁇ cm -3 or more, preferably 2.2 g ⁇ cm -3 or less, more preferably 2.1 g ⁇ cm -3 or less, 2.0 g ⁇ cm -3 or less Further preferred is 1.9 g ⁇ cm ⁇ 3 or less.
- the density of the negative electrode active material existing on the current collector is in the above range, the negative electrode active material particles are prevented from being destroyed, and an increase in initial irreversible capacity or to the vicinity of the current collector / negative electrode active material interface. While the deterioration of the high current density charge / discharge characteristics due to the reduced permeability of the non-aqueous electrolyte solution can be suppressed, the decrease in battery capacity and the increase in resistance can be suppressed.
- the thickness of the negative electrode plate is designed according to the positive electrode plate to be used, and is not particularly limited.
- the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core is usually 15 ⁇ m or more, preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more, and usually 300 ⁇ m or less, preferably 280 ⁇ m or less, more preferably 250 ⁇ m or less.
- Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.
- Positive electrode ⁇ Positive electrode active material>
- the positive electrode active material used for the positive electrode is described below.
- the positive electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions.
- a material containing lithium and at least one transition metal is preferable. Specific examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds.
- V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. are preferable as the transition metal of the lithium transition metal composite oxide.
- Specific examples include lithium-cobalt composite oxides such as LiCoO 2 and LiNiO 2 .
- Lithium / nickel composite oxide, LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 4 and other lithium / manganese composite oxides, part of transition metal atoms that are the main components of these lithium transition metal composite oxides are Na, K , B, F, Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Nb, Mo, Sn, W, etc. And the like.
- substituted ones for example, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiNi 0.45 Co 0.10 Al 0.45 O 2 , LiMn 1.8 Al 0.2 O 4 , LiMn 1.5 Ni 0.5 O 4 and the like.
- transition metal of the lithium-containing transition metal phosphate compound V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable, and specific examples include, for example, LiFePO 4 , Li 3 Fe 2 (PO 4 ). 3 , iron phosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn , Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other elements.
- lithium phosphate in the positive electrode active material because continuous charging characteristics are improved.
- the lower limit of the amount of lithium phosphate used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass with respect to the total of the positive electrode active material and lithium phosphate. %, And the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.
- Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.
- these surface adhering substances are dissolved or suspended in a solvent, impregnated and added to the positive electrode active material, and dried.
- the surface adhering substance precursor is dissolved or suspended in a solvent and impregnated and added to the positive electrode active material, It can be made to adhere to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing simultaneously.
- the method of making carbonaceous adhere mechanically later in the form of activated carbon etc. can also be used, for example.
- the amount of the surface adhering substance is by mass with respect to the positive electrode active material, preferably 0.1 ppm or more, more preferably 1 ppm or more, still more preferably 10 ppm or more, and the upper limit, preferably 20% or less, more preferably as the lower limit. Is used at 10% or less, more preferably 5% or less.
- the surface adhering substance can suppress the oxidation reaction of the electrolyte solution on the surface of the positive electrode active material and can improve the battery life. However, when the amount of the adhering quantity is too small, the effect is not sufficiently manifested. If it is too high, the resistance may increase in order to inhibit the entry and exit of lithium ions.
- a material in which a material having a composition different from this is attached to the surface of the positive electrode active material is also referred to as a “positive electrode active material”.
- shape examples of the shape of the particles of the positive electrode active material include a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, and a column shape as conventionally used. Moreover, primary particles may aggregate to form secondary particles.
- the tap density of the positive electrode active material is preferably 0.5 g / cm 3 or more, more preferably 0.8 g / cm 3 or more, and further preferably 1.0 g / cm 3 or more.
- the tap density of the positive electrode active material is within the above range, the amount of the dispersion medium and the necessary amount of the conductive material and the binder necessary for forming the positive electrode active material layer can be suppressed. As a result, the filling rate of the positive electrode active material and the battery Capacity can be secured.
- a complex oxide powder having a high tap density a high-density positive electrode active material layer can be formed.
- the tap density is preferably as high as possible, and there is no particular upper limit, but it is preferably 4.0 g / cm 3 or less, more preferably 3.7 g / cm 3 or less, and even more preferably 3.5 g / cm 3 or less. When it is within the above range, it is possible to suppress a decrease in load characteristics.
- the tap density is defined as the powder packing density (tap density) g / cc when 5 to 10 g of the positive electrode active material powder is put in a 10 ml glass graduated cylinder and tapped 200 times with a stroke of about 20 mm. Ask.
- the median diameter d50 of the positive electrode active material particles is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably. Is 0.8 ⁇ m or more, most preferably 1.0 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 27 ⁇ m or less, still more preferably 25 ⁇ m or less, and most preferably 22 ⁇ m or less. While being in the above range, a high tap density product can be obtained and the battery performance can be prevented from deteriorating.
- the median diameter d50 is measured by a known laser diffraction / scattering particle size distribution measuring apparatus.
- LA-920 manufactured by HORIBA is used as a particle size distribution meter
- a 0.1% by mass sodium hexametaphosphate aqueous solution is used as a dispersion medium for measurement, and a measurement refractive index of 1.24 is set after ultrasonic dispersion for 5 minutes. Measured.
- the average primary particle diameter of the positive electrode active material is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 0.8.
- the upper limit is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less.
- the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles and obtained by taking the average value. It is done.
- SEM scanning electron microscope
- BET specific surface area of the positive electrode active material is preferably 0.1 m 2 / g or more, more preferably 0.2 m 2 / g or more, further preferably 0.3 m 2 / g or more, the upper limit is 50 m 2 / g or less , Preferably 40 m 2 / g or less, more preferably 30 m 2 / g or less.
- the BET specific surface area is in the above range, the battery performance can be secured and the applicability of the positive electrode active material can be kept good.
- the BET specific surface area is determined by using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 150 ° C. for 30 minutes under nitrogen flow, and then atmospheric pressure. It is defined by a value measured by a nitrogen adsorption BET one-point method using a gas flow method using a nitrogen-helium mixed gas accurately prepared so that the value of the relative pressure of nitrogen to 0.3 is 0.3.
- a surface area meter for example, a fully automatic surface area measuring device manufactured by Okura Riken
- Method for producing positive electrode active material As a manufacturing method of the positive electrode active material, a general method is used as a manufacturing method of the inorganic compound. In particular, various methods are conceivable for preparing a spherical or elliptical active material. For example, a transition metal source material is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring. And a spherical precursor is prepared and recovered, and dried as necessary. Then, a Li source such as LiOH, Li 2 CO 3 , LiNO 3 is added, and the active material is obtained by baking at a high temperature. .
- the positive electrode active material may be used alone, or one or more of the different compositions may be used in any combination or ratio.
- a combination of LiCoO 2 and LiMn 2 O 4 such as LiNi 0.33 Co 0.33 Mn 0.33 O 2 or a part of this Mn substituted with another transition metal or the like Or a combination with LiCoO 2 or a part of this Co substituted with another transition metal or the like.
- the positive electrode can be produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector. Manufacture of the positive electrode using a positive electrode active material can be performed by a conventional method.
- a positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying it to a positive electrode current collector and drying it as a slurry by dissolving or dispersing in a slurry.
- the content of the positive electrode active material in the positive electrode active material layer is preferably 80% by mass or more, more preferably 82% by mass or more, particularly preferably 84% by mass or more, and preferably 99% by mass or less. Preferably it is 98 mass% or less. Within the above range, the electric capacity of the positive electrode active material in the positive electrode active material layer can be secured, and the strength of the positive electrode can be maintained.
- the positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.
- Density of the positive electrode active material layer is preferably 1.5 g / cm 3 or more as a lower limit, more preferably 2 g / cm 3, and even more preferably at 2.2 g / cm 3 or more, preferably 5 g / cm 3 or less More preferably, it is 4.5 g / cm 3 or less, and further preferably 4 g / cm 3 or less. Within the above range, good charge / discharge characteristics can be obtained, and an increase in electrical resistance can be suppressed.
- a known conductive material can be arbitrarily used as the conductive material. Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the conductive material is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more in the positive electrode active material layer, and the upper limit is usually 50% by mass or less, preferably It is used so as to contain 30% by mass or less, more preferably 15% by mass or less. Sufficient electrical conductivity and battery capacity can be ensured within the above range.
- the binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, any material that can be dissolved or dispersed in the liquid medium used during electrode production may be used.
- Resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluorine rubber, isoprene rubber , Rubber polymers such as butadiene rubber and ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / butadiene / Ethylene copolymer, styrene Thermoplastic elastomeric
- the ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, and the upper limit is usually 80% by mass or less, preferably Is 60% by mass or less, more preferably 40% by mass or less, and most preferably 10% by mass or less.
- the ratio of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. On the other hand, if it is too high, battery capacity and conductivity may be reduced.
- the solvent for forming the slurry As the solvent for forming the slurry, the positive electrode active material, the conductive material, the binder, and a solvent capable of dissolving or dispersing the thickener used as necessary may be used. There is no restriction, and either an aqueous solvent or an organic solvent may be used. Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like.
- organic medium examples include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
- Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; and aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
- amines such as diethylenetriamine and N, N-dimethylaminopropylamine
- ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF)
- NMP N-methylpyrrolidone
- Amides such as dimethylformamide and dimethylacetamide
- aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
- a thickener is usually used to adjust the viscosity of the slurry.
- the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
- the ratio of the thickener to the active material is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more.
- the upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less.
- the material of the positive electrode current collector is not particularly limited, and a known material can be arbitrarily used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.
- the shape of the current collector examples include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal in the case of a metal material.
- a thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred.
- the thickness of the thin film is arbitrary, from the viewpoint of strength and handleability as a current collector, it is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and the upper limit is usually 1 mm or less, preferably 100 ⁇ m or less. More preferably, it is 50 ⁇ m or less.
- a conductive additive is applied to the surface of the current collector.
- the conductive assistant include noble metals such as carbon, gold, platinum, and silver.
- the ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but the value of (thickness of the positive electrode active material layer on one side immediately before electrolyte injection) / (thickness of the current collector) is 20
- the lower limit is preferably 15 or less, most preferably 10 or less, and the lower limit is preferably 0.5 or more, more preferably 0.8 or more, and most preferably 1 or more.
- the current collector may generate heat due to Joule heat during high current density charge / discharge. Within the above range, heat generation of the current collector during high current density charge / discharge can be suppressed, and battery capacity can be secured.
- the area of the positive electrode active material layer is larger than the outer surface area of the battery outer case from the viewpoint of increasing the stability at high output and high temperature.
- the sum of the electrode areas of the positive electrode with respect to the surface area of the exterior of the secondary battery is preferably 15 times or more, more preferably 40 times or more.
- the outer surface area of the outer case is the total area obtained by calculation from the vertical, horizontal, and thickness dimensions of the case part filled with the power generation element excluding the protruding part of the terminal in the case of a bottomed square shape. .
- the geometric surface area approximates the case portion filled with the power generation element excluding the protruding portion of the terminal as a cylinder.
- the total electrode area of the positive electrode is the geometric surface area of the positive electrode mixture layer facing the mixture layer containing the negative electrode active material, and in the structure in which the positive electrode mixture layer is formed on both sides via the current collector foil. , The sum of the areas where each surface is calculated separately.
- the thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the composite layer obtained by subtracting the metal foil thickness of the core material is preferably as a lower limit with respect to one side of the current collector. Is 10 ⁇ m or more, more preferably 20 ⁇ m or more, and the upper limit is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less.
- Electrode surface coating (Positive electrode surface coating) Moreover, you may use what adhered the substance of the composition different from this to the surface of the said positive electrode plate.
- Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.
- a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit.
- the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.
- the material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
- a resin, glass fiber, inorganic material, etc. formed of a material that is stable with respect to the non-aqueous electrolyte solution of the present invention is used, and a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties is used. Is preferred.
- polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the thickness of the separator is arbitrary, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and usually 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less.
- insulation and mechanical strength can be secured, while battery performance such as rate characteristics and energy density can be secured.
- the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Moreover, it is 90% or less normally, 85% or less is preferable and 75% or less is still more preferable.
- insulation and mechanical strength can be secured, while film resistance can be suppressed and good rate characteristics can be obtained.
- the average pore diameter of the separator is also arbitrary, but is usually 0.5 ⁇ m or less, preferably 0.2 ⁇ m or less, and usually 0.05 ⁇ m or more. If the average pore diameter exceeds the above range, a short circuit tends to occur. When the average pore diameter is in the above range, the film resistance can be suppressed and good rate characteristics can be obtained while preventing a short circuit.
- inorganic materials for example, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used. Used.
- a thin film shape such as a nonwoven fabric, a woven fabric, or a microporous film is used.
- the thin film shape those having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m are preferably used.
- a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
- a porous layer may be formed by using alumina particles having a 90% particle size of less than 1 ⁇ m on both surfaces of the positive electrode and using a fluororesin as a binder.
- the electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable.
- the ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupation ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. .
- the current collecting structure is not particularly limited, but in order to more effectively realize the high current density charge / discharge characteristics by the non-aqueous electrolyte solution of the present invention, a structure that reduces the resistance of the wiring part and the joint part is used. It is preferable. Thus, when internal resistance is reduced, the effect using the non-aqueous electrolyte solution of this invention is exhibited especially favorable.
- the electrode group has the laminated structure described above, a structure formed by bundling the metal core portions of the electrode layers and welding them to the terminals is preferably used.
- the area of one electrode increases, the internal resistance increases. Therefore, it is also preferable to provide a plurality of terminals in the electrode to reduce the resistance.
- the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures for the positive electrode and the negative electrode, respectively, and bundling the terminals.
- the material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used.
- the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things.
- the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers.
- a resin different from the resin used for the laminate film may be interposed between the resin layers.
- a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used.
- Resins are preferably used.
- the shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
- PTC Positive temperature Coefficient
- thermal fuse thermal fuse
- thermistor whose resistance increases when abnormal heat generation or excessive current flows, cut off current flowing in the circuit due to sudden rise in battery internal pressure or internal temperature in abnormal heat generation
- a valve current cutoff valve or the like
- the protective element is designed so as not to cause abnormal heat generation or thermal runaway even without the protective element.
- the graphite used has a d50 value of 10.9 ⁇ m, a specific surface area of 3.41 m 2 / g, and a tap density of 0.985 g / cm 3 .
- the positive electrode, the negative electrode, and the separator were stacked in the order of the negative electrode, the separator, and the positive electrode.
- the separator was made of polypropylene, had a thickness of 20 ⁇ m, and a porosity of 54%.
- the battery element thus obtained was wrapped in a cylindrical aluminum laminate film, injected with an electrolyte described later, and then vacuum sealed to produce a sheet-like non-aqueous electrolyte secondary battery. Furthermore, in order to improve the adhesion between the electrodes, the sheet-like battery was sandwiched between glass plates and pressurized.
- the battery was stored at 60 ° C. for 12 hours to stabilize the battery. Thereafter, a charge / discharge cycle of 1/3 C constant current-constant voltage charge up to 4.2 V at 25 ° C., followed by 1/3 C constant current discharge up to 3.0 V was performed. The last discharge capacity at this time was defined as the initial capacity.
- 1C is a current value when discharging the entire capacity of the battery in one hour.
- ⁇ Cycle capacity maintenance rate evaluation test> The battery that had been initially charged and discharged was charged to 4.2 V by a 2C constant current method at 60 ° C., and then charged and discharged to discharge to 3.0 V by a 2C constant current method. Thereafter, a charge / discharge cycle of 1/3 C constant current-constant voltage charge up to 4.2 V at 25 ° C. and subsequent 1/3 C constant current discharge up to 3.0 V was performed. The last discharge capacity at this time was taken as the post-cycle capacity, and the post-cycle capacity relative to the initial capacity was taken as the cycle capacity retention rate (%).
- ⁇ Low-temperature resistance characteristic evaluation test> The battery after initial and after cycling is adjusted to 3.72 V, and from that state, constant current discharge is performed at ⁇ 30 ° C. at various current values for 10 seconds. The voltage after 10 seconds is plotted with respect to various current values, and the current value such that the voltage after 10 seconds becomes 3V is obtained. The slope of the straight line obtained by connecting the point thus obtained and the point of the initial value (open circuit state) was defined as the low temperature resistance characteristic ( ⁇ ).
- Table 1 shows the results of studies on synthesis examples and reference synthesis examples. It was found that the target sulfonic acid ester was obtained with high purity by crystallization. On the other hand, in Reference Synthesis Example 1, the target product was not obtained as a solid, and the oil remained as it was, and since the alcohol raw material and amine remained in this oil, the yield exceeded 100%. As a result, the purity was as low as 66.5%. In Reference Synthesis Example 2, no precipitation of the target product was observed, and no solid deposition was observed even after concentration in a water bath at 30 ° C. under reduced pressure. From these results, it is not possible to obtain a high-purity target product without a crystallization treatment after the reaction, and it is impossible to obtain a target product unless it is dissolved in a crystallization solvent and then cooled. Became clear.
- Example 1 Under a dry argon atmosphere, fully dried LiPF 6 was dissolved in a mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (volume ratio 3: 3: 4) so that the total amount of the nonaqueous electrolyte solution was 1 mol / L. (This electrolyte may be referred to as a “reference electrolyte”).
- a non-aqueous electrolyte solution was prepared by adding the compound represented by the formula (A) obtained in Synthesis Example 1 to the reference electrolyte solution so as to be 0.73% by mass in 100% by mass of the non-aqueous electrolyte solution. .
- a battery was prepared by the above-described method using this electrolytic solution, and a cycle capacity retention rate, a high temperature storage test, and a low temperature resistance characteristic were measured. The results are shown in Table 2.
- Example 2 The same method as in Example 1 except that vinylene carbonate (hereinafter referred to as VC) was further added to the non-aqueous electrolyte solution of Example 1 so as to be 0.5% by mass in 100% by mass of the non-aqueous electrolyte solution.
- VC vinylene carbonate
- a battery was prepared, and a cycle capacity retention rate, a high temperature storage test, and a low temperature resistance characteristic were measured. The results are shown in Table 2.
- Example 3 A method similar to that of Example 1 except that the compound of formula (B) of Synthesis Example 2 was added to the nonaqueous electrolytic solution in an amount of 1.03% by mass instead of the compound of formula (A). A battery was prepared, and a cycle capacity retention rate, a high temperature storage test, and a low temperature resistance characteristic were measured. The results are shown in Table 2.
- Example 4 The same method as in Example 1 except that the compound of formula (C) of Synthesis Example 3 was added to 1.07% by mass with respect to the non-aqueous electrolyte instead of the compound of formula (A). A battery was prepared, and a cycle capacity retention rate, a high temperature storage test, and a low temperature resistance characteristic were measured. The results are shown in Table 2.
- Example 5 The same method as in Example 1, except that the compound of formula (D) in Synthesis Example 4 was added to the non-aqueous electrolyte solution in place of the compound of formula (A) so as to be 0.78% by mass. A battery was prepared, and a cycle capacity retention rate, a high temperature storage test, and a low temperature resistance characteristic were measured. The results are shown in Table 2.
- Example 1 instead of the compound represented by the formula (A), the compound represented by the following formula (E) was added to Example 1 except that the compound was added to 0.70% by mass in 100% by mass of the non-aqueous electrolyte solution.
- a battery was prepared in the same manner, and the cycle capacity retention rate, high temperature storage test, and low temperature resistance characteristics were measured. The results thus obtained are shown in Table 2.
- Example 1 A battery was prepared in the same manner as in Example 1 except that VC was added to be 0.50% by mass in 100% by mass of the non-aqueous electrolyte instead of the compound represented by the formula (A). The cycle capacity retention rate, high temperature storage test, and low temperature resistance characteristics were measured. The results are shown in Table 2.
- the cycle capacity retention rate and low-temperature resistance characteristics of the non-aqueous electrolyte secondary battery can be improved. Therefore, the non-aqueous electrolyte solution of the present invention and the non-aqueous electrolyte secondary battery using the same can be used for various known applications. Specific examples include notebook computers, tablet computers, electronic book players, mobile phones, smartphones, portable CD / DVD / BD players, portable LCD TVs, handy cleaners, transceivers, electronic notebooks, calculators, memory cards, radios, and backups. Examples include power supplies, motors, automobiles, motorbikes, motorbikes, bicycles, lighting equipment, toys, game machines, watches, electric tools, cameras, load leveling power supplies, and natural energy storage power supplies.
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Abstract
Description
リチウム二次電池を構成する成分は主に正極、負極、セパレータ、及び電解液に大別される。これらのうち、電解液には一般に、LiPF6、LiBF4、LiClO4、LiCF3SO3、LiAsF6、LiN(CF3SO2)2、LiCF3(CF2)3SO3等の電解質を、エチレンカーボネート、プロピレンカーボネート等の環状カーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等の鎖状カーボネート;γ-ブチロラクトン、γ-バレロラクトン等の環状エステル類;酢酸メチル、プロピオン酸メチル等の鎖状エステル類等の非水系溶媒に溶解させた非水系電解液が用いられている。
例えば、特許文献1及び2には、負極に炭素材料を用いた非水電解質において、ヒドロキシ酸誘導体を使用する技術が紹介されている。また、特許文献3及び4には、非水電解質に特定のスルホン酸エステルを添加する技術が紹介されている。
本発明は、かかる背景技術に鑑みてなされたものであり、サイクル容量維持率と低温抵抗特性に優れた非水系電解液、及びそれを用いた非水系電解液二次電池を提供することを目的とする。
(a)電解質とこれを溶解する非水系溶媒を含有してなる非水系電解液であって、式(1):
式中、
Xは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
Yは、硫黄原子、リン原子又は炭素原子を表し、
nは、1又は2の整数を表し、mは2~4の整数を表し、lは1又は2の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す
で表される化合物を含有することを特徴とする非水系電解液。
(b)前記Xが、カルボニル基を含む有機基である、(b)の非水系電解液。
(c)前記Yが、硫黄原子である、(a)又は(b)の非水系電解液。
(d)前記Zが、炭素数4~6のアルキレン基である、(a)乃至(c)のいずれかの非水系電解液。
(e)前記式(1)で表される化合物の少なくとも1種が、非水系電解液100質量%中、0.01~5質量%で含有されている、(a)乃至(d)のいずれかの非水系電解液。
(f)非水系電解液が更に不飽和結合を有する環状カーボネートを含有する、(a)乃至(e)のいずれかの非水系電解液。
(g)金属イオンを吸蔵・放出可能な負極及び正極、並びに(a)乃至(f)のいずれかの非水系電解液を含む非水系電解液二次電池。
(h)金属イオンを吸蔵及び放出可能な正極が、少なくとも1種以上の層状遷移金属酸化物を含む、(g)の非水系電解液二次電池。
(i)金属イオンを吸蔵及び放出可能な負極が、少なくとも1種以上の炭素化合物を含む、(g)の非水系電解液二次電池。
(j)式(10):
式中、
Wは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
mは、2~4の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す
で表されるスルホン酸エステルの製造方法であって、
式(11):
式中、Z及びmは、式(10)と同義である
で表されるスルホン酸クロリドと、式(12):
W-OH (12)
式中、Wは、式(10)と同義である
で表されるアルコール性水酸基を有する化合物を反応させる工程、及び
晶析により式(10)で表されるスルホン酸エステルを固体として取り出す工程を含むことを特徴とするスルホン酸エステルの製造方法。
(k)晶析を、式(10)で表されるスルホン酸エステルを含む溶液の温度を下げることによって行う、(j)のスルホン酸エステルの製造方法。
(l)式(10)で表されるスルホン酸エステルを含む溶液が、メタノール溶液である、(k)のスルホン酸エステルの製造方法。
(m)晶析を20℃以下の温度条件で行う、(j)~(k)のいずれかのスルホン酸エステルの製造方法。
(n)式(10)におけるZが直鎖構造の有機基である、(j)~(m)のいずれかのスルホン酸エステルの製造方法。
(o)式(11)で表されるスルホン酸クロリドが、式(21):
pは、4~6の整数を表す
で表される、(j)~(o)のいずれかのスルホン酸エステルの製造方法。
(p)
式(12)で表されるアルコール性水酸基を有する化合物が、式(22):
式中、
Raは、独立して、炭素数1~4のアルキル基を表し、
Rbは、独立して、炭素数1~4のアルキル基を表す
で表される、(j)~(o)のいずれかのスルホン酸エステルの製造方法。
(q)式(12)で表されるアルコール性水酸基を有する化合物が、グリセロールカーボネートである、(j)~(p)のいずれかのスルホン酸エステルの製造方法。
(r)式(20):
式中、
Raは、独立して、炭素数1~4のアルキル基を表し、
Rbは、独立して、炭素数1~4のアルキル基を表し、
pは、4~6の整数を表す
で表されることを特徴とする化合物。
(s)式(30):
式中、pは、4~6の整数を表す
で表される化合物。
すなわち、本発明の非水系電解液を用いることで、非水系電解液二次電池のサイクル容量維持率や、副反応由来の低温抵抗特性低下を改善することが期待できる。
本発明は、電解質(例えばリチウム塩)とこれを溶解する非水系溶媒を含有してなる非水系電解液であって、式(1)で表される化合物を含有することを特徴とする非水系電解液である。
電解質としては、典型的にはリチウム塩が挙げられるが、これに限られず、ナトリウム、カリウム、カルシウム、バリウム等の金属塩であってもよい。リチウム塩は、非水系電解液の用途に用いることが知られているものであれば特に制限がない。具体的には以下が挙げられる。
例えば、LiPF6、LiBF4、LiClO4、LiAlF4、LiSbF6、LiTaF6、LiWF7等の無機リチウム塩;LiWOF5等のタングステン酸リチウム類;HCO2Li、CH3CO2Li、CH2FCO2Li、CHF2CO2Li、CF3CO2Li、CF3CH2CO2Li、CF3CF2CO2Li、CF3CF2CF2CO2Li、CF3CF2CF2CF2CO2Li等のカルボン酸リチウム塩類;FSO3Li、CH3SO3Li、CH2FSO3Li、CHF2SO3Li、CF3SO3Li、CF3CF2SO3Li、CF3CF2CF2SO3Li、CF3CF2CF2CF2SO3Li等のスルホン酸リチウム塩類;LiN(FCO)2、LiN(FCO)(FSO2)、LiN(FSO2)2、LiN(FSO2)(CF3SO2)、LiN(CF3SO2)2、LiN(C2F5SO2)2、リチウム環状1,2-パーフルオロエタンジスルホニルイミド、リチウム環状1,3-パーフルオロプロパンジスルホニルイミド、LiN(CF3SO2)(C4F9SO2)等のリチウムイミド塩類;LiC(FSO2)3、LiC(CF3SO2)3、LiC(C2F5SO2)3等のリチウムメチド塩類;リチウムジフルオロオキサラトボレート、リチウムビス(オキサラト)ボレート等のリチウムオキサラトボレート塩類;リチウムテトラフルオロオキサラトホスフェート、リチウムジフルオロビス(オキサラト)ホスフェート、リチウムトリス(オキサラト)ホスフェート等のリチウムオキサラトホスフェート塩類;その他、LiPF4(CF3)2、LiPF4(C2F5)2、LiPF4(CF3SO2)2、LiPF4(C2F5SO2)2、LiBF3CF3、LiBF3C2F5、LiBF3C3F7、LiBF2(CF3)2、LiBF2(C2F5)2、LiBF2(CF3SO2)2、LiBF2(C2F5SO2)2等の含フッ素有機リチウム塩類;等が挙げられる。
非水系溶媒としては、環状カーボネート、鎖状カーボネート、環状及び鎖状カルボン酸エステル、エーテル系化合物、スルホン系化合物等を使用することが可能である。
環状カーボネートとしては、炭素数2~4のアルキレン基を有するものが挙げられる。
炭素数2~4の環状カーボネートの具体的な例としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の炭素数2~4のアルキレン基を有するアルキレンカーボネート類が挙げられる。中でも、エチレンカーボネートとプロピレンカーボネートがリチウムイオン解離度の向上に由来する電池特性向上の点から特に好ましい。
環状カーボネートは、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併有してもよい。
鎖状カーボネートとしては、炭素数3~7のものが好ましい。
具体的には、炭素数3~7の鎖状カーボネートとしては、ジメチルカーボネート、ジエチルカーボネート、ジ-n-プロピルカーボネート、ジイソプロピルカーボネート、n-プロピルイソプロピルカーボネート、エチルメチルカーボネート、メチル-n-プロピルカーボネート、n-ブチルメチルカーボネート、イソブチルメチルカーボネート、t-ブチルメチルカーボネート、エチル-n-プロピルカーボネート、n-ブチルエチルカーボネート、イソブチルエチルカーボネート、t-ブチルエチルカーボネート等が挙げられる。
また、フッ素原子を有する鎖状カーボネート類(以下、「フッ素化鎖状カーボネート」と略記する場合がある)も好適に用いることができる。フッ素化鎖状カーボネートが有するフッ素原子の数は、1以上であれば特に制限されないが、通常6以下であり、好ましくは4以下である。フッ素化鎖状カーボネートが複数のフッ素原子を有する場合、それらは互いに同一の炭素に結合していてもよく、異なる炭素に結合していてもよい。フッ素化鎖状カーボネートとしては、フッ素化ジメチルカーボネート誘導体、フッ素化エチルメチルカーボネート誘導体、フッ素化ジエチルカーボネート誘導体等が挙げられる。
フッ素化エチルメチルカーボネート誘導体としては、2-フルオロエチルメチルカーボネート、エチルフルオロメチルカーボネート、2,2-ジフルオロエチルメチルカーボネート、2-フルオロエチルフルオロメチルカーボネート、エチルジフルオロメチルカーボネート、2,2,2-トリフルオロエチルメチルカーボネート、2,2-ジフルオロエチルフルオロメチルカーボネート、2-フルオロエチルジフルオロメチルカーボネート、エチルトリフルオロメチルカーボネート等が挙げられる。
鎖状カーボネートの配合量は、非水系溶媒100体積%中、好ましくは5体積%以上、より好ましくは10体積%以上、更に好ましくは15体積%以上である。このように下限を設定することにより、非水系電解液の粘度を適切な範囲とし、イオン伝導度の低下を抑制し、ひいては非水系電解液二次電池の大電流放電特性を良好な範囲としやすくなる。また、鎖状カーボネートは、非水系溶媒100体積%中、90体積%以下、より好ましくは85体積%以下であることが好ましい。このように上限を設定することにより、非水系電解液の誘電率の低下に由来する電気伝導率の低下を回避し、非水系電解液二次電池の大電流放電特性を良好な範囲としやすくなる。
環状カルボン酸エステルとしては、その構造式中の全炭素原子数が3~12のものが挙げられる。
具体的には、ガンマブチロラクトン、ガンマバレロラクトン、ガンマカプロラクトン、イプシロンカプロラクトン等が挙げられる。中でも、ガンマブチロラクトンがリチウムイオン解離度の向上に由来する電池特性向上の点から特に好ましい。
鎖状カルボン酸エステルとしては、その構造式中の全炭素数が3~7のものが挙げられる。
具体的には、酢酸メチル、酢酸エチル、酢酸-n-プロピル、酢酸イソプロピル、酢酸-n-ブチル、酢酸イソブチル、酢酸-t-ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸-n-プロピル、プロピオン酸イソプロピル、プロピオン酸-n-ブチル、プロピオン酸イソブチル、プロピオン酸-t-ブチル、酪酸メチル、酪酸エチル、酪酸-n-プロピル、酪酸イソプロピル、イソ酪酸メチル、イソ酪酸エチル、イソ酪酸-n-プロピル、イソ酪酸イソプロピル等が挙げられる。
鎖状カルボン酸エステルの配合量は、非水系溶媒100体積%中、好ましくは10体積%以上、より好ましくは15体積%以上である。このように下限を設定することで、非水系電解液の電気伝導率を改善し、非水系電解液二次電池の大電流放電特性を向上させやすくなる。また、鎖状カルボン酸エステルの配合量は、非水系溶媒100体積%中、好ましくは60体積%以下、より好ましくは50体積%以下である。このように上限を設定することで、負極抵抗の増大を抑制し、非水系電解液二次電池の大電流放電特性、サイクル特性を良好な範囲としやすくなる。
エーテル系化合物としては、一部の水素がフッ素にて置換されていてもよい炭素数3~10の鎖状エーテル、及び炭素数3~6の環状エーテルが好ましい。
炭素数3~10の鎖状エーテルとしては、ジエチルエーテル、ジ(2-フルオロエチル)エーテル、ジ(2,2-ジフルオロエチル)エーテル、ジ(2,2,2-トリフルオロエチル)エーテル、エチル(2-フルオロエチル)エーテル、エチル(2,2,2-トリフルオロエチル)エーテル、エチル(1,1,2,2-テトラフルオロエチル)エーテル、(2-フルオロエチル)(2,2,2-トリフルオロエチル)エーテル、(2-フルオロエチル)(1,1,2,2-テトラフルオロエチル)エーテル、(2,2,2-トリフルオロエチル)(1,1,2,2-テトラフルオロエチル)エーテル、エチル-n-プロピルエーテル、エチル(3-フルオロ-n-プロピル)エーテル、エチル(3,3,3-トリフルオロ-n-プロピル)エーテル、エチル(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、エチル(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、2-フルオロエチル-n-プロピルエーテル、(2-フルオロエチル)(3-フルオロ-n-プロピル)エーテル、(2-フルオロエチル)(3,3,3-トリフルオロ-n-プロピル)エーテル、(2-フルオロエチル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(2-フルオロエチル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、2,2,2-トリフルオロエチル-n-プロピルエーテル、(2,2,2-トリフルオロエチル)(3-フルオロ-n-プロピル)エーテル、(2,2,2-トリフルオロエチル)(3,3,3-トリフルオロ-n-プロピル)エーテル、(2,2,2-トリフルオロエチル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(2,2,2-トリフルオロエチル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、1,1,2,2-テトラフルオロエチル-n-プロピルエーテル、(1,1,2,2-テトラフルオロエチル)(3-フルオロ-n-プロピル)エーテル、(1,1,2,2-テトラフルオロエチル)(3,3,3-トリフルオロ-n-プロピル)エーテル、(1,1,2,2-テトラフルオロエチル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(1,1,2,2-テトラフルオロエチル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ-n-プロピルエーテル、(n-プロピル)(3-フルオロ-n-プロピル)エーテル、(n-プロピル)(3,3,3-トリフルオロ-n-プロピル)エーテル、(n-プロピル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(n-プロピル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ(3-フルオロ-n-プロピル)エーテル、(3-フルオロ-n-プロピル)(3,3,3-トリフルオロ-n-プロピル)エーテル、(3-フルオロ-n-プロピル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(3-フルオロ-n-プロピル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ(3,3,3-トリフルオロ-n-プロピル)エーテル、(3,3,3-トリフルオロ-n-プロピル)(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(3,3,3-トリフルオロ-n-プロピル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ(2,2,3,3-テトラフルオロ-n-プロピル)エーテル、(2,2,3,3-テトラフルオロ-n-プロピル)(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ(2,2,3,3,3-ペンタフルオロ-n-プロピル)エーテル、ジ-n-ブチルエーテル、ジメトキシメタン、メトキシエトキシメタン、メトキシ(2-フルオロエトキシ)メタン、メトキシ(2,2,2-トリフルオロエトキシ)メタンメトキシ(1,1,2,2-テトラフルオロエトキシ)メタン、ジエトキシメタン、エトキシ(2-フルオロエトキシ)メタン、エトキシ(2,2,2-トリフルオロエトキシ)メタン、エトキシ(1,1,2,2-テトラフルオロエトキシ)メタン、ジ(2-フルオロエトキシ)メタン、(2-フルオロエトキシ)(2,2,2-トリフルオロエトキシ)メタン、(2-フルオロエトキシ)(1,1,2,2-テトラフルオロエトキシ)メタンジ(2,2,2-トリフルオロエトキシ)メタン、(2,2,2-トリフルオロエトキシ)(1,1,2,2-テトラフルオロエトキシ)メタン、ジ(1,1,2,2-テトラフルオロエトキシ)メタン、ジメトキシエタン、メトキシエトキシエタン、メトキシ(2-フルオロエトキシ)エタン、メトキシ(2,2,2-トリフルオロエトキシ)エタン、メトキシ(1,1,2,2-テトラフルオロエトキシ)エタン、ジエトキシエタン、エトキシ(2-フルオロエトキシ)エタン、エトキシ(2,2,2-トリフルオロエトキシ)エタン、エトキシ(1,1,2,2-テトラフルオロエトキシ)エタン、ジ(2-フルオロエトキシ)エタン、(2-フルオロエトキシ)(2,2,2-トリフルオロエトキシ)エタン、(2-フルオロエトキシ)(1,1,2,2-テトラフルオロエトキシ)エタン、ジ(2,2,2-トリフルオロエトキシ)エタン、(2,2,2-トリフルオロエトキシ)(1,1,2,2-テトラフルオロエトキシ)エタン、ジ(1,1,2,2-テトラフルオロエトキシ)エタン、エチレングリコールジ-n-プロピルエーテル、エチレングリコールジ-n-ブチルエーテル、ジエチレングリコールジメチルエーテル等が挙げられる。
中でも、ジメトキシメタン、ジエトキシメタン、エトキシメトキシメタン、エチレングリコールジ-n-プロピルエーテル、エチレングリコールジ-n-ブチルエーテル、ジエチレングリコールジメチルエーテルが、リチウムイオンへの溶媒和能力が高く、イオン解離性を向上させる点で好ましく、特に好ましくは、粘性が低く、高いイオン伝導度を与えることから、ジメトキシメタン、ジエトキシメタン、エトキシメトキシメタンである。
スルホン系化合物としては、炭素数3~6の環状スルホン、及び炭素数2~6の鎖状スルホンが好ましい。1分子中のスルホニル基の数は、1又は2であることが好ましい。
炭素数3~6の環状スルホンとしては、モノスルホン化合物であるトリメチレンスルホン類、テトラメチレンスルホン類、ヘキサメチレンスルホン類;ジスルホン化合物であるトリメチレンジスルホン類、テトラメチレンジスルホン類、ヘキサメチレンジスルホン類等が挙げられる。中でも、誘電率と粘性の観点から、テトラメチレンスルホン類、テトラメチレンジスルホン類、ヘキサメチレンスルホン類、ヘキサメチレンジスルホン類がより好ましく、テトラメチレンスルホン類(スルホラン類)が特に好ましい。
中でも、2-メチルスルホラン、3-メチルスルホラン、2-フルオロスルホラン、3-フルオロスルホラン、2,2-ジフルオロスルホラン、2,3-ジフルオロスルホラン、2,4-ジフルオロスルホラン、2,5-ジフルオロスルホラン、3,4-ジフルオロスルホラン、2-フルオロ-3-メチルスルホラン、2-フルオロ-2-メチルスルホラン、3-フルオロ-3-メチルスルホラン、3-フルオロ-2-メチルスルホラン、4-フルオロ-3-メチルスルホラン、4-フルオロ-2-メチルスルホラン、5-フルオロ-3-メチルスルホラン、5-フルオロ-2-メチルスルホラン、2-フルオロメチルスルホラン、3-フルオロメチルスルホラン、2-ジフルオロメチルスルホラン、3-ジフルオロメチルスルホラン、2-トリフルオロメチルスルホラン、3-トリフルオロメチルスルホラン、2-フルオロ-3-(トリフルオロメチル)スルホラン、3-フルオロ-3-(トリフルオロメチル)スルホラン、4-フルオロ-3-(トリフルオロメチル)スルホラン、5-フルオロ-3-(トリフルオロメチル)スルホラン等がイオン伝導度が高く入出力が高い点で好ましい。
全非水系溶媒中に占めるジメチルカーボネートのエチルメチルカーボネートに対する体積比(ジメチルカーボネート/エチルメチルカーボネート)は、電解液の電気伝導度の向上と保存後の電池特性を向上の点で、1.1以上が好ましく、1.5以上がより好ましく、2.5以上が更に好ましい。上記体積比(ジメチルカーボネート/エチルメチルカーボネート)は、低温での電池特性を向上の点で、40以下が好ましく、20以下がより好ましく、10以下が更に好ましく、8以下が特に好ましい。
本明細書において、非水系溶媒の体積は25℃での測定値であるが、エチレンカーボネートのように25℃で固体のものは融点での測定値を用いる。
本発明の非水系電解液は、式(1)で表される化合物を含有することを特徴とする。式(1)で表される化合物は、カルボン酸エステル構造、スルホン酸エステル構造、及び/又はリン酸エステル構造を有する化合物である。これらの構造を複数有することによって、式(1)で表される化合物が負極表面上で電気化学的に還元される際に、負極皮膜の熱的安定性を高めるために好適な多価金属塩(例えばリチウム塩)の生成を促進する効果が発現されるものと考えられる。また、これらの構造は、収率良く効率的に形成することができるため、式(1)で表される化合物の合成を容易にし、製造コストを抑える役割も果たしているといえる。
多価金属塩(例えばリチウム塩)の電解液への溶解性が抑制されることで、負極皮膜がより安定化され、副反応が抑制されると考えられる。その結果、サイクル容量維持率、低温抵抗特性が向上すると考えられる。
本発明に係る化合物は、下記式(1)で表される。
Xは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
Yは、硫黄原子、リン原子又は炭素原子を表し、
nは、1又は2の整数を表し、mは2~4の整数を表し、lは1又は2の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す。
上記のXの具体例の中でも、スルホニル基又はカルボニル基を含有する以下に示す構造がより好ましい。これらの構造は負極表面上で結合開裂しやすく、これらを複数有することによって、負極皮膜の熱的安定性を極度に高めることができる。
また、n及びlは1又は2の整数であるが、Yが硫黄原子である場合、nとlはそれぞれ1と2、又はそれぞれ1と1を表し、nとlがそれぞれ2と1を表す場合が好ましい。Yが炭素原子である場合、nとlはともに1を表す。
mは2~4の整数であるが、負極皮膜の熱安定性の点から特に2であることが好ましい。
Zの有機基としては、アルキレン基、エーテル基、エステル基が好ましく、アルキレン基、エーテル基がより好ましく、アルキレン基が更に好ましく、炭素数4~6の直鎖状のアルキレン基が特に好ましい。ここで、Zは、Y同士をつなぐ連結基であって、複数あるYは、Z中のいずれの原子に結合してもよく、Z中の同一の原子に結合していても、異なる原子に結合していてもよい。好ましくは、Z中の異なる原子に結合している。
式(1)で表される化合物の製造方法について、式(10):
式中、
Wは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
mは、2~4の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す
で表されるスルホン酸エステルを例にとって説明する。
式中、Wは、Wに結合している部分を水酸基で置き換えたとき、その水酸基がアルコール性水酸基である。
式中、
Wは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
mは、2~4の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す
で表されるスルホン酸エステルの製造方法であって、
式(11):
式中、
m及びZは、式(10)と同義である
で表されるスルホン酸クロリドと、式(12):
W-OH
式中、Wは、式(10)と同義である
で表されるアルコール性水酸基を有する化合物を反応させる工程、及び
晶析により式(10)で表されるスルホン酸エステルを固体として取り出す工程を含むことを特徴とするスルホン酸エステルの製造方法に関する。
式中、
Raは、独立して、炭素数1~4のアルキル基を表し、
Rbは、独立して、炭素数1~4のアルキル基を表し、
pは、4~6の整数を表す
で表される化合物は、式(21):
式中、pは4~6の整数を表す
で表されるスルホン酸クロリドを、式(22):
式中、
Raは、独立して、炭素数1~4のアルキル基を表し、
Rbは、独立して、炭素数1~4のアルキル基を表す
で表されるアルコール性水酸基を有する化合物を反応させることにより得ることができる。
式中、pは4~6の整数を表す
で表される化合物は、式(31):
式中、pは4~6の整数を表す
で表されるスルホン酸クロリドを、グリセロールカーボネートと反応させることにより得ることができる。
スルホン酸クロリドとアルコール性水酸基を有する化合物との反応は、無溶媒又は溶媒中で行うことができる。反応は、非水溶媒中、反応促進剤として塩基を加え、低温で行うことが好ましい。
溶媒中で反応を行う場合、非水溶媒を使用することができ、スルホン酸クロリドと反応しないものを用いるのが好ましい。例えば、ペンタン、ヘキサン、ヘプタン、オクタン、石油エーテル等の脂肪族炭化水素;ジエチルエーテル、ジイソプロピルエーテル、t-ブチルメチルエーテル、アニソール、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル等のエーテル;塩化メチレン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、トリクロロエタン、ブロモプロパン、クロロベンゼン、ジクロロベンゼン等の含ハロゲン化炭化水素;アセトニトリル、プロピオニトリル、ブチロニトリル、ベンゾニトリル等の含シアノ炭化水素;酢酸エチル、酢酸ブチル等のエステル類;ベンゼン、トルエン、ニトロベンゼン等の芳香族炭化水素;アセトン、メチルエチルケトン等のケトン類;が挙げられる。これらの溶媒は、単独で用いても、2種以上を併用してもよい。また、スルホン酸クロリドが分解しない量であれば水を混合して用いてもよい。コストの点から、脂肪族炭化水素、エーテル、含シアノ炭化水素、エステル類、芳香族炭化水素、ケトン類が好ましく、より好ましくは脂肪族炭化水素、エーテル、エステル類、芳香族炭化水素、ケトン類である。
塩基を用いる場合、塩基としては、炭酸カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸塩;水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水素化ナトリウム等の水酸化物塩;水素化ナトリウム、水素化カリウム、金属ナトリウム、金属カリウム等の無機塩基、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、ナトリウム-t-ブトキシド等の金属アルコキシド類;トリエチルアミン、トリメチルアミン等のアミン類;ピリジン、ピコリン等のピリジン類;N,N-ジメチルアニリン等のアニリン;メチルリチウム、エチルリチウム、プロピルリチウム、ブチルリチウム等のアルキル金属化合物;フェニルリチウム等のアリール金属化合物等を挙げることができる。塩基は、用いる溶媒の種類によって、適宜選択することができる。反応溶媒への溶解性と取扱いの容易さの点から、アミン類、ピリジン類、アニリン類が好ましく、より好ましくはアミン類、ピリジン類である。
エステル化反応の上限温度は、好ましくは80℃以下、より好ましくは60℃以下、更に好ましくは50℃以下である。本反応は発熱反応であるため、このように上限温度を設定することで、反応暴走を抑えることができ、更に生成したスルホン酸エステルの熱分解も抑制できる。また、エステル化反応の下限温度は、好ましくは-30℃以上、より好ましくは-25℃以上、更に好ましくは-20℃以上である。このように下限温度を設定することで、反応停止や反応の溜まり込みが起こる危険性を回避することができる。
エステル化反応の時間は、好ましくは30分以上、より好ましくは1時間以上である。スルホン酸クロリドには、反応点が複数あるため、反応時間が短いと一部の反応点しか反応していない生成物が混在してしまう可能性があるが、そのような事態を容易に回避することができる。一方、反応の上限は特に限定されないが、生成したスルホン酸エステルが分解したり、時間が延びることによる生産性の低下を回避するため、反応時間は48時間以下とすることができ、好ましくは24時間以下、より好ましくは10時間以下である。
本発明の反応に用いられる試薬は、市販のものをそのまま用いても、精製して用いてもよい。他の化合物から製造して用いてもよい。純度については特に限定はされないが、反応点が複数ある反応のため、原料由来の不純物が少ない高純度の試薬が好ましく、90質量%以上であることが好ましい。
スルホン酸クロリドは、市販品をそのまま用いても、精製して用いてもよい。市販品がない場合は、別途製造して用いてもよい。別途製造する場合、例えば以下の方法が挙げられる。
a) 対応するアルキルチオロニウム塩の酸化的塩素化により製造する方法:例)Synlett (2013), 24(16), 2165-2169.; Journal of the Chemical Society (1952), 3334-40.
b) 対応するチオールの酸化的塩素化により製造する方法:例) Inorganica Chimica Acta (2011), 369(1), 45-48.; Industrial & Engineering Chemistry Process Design and Development (1964), 3(2), 164-9.
c) 対応するスルホン酸やその金属塩を塩化チオニルや五塩化リンなどで塩素化して製造する方法:例) Tetrahedron Letters (2009), 50(50), 7028-7031.;Journal of Organic Chemistry (1960), 25, 399-402.
アルキルチオロニウム塩の酸化的塩素化に用いる試薬は、塩素カチオンを生成する試薬であれば特に制限はないが、塩素ガス、次亜塩素酸ソーダ水溶液、亜塩素酸ソーダ、NCS、トリクロロイソシアヌル酸が反応速度や反応効率が高いことから好ましい。また、反応の後処理の容易さと酸化剤試薬のコスト、環境負荷の観点から次亜塩素酸水溶液、亜塩素酸ソーダがより好ましく、取扱いの容易さから次亜塩素酸水溶液が最も好ましい。これらの酸化的塩素化剤は、市販をそのまま用いても精製して用いてもよく、他の化合物から製造して用いてもよい。次亜塩素酸ソーダ水溶液は種々の濃度の水溶液が市販されているが、次亜塩素酸ソーダの濃度が濃いほど釜効率が向上し、生産性を上げることが可能であるため、好ましくは5質量%以上、より好ましくは10質量%以上、最も好ましくは12質量%以上である。
アルキルチオロニウム塩の対イオンは特に限定されないが、ハロゲン化物イオン、硫酸イオンなどが報告されており、対応するハロアルカンから容易に合成できる観点から、塩化物イオン、臭化物イオン、ヨウ化物イオンが好ましい。これらの対イオンは単独でも、2種以上の対イオンの混合物でもよい。
本発明において、晶析とは、式(10)で表されるスルホン酸エステルを含む溶液から、このスルホン酸エステルを固体として取り出す操作をいう。対応するスルホン酸クロリドとアルコール性水酸基を有する化合物の反応生成物を、場合によって濾過し、濃縮した後、溶媒と混合し、これを晶析工程に付すことができる。
溶媒は、目的物であるスルホン酸エステルを溶解することができる非水溶媒であれば特に限定されないが、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、sec-ブタノール、t-ブタノール、1-ペンタノール、3-ペンタノール、2-メチル-1-ブタノール、3-メチル-1-ブタノール、3-メチル-2-ブタノール、2-メチル-2-ブタノール、シクロヘキサノール、エチレングリコール、トリメチレングリコール等のアルコール;ジエチルエーテル、ジイソプロピルエーテル、t-ブチルメチルエーテル、アニソール、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル等のエーテル;塩化メチレン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、トリクロロエタン、ブロモプロパン、クロロベンゼン、ジクロロベンゼン等の含ハロゲン化炭化水素;アセトニトリル、プロピオニトリル、ブチロニトリル、ベンゾニトリル等の含シアノ炭化水素;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン等のケトン類が挙げられる。これらの溶媒は、単独で用いても、2種以上を併用してもよい。中でも反応に用いる塩基やその塩の溶解性、晶析後の乾燥工程の容易さからメタノール、エタノール等の低沸アルコール類が好ましい。
貧溶媒は、目的物であるスルホン酸エステルの溶解度が溶媒よりも低く、溶媒と混和する限り、特に制限はないが、溶解度の観点から、ペンタン、ヘキサン、ヘプタン、オクタン、石油エーテル等の脂肪族炭化水素;ベンゼン、トルエン、ニトロベンゼン等の芳香族炭化水素が挙げられる。これらの溶媒は、単独で用いても、2種以上を併用してもよい。また、溶媒と貧溶媒の体積はどちらが多くてもよい。また、溶媒と混ざる限り、少量であれば水を用いても良い。
晶析により得られた式(10)で表されるスルホン酸エステルの固体には、晶析工程で用いた溶媒が残存している可能性があるため、乾燥により除去することが好ましい。除去の方法は特に限定されないが、減圧条件下にて溶媒を除去する方法が好ましい。温度条件は、好ましくは80℃以下、より好ましくは60℃以下、更に好ましくは50℃以下であり、また、好ましくは0℃以上、より好ましくは5℃以上、更に好ましくは10℃以上である。このような範囲であれば、目的物であるスルホン酸エステルの熱分解を回避しつつ、溶媒を十分に除去することができる。除去の時間は、十分な除去及び生産効率の両方の点から、好ましくは、30分以上、より好ましくは1時間以上、更に好ましくは2時間以上であり、また、好ましくは48時間以下、より好ましくは36時間以下、更に好ましくは24時間以下である。
式(1)で表される化合物は、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併有してもよい。非水系電解液100質量%中の式(1)で表される化合物の配合量に制限はなく、本発明の効果を著しく損なわない限り任意である。配合量は0.001質量%以上とすることができ、好ましくは0.01質量%以上、より好ましくは0.02質量%以上、また、5質量%以下とすることができ、好ましくは4質量%以下、より好ましくは2質量%以下である。上記範囲を満たした場合、出力特性、負荷特性、低温特性、サイクル特性、高温保存特性等の効果がより向上する。
この際、式(1)で表される化合物は、生産性を著しく低下させない範囲内で、予め精製して、不純物が極力少ないものを用いることが好ましい。
本発明の非水系電解液二次電池において、式(1)で表される化合物以外に、目的に応じて適宜助剤を用いてもよい。助剤としては、以下に示される炭素-炭素不飽和結合を有する環状カーボネート、フッ素原子を有する不飽和環状カーボネート、モノフルオロリン酸塩及びジフルオロリン酸塩、過充電防止剤、並びにその他の助剤等が挙げられる。
本発明の非水系電解液において、非水系電解液二次電池の負極表面に皮膜を形成し、電池の長寿命化を達成するために、式(1)で表される化合物に加えて、炭素-炭素不飽和結合を有する環状カーボネート(以下、「不飽和環状カーボネート」と略記する場合がある)を用いるとより効果的である。
不飽和環状カーボネートとしては、ビニレンカーボネート類、芳香環又は炭素-炭素二重結合を有する置換基で置換されたエチレンカーボネート類、フェニルカーボネート類、ビニルカーボネート類、アリルカーボネート類等が挙げられる。
フッ素原子を有する不飽和環状カーボネートとして、不飽和結合とフッ素原子とを有する環状カーボネート(以下、「フッ素化不飽和環状カーボネート」と略記する場合がある)を用いることも好ましい。フッ素化不飽和環状カーボネートが有するフッ素原子の数は1以上であれば、特に制限されない。中でも、フッ素原子が通常6以下、好ましくは4以下であり、1個又は2個のものが最も好ましい。
フッ素化ビニレンカーボネート誘導体としては、4-フルオロビニレンカーボネート、4-フルオロ-5-メチルビニレンカーボネート、4-フルオロ-5-フェニルビニレンカーボネート、4-アリル-5-フルオロビニレンカーボネート、4-フルオロ-5-ビニルビニレンカーボネート等が挙げられる。
モノフルオロリン酸塩及びジフルオロリン酸塩のカウンターカチオンとしては特に限定はないが、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、及び、NR5R6R7R8(式中、R5~R8は、各々独立に、水素原子又は炭素数1~12の有機基を表す。)で表されるアンモニウム等が例示として挙げられる。
本発明の非水系電解液において、非水系電解液二次電池が過充電等の状態になった際に電池の破裂・発火を効果的に抑制するために、過充電防止剤を用いることができる。
過充電防止剤としては、ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、t-ブチルベンゼン、t-アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物;2-フルオロビフェニル、o-シクロヘキシルフルオロベンゼン、p-シクロヘキシルフルオロベンゼン等の上記芳香族化合物の部分フッ素化物;2,4-ジフルオロアニソール、2,5-ジフルオロアニソール、2,6-ジフルオロアニソール、3,5-ジフルオロアニソール等の含フッ素アニソール化合物等が挙げられる。中でも、ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、t-ブチルベンゼン、t-アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物が好ましい。これらは1種を単独で用いても、2種以上を併用してもよい。2種以上併用する場合は、特に、シクロヘキシルベンゼンとt-ブチルベンゼン又はt-アミルベンゼンとの組み合わせ、ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、t-ブチルベンゼン、t-アミルベンゼン等の酸素を含有しない芳香族化合物から選ばれる少なくとも1種と、ジフェニルエーテル、ジベンゾフラン等の含酸素芳香族化合物から選ばれる少なくとも1種を併用するのが過充電防止特性と高温保存特性のバランスの点から好ましい。
本発明の非水系電解液には、公知のその他の助剤を用いることができる。その他の助剤としては、エリスリタンカーボネート、スピロ-ビス-ジメチレンカーボネート、メトキシエチル-メチルカーボネート等のカーボネート化合物;無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸、無水グルタコン酸、無水イタコン酸、無水ジグリコール酸、シクロヘキサンジカルボン酸無水物、及びフェニルコハク酸無水物等のカルボン酸無水物;2,4,8,10-テトラオキサスピロ[5.5]ウンデカン、3,9-ジビニル-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン等のスピロ化合物;エチレンサルファイト、1,3-プロパンスルトン、1-フルオロ-1,3-プロパンスルトン、2-フルオロ-1,3-プロパンスルトン、3-フルオロ-1,3-プロパンスルトン、1-プロペン-1,3-スルトン、1-フルオロ-1-プロペン-1,3-スルトン、2-フルオロ-1-プロペン-1,3-スルトン、3-フルオロ-1-プロペン-1,3-スルトン、1,4-ブタンスルトン、1-ブテン-1,4-スルトン、3-ブテン-1,4-スルトン、フルオロスルホン酸メチル、フルオロスルホン酸エチル、メタンスルホン酸メチル、メタンスルホン酸エチル、ブスルファン、スルホレン、ジフェニルスルホン、N,N-ジメチルメタンスルホンアミド、N,N-ジエチルメタンスルホンアミド等の含硫黄化合物;1-メチル-2-ピロリジノン、1-メチル-2-ピペリドン、3-メチル-2-オキサゾリジノン、1,3-ジメチル-2-イミダゾリジノン及びN-メチルスクシンイミド等の含窒素化合物;ヘプタン、オクタン、ノナン、デカン、シクロヘプタン等の炭化水素化合物、フルオロベンゼン、ジフルオロベンゼン、ヘキサフルオロベンゼン、ベンゾトリフルオライド等の含フッ素芳香族化合物等が挙げられる。これらは1種を単独で用いても、2種以上を併用してもよい。これらの助剤を添加することにより、高温保存後の容量維持特性やサイクル特性を向上させることができる。
本発明の非水系電解液は、非水系電解液二次電池の中でも二次電池用、例えばリチウム二次電池用の電解液として好適である。本発明の非水系電解液二次電池は、公知の構造を採ることができ、典型的には、金属イオン(例えば、リチウムイオン)を吸蔵・放出可能な負極及び正極と、本発明の非水系電解液とを備える。
負極に使用される負極活物質は、電気化学的に金属イン(例えばリチウムイオン)を吸蔵・放出可能なものであれば、特に制限はない。具体例としては、炭素質材料、合金系材料、リチウム含有金属複合酸化物材料等が挙げられる。これらは1種を単独で用いてもよく、また2種以上を任意に組み合わせて併用してもよい。
負極活物質としては、炭素質材料、合金系材料、リチウム含有金属複合酸化物材料等が挙げられる。
負極活物質として用いられる炭素質材料としては、
(1)天然黒鉛、
(2)人造炭素質物質並びに人造黒鉛質物質を400~3200℃の範囲で1回以上熱処理した炭素質材料、
(3)負極活物質層が少なくとも2種以上の異なる結晶性を有する炭素質からなり、かつ/又はその異なる結晶性の炭素質が接する界面を有している炭素質材料、
(4)負極活物質層が少なくとも2種以上の異なる配向性を有する炭素質からなり、かつ/又はその異なる配向性の炭素質が接する界面を有している炭素質材料、から選ばれるものが、初期不可逆容量、高電流密度充放電特性のバランスがよく好ましい。
上記(2)の人造炭素質物質並びに人造黒鉛質物質としては、天然黒鉛、石炭系コークス、石油系コークス、石炭系ピッチ、石油系ピッチ及びこれらピッチを酸化処理したもの、ニードルコークス、ピッチコークス及びこれらを一部黒鉛化した炭素材、ファーネスブラック、アセチレンブラック、ピッチ系炭素繊維等の有機物の熱分解物、炭化可能な有機物及びこれらの炭化物、又は炭化可能な有機物をベンゼン、トルエン、キシレン、キノリン、n-へキサン等の低分子有機溶媒に溶解させた溶液及びこれらの炭化物等が挙げられる。
上記金属酸化物が、一般式(A)で表されるリチウムチタン複合酸化物であり、一般式(A)中、0.7≦x≦1.5、1.5≦y≦2.3、0≦z≦1.6であることが、リチウムイオンのドープ・脱ドープの際の構造が安定であることから好ましい。
[一般式(A)中、Mは、Na、K、Co、Al、Fe、Ti、Mg、Cr、Ga、Cu、Zn及びNbからなる群より選ばれる少なくとも1種の元素を表す。]
上記の一般式(A)で表される組成の中でも、
(a)1.2≦x≦1.4、1.5≦y≦1.7、z=0
(b)0.9≦x≦1.1、1.9≦y≦2.1、z=0
(c)0.7≦x≦0.9、2.1≦y≦2.3、z=0
の構造が、電池性能のバランスが良好なため特に好ましい。
負極活物質として炭素質材料を用いる場合、以下の物性を有するものであることが望ましい。
炭素質材料の学振法によるX線回折で求めた格子面(002面)のd値(層間距離)が、0.335nm以上であることが好ましく、また、通常0.360nm以下であり、0.350nm以下が好ましく、0.345nm以下が更に好ましい。また、学振法によるX線回折で求めた炭素質材料の結晶子サイズ(Lc)は、1.0nm以上であることが好ましく、中でも1.5nm以上であることが更に好ましい。
炭素質材料の体積基準平均粒径は、レーザー回折・散乱法により求めた体積基準の平均粒径(メジアン径)であり、通常1μm以上であり、3μm以上が好ましく、5μm以上が更に好ましく、7μm以上が特に好ましく、また、通常100μm以下であり、50μm以下が好ましく、40μm以下がより好ましく、30μm以下が更に好ましく、25μm以下が特に好ましい。
体積基準平均粒径の測定は、界面活性剤であるポリオキシエチレン(20)ソルビタンモノラウレートの0.2質量%水溶液(約10mL)に炭素粉末を分散させて、レーザー回折・散乱式粒度分布計(堀場製作所社製LA-700)を用いて行なう。該測定で求められるメジアン径を、本発明の炭素質材料の体積基準平均粒径と定義する。
炭素質材料のラマンR値は、アルゴンイオンレーザーラマンスペクトル法を用いて測定した値であり、通常0.01以上であり、0.03以上が好ましく、0.1以上が更に好ましく、また、通常1.5以下であり、1.2以下が好ましく、1以下が更に好ましく、0.5以下が特に好ましい。
また、炭素質材料の1580cm-1付近のラマン半値幅は特に制限されないが、通常10cm-1以上であり、15cm-1以上が好ましく、また、通常100cm-1以下であり、80cm-1以下が好ましく、60cm-1以下が更に好ましく、40cm-1以下が特に好ましい。
・アルゴンイオンレーザー波長 :514.5nm
・試料上のレーザーパワー :15~25mW
・分解能 :10~20cm-1
・測定範囲 :1100cm-1~1730cm-1
・ラマンR値、ラマン半値幅解析:バックグラウンド処理
・スムージング処理 :単純平均、コンボリューション5ポイント
炭素質材料のBET比表面積は、BET法を用いて測定した比表面積の値であり、通常0.1m2・g-1以上であり、0.7m2・g-1以上が好ましく、1.0m2・g-1以上が更に好ましく、1.5m2・g-1以上が特に好ましく、また、通常100m2・g-1以下であり、25m2・g-1以下が好ましく、15m2・g-1以下が更に好ましく、10m2・g-1以下が特に好ましい。
BET法による比表面積の測定は、表面積計(大倉理研製全自動表面積測定装置)を用いて、試料に対して窒素流通下350℃で15分間、予備乾燥を行なった後、大気圧に対する窒素の相対圧の値が0.3となるように正確に調製した窒素ヘリウム混合ガスを用いて、ガス流動法による窒素吸着BET1点法によって行なう。該測定で求められる比表面積を、本発明の炭素質材料のBET比表面積と定義する。
炭素質材料の球形の程度として円形度を測定した場合、以下の範囲に収まることが好ましい。なお、円形度は、「円形度=(粒子投影形状と同じ面積を持つ相当円の周囲長)/(粒子投影形状の実際の周囲長)」で定義され、円形度が1のときに理論的真球となる。炭素質材料の粒径が3~40μmの範囲にある粒子の円形度は1に近いほど望ましく、また、0.1以上が好ましく、中でも0.5以上が好ましく、0.8以上がより好ましく、0.85以上が更に好ましく、0.9以上が特に好ましい。高電流密度充放電特性は、円形度が大きいほど、充填性が向上し、粒子間の抵抗を抑えることができるため、高電流密度充放電特性は向上する。従って、円形度が上記範囲のように高いほど好ましい。
炭素質材料のタップ密度は、通常0.1g・cm-3以上であり、0.5g・cm-3以上が好ましく、0.7g・cm-3以上が更に好ましく、1g・cm-3以上が特に好ましく、また、2g・cm-3以下が好ましく、1.8g・cm-3以下が更に好ましく、1.6g・cm-3以下が特に好ましい。タップ密度が上記範囲であると、電池容量を確保することができるとともに、粒子間の抵抗の増大を抑制することができる。
炭素質材料の配向比は、通常0.005以上であり、0.01以上が好ましく、0.015以上が更に好ましく、また、通常0.67以下である。配向比が、上記範囲であると、優れた高密度充放電特性を確保することができる。なお、上記範囲の上限は、炭素質材料の配向比の理論上限値である。
・ターゲット:Cu(Kα線)グラファイトモノクロメーター
・スリット :
発散スリット=0.5度
受光スリット=0.15mm
散乱スリット=0.5度
・測定範囲及びステップ角度/計測時間:
(110)面:75度≦2θ≦80度 1度/60秒
(004)面:52度≦2θ≦57度 1度/60秒
炭素質材料のアスペクト比は、通常1以上、また、通常10以下であり、8以下が好ましく、5以下が更に好ましい。上記範囲であると、極板化時のスジ引きを抑制し、更に均一な塗布が可能となるため、優れた高電流密度充放電特性を確保することができる。なお、上記範囲の下限は、炭素質材料のアスペクト比の理論下限値である。
本発明で定義される菱面体晶率は、X線広角回折法(XRD)による菱面体晶構造黒鉛層(ABCスタッキング層)と六方晶構造黒鉛層(ABスタッキング層)の割合から次式を用いて求めることができる。
菱面体晶率(%)=XRDのABC(101)ピークの積分強度÷
XRDのAB(101)ピーク積分強度×100
0.2mmの試料板に負極活物質粉体が配向しないように充填し、X線回折装置(例えば、PANalytical社製X'Pert Pro MPDでCuKα線にて、出力45kV、40mA)で測定する。得られた回折パターンを使用し解析ソフトJADE5.0を用い、非対称ピアソンVII関数を用いたプロファイルフィッティングにより前記ピーク積分強度をそれぞれ算出し、前記式から菱面体晶率を求める。
・ターゲット:Cu(Kα線)グラファイトモノクロメーター
・ スリット:
ソーラースリット 0.04度
発散スリット 0.5度
横発散マスク 15mm
散乱防止スリット 1度
・測定範囲及びステップ角度/計測時間:
(101)面:41度≦2θ≦47.5度 0.3度/60秒
・バックグラウンド補正:42.7から45.5度の間を直線で結び、バックグラウンドとし差し引く。
・菱面体晶構造黒鉛粒子層のピーク:43.4度付近のピークのことを指す。
・六方晶構造黒鉛粒子層のピーク:44.5度付近のピークのことを指す。
電極の製造は、本発明の効果を著しく損なわない限り、公知のいずれの方法を用いることができる。例えば、負極活物質に、バインダー、溶媒、必要に応じて、増粘剤、導電材、充填材等を加えてスラリーとし、これを集電体に塗布、乾燥した後にプレスすることによって形成することができる。
また、合金系材料を用いる場合には、蒸着法、スパッタ法、メッキ法等の手法により、上述の負極活物質を含有する薄膜層(負極活物質層)を形成する方法も用いられる。
負極活物質を保持させる集電体としては、公知のものを任意に用いることができる。負極の集電体としては、例えば、アルミニウム、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の金属材料が挙げられるが、加工し易さとコストの点から特に銅が好ましい。
また、集電体の形状は、集電体が金属材料の場合は、例えば、金属箔、金属円柱、金属コイル、金属板、金属薄膜、エキスパンドメタル、パンチメタル、発泡メタル等が挙げられる。中でも、好ましくは金属薄膜、より好ましくは銅箔であり、更に好ましくは圧延法による圧延銅箔と、電解法による電解銅箔があり、どちらも集電体として用いることができる。
集電体の厚さは、電池容量の確保、取扱い性の観点から、通常1μm以上、好ましくは5μm以上であり、通常100μm以下、好ましくは50μm以下である。
集電体と負極活物質層の厚さの比は特に制限されないが、「(非水系電解液注液直前の片面の負極活物質層厚さ)/(集電体の厚さ)」の値が、150以下が好ましく、20以下が更に好ましく、10以下が特に好ましく、また、0.1以上が好ましく、0.4以上が更に好ましく、1以上が特に好ましい。集電体と負極活物質層の厚さの比が、上記範囲であると、電池容量を確保することができるとともに、高電流密度充放電時における集電体の発熱を抑制することができる。
負極活物質を結着するバインダーとしては、非水系電解液や電極製造時に用いる溶媒に対して安定な材料であれば、特に制限されない。
具体例としては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリメチルメタクリレート、芳香族ポリアミド、ポリイミド、セルロース、ニトロセルロース等の樹脂系高分子;SBR(スチレン・ブタジエンゴム)、イソプレンゴム、ブタジエンゴム、フッ素ゴム、NBR(アクリロニトリル・ブタジエンゴム)、エチレン・プロピレンゴム等のゴム状高分子;スチレン・ブタジエン・スチレンブロック共重合体又はその水素添加物;EPDM(エチレン・プロピレン・ジエン三元共重合体)、スチレン・エチレン・ブタジエン・スチレン共重合体、スチレン・イソプレン・スチレンブロック共重合体又はその水素添加物等の熱可塑性エラストマー状高分子;シンジオタクチック-1,2-ポリブタジエン、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、プロピレン・α-オレフィン共重合体等の軟質樹脂状高分子;ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素化ポリフッ化ビニリデン、ポリテトラフルオロエチレン・エチレン共重合体等のフッ素系高分子;アルカリ金属イオン(特にリチウムイオン)のイオン伝導性を有する高分子組成物等が挙げられる。これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
スラリーを形成するための溶媒としては、負極活物質、バインダー、並びに必要に応じて使用される増粘剤及び導電材を溶解又は分散することが可能な溶媒であれば、その種類に特に制限はなく、水系溶媒と有機系溶媒のどちらを用いてもよい。
水系溶媒としては、水、アルコール等が挙げられ、有機系溶媒としてはN-メチルピロリドン(NMP)、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、シクロヘキサノン、酢酸メチル、アクリル酸メチル、ジエチルトリアミン、N,N-ジメチルアミノプロピルアミン、テトラヒドロフラン(THF)、トルエン、アセトン、ジエチルエーテル、ジメチルアセトアミド、ヘキサメチルホスファルアミド、ジメチルスルホキシド、ベンゼン、キシレン、キノリン、ピリジン、メチルナフタレン、ヘキサン等が挙げられる。
特に水系溶媒を用いる場合、増粘剤に併せて分散剤等を含有させ、SBR等のラテックスを用いてスラリー化することが好ましい。なお、これらの溶媒は、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
増粘剤は、通常、スラリーの粘度を調製するために使用される。増粘剤としては、特に制限されないが、具体的には、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、酸化スターチ、リン酸化スターチ、カゼイン及びこれらの塩等が挙げられる。これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
負極活物質を電極化した際の電極構造は特に制限されないが、集電体上に存在している負極活物質の密度は、1g・cm-3以上が好ましく、1.2g・cm-3以上が更に好ましく、1.3g・cm-3以上が特に好ましく、また、2.2g・cm-3以下が好ましく、2.1g・cm-3以下がより好ましく、2.0g・cm-3以下が更に好ましく、1.9g・cm-3以下が特に好ましい。集電体上に存在している負極活物質の密度が、上記範囲であると、負極活物質粒子の破壊を防止して、初期不可逆容量の増加や、集電体/負極活物質界面付近への非水系電解液の浸透性低下による高電流密度充放電特性悪化を抑制することができる一方、電池容量の低下や抵抗の増大を抑制することができる。
負極板の厚さは用いられる正極板に合わせて設計されるものであり、特に制限されないが、芯材の金属箔厚さを差し引いた合材層の厚さは通常15μm以上、好ましくは20μm以上、より好ましくは30μm以上、また、通常300μm以下、好ましくは280μm以下、より好ましくは250μm以下が望ましい。
また、上記負極板の表面に、これとは異なる組成の物質が付着したものを用いてもよい。表面付着物質としては酸化アルミニウム、酸化ケイ素、酸化チタン、酸化ジルコニウム、酸化マグネシウム、酸化カルシウム、酸化ホウ素、酸化アンチモン、酸化ビスマス等の酸化物、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウム等の硫酸塩、炭酸リチウム、炭酸カルシウム、炭酸マグネシウム等の炭酸塩等が挙げられる。
<正極活物質>
以下に正極に使用される正極活物質について述べる。
(組成)
正極活物質としては、電気化学的にリチウムイオンを吸蔵・放出可能なものであれば特に制限されないが、例えば、リチウムと少なくとも1種の遷移金属を含有する物質が好ましい。具体例としては、リチウム遷移金属複合酸化物、リチウム含有遷移金属リン酸化合物が挙げられる。
また、上記正極活物質の表面に、これとは異なる組成の物質が付着したものを用いてもよい。表面付着物質としては酸化アルミニウム、酸化ケイ素、酸化チタン、酸化ジルコニウム、酸化マグネシウム、酸化カルシウム、酸化ホウ素、酸化アンチモン、酸化ビスマス等の酸化物、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウム等の硫酸塩、炭酸リチウム、炭酸カルシウム、炭酸マグネシウム等の炭酸塩、炭素等が挙げられる。
本発明においては、正極活物質の表面に、これとは異なる組成の物質が付着したものも「正極活物質」という。
正極活物質の粒子の形状は、従来用いられるような、塊状、多面体状、球状、楕円球状、板状、針状、柱状等が挙げられる。また、一次粒子が凝集して、二次粒子を形成していてもよい。
正極活物質のタップ密度は、好ましくは0.5g/cm3以上、より好ましくは0.8g/cm3以上、更に好ましくは1.0g/cm3以上である。該正極活物質のタップ密度が上記範囲であると、正極活物質層形成時に必要な分散媒量及び導電材や結着剤の必要量を抑えることができ、結果正極活物質の充填率及び電池容量を確保することができる。タップ密度の高い複合酸化物粉体を用いることにより、高密度の正極活物質層を形成することができる。タップ密度は一般に大きいほど好ましく、特に上限はないが、好ましくは4.0g/cm3以下、より好ましくは3.7g/cm3以下、更に好ましくは3.5g/cm3以下である。上記範囲であると負荷特性の低下を抑制することができる。
なお、本発明では、タップ密度は、正極活物質粉体5~10gを10mlのガラス製メスシリンダーに入れ、ストローク約20mmで200回タップした時の粉体充填密度(タップ密度)g/ccとして求める。
正極活物質の粒子のメジアン径d50(一次粒子が凝集して二次粒子を形成している場合には二次粒子径)は好ましくは0.3μm以上、より好ましくは0.5μm以上、更に好ましくは0.8μm以上、最も好ましくは1.0μm以上であり、上限は、好ましくは30μm以下、より好ましくは27μm以下、更に好ましくは25μm以下、最も好ましくは22μm以下である。上記範囲であると、高タップ密度品が得られ、電池性能の低下を抑制できる一方、電池の正極作成、即ち活物質と導電材やバインダー等を溶媒でスラリー化して薄膜状に塗布する際に、スジ引き等の問題を防止することができる。ここで、異なるメジアン径d50をもつ該正極活物質を2種類以上混合することで、正極作成時の充填性を更に向上させることができる。
一次粒子が凝集して二次粒子を形成している場合には、該正極活物質の平均一次粒子径としては、好ましくは0.05μm以上、より好ましくは0.1μm以上、更に好ましくは0.2μm以上であり、上限は、好ましくは5μm以下、より好ましくは4μm以下、更に好ましくは3μm以下、最も好ましくは2μm以下である。上記範囲であると、粉体充填性及び比表面積を確保し、電池性能の低下を抑制することができる一方、適度な結晶性が得られることによって、充放電の可逆性を確保することができる。
正極活物質のBET比表面積は、好ましくは0.1m2/g以上、より好ましくは0.2m2/g以上、更に好ましくは0.3m2/g以上であり、上限は50m2/g以下、好ましくは40m2/g以下、更に好ましくは30m2/g以下である。BET比表面積が上記範囲であると、電池性能を確保できるとともに、正極活性物質の塗布性を良好に保つことができる。
なお、本発明では、BET比表面積は、表面積計(例えば、大倉理研製全自動表面積測定装置)を用い、試料に対して窒素流通下150℃で30分間、予備乾燥を行なった後、大気圧に対する窒素の相対圧の値が0.3となるように正確に調製した窒素ヘリウム混合ガスを用い、ガス流動法による窒素吸着BET1点法によって測定した値で定義される。
正極活物質の製造法としては、無機化合物の製造法として一般的な方法が用いられる。特に球状ないし楕円球状の活物質を作成するには種々の方法が考えられるが、例えば、遷移金属の原料物質を水等の溶媒中に溶解ないし粉砕分散して、攪拌をしながらpHを調節して球状の前駆体を作成回収し、これを必要に応じて乾燥した後、LiOH、Li2CO3、LiNO3等のLi源を加えて高温で焼成して活物質を得る方法等が挙げられる。
以下に、正極の構成について述べる。本発明において、正極は、正極活物質と結着剤とを含有する正極活物質層を、集電体上に形成して作製することができる。正極活物質を用いる正極の製造は、常法により行うことができる。即ち、正極活物質と結着剤、並びに必要に応じて導電材及び増粘剤等を乾式で混合してシート状にしたものを正極集電体に圧着するか、又はこれらの材料を液体媒体に溶解又は分散させてスラリーとして、これを正極集電体に塗布し、乾燥することにより、正極活物質層を集電体上に形成されることにより正極を得ることができる。
塗布、乾燥によって得られた正極活物質層は、正極活物質の充填密度を上げるために、ハンドプレス、ローラープレス等により圧密化することが好ましい。正極活物質層の密度は、下限として好ましくは1.5g/cm3以上、より好ましくは2g/cm3、更に好ましくは2.2g/cm3以上であり、また、好ましくは5g/cm3以下、より好ましくは4.5g/cm3以下、更に好ましくは4g/cm3以下の範囲である。上記範囲であると、良好な充放電特性が得られるとともに、電気抵抗の増大を抑制することができる。
導電材としては、公知の導電材を任意に用いることができる。具体例としては、銅、ニッケル等の金属材料;天然黒鉛、人造黒鉛等の黒鉛(グラファイト);アセチレンブラック等のカーボンブラック;ニードルコークス等の無定形炭素等の炭素材料等が挙げられる。なお、これらは、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。導電材は、正極活物質層中に、通常0.01質量%以上、好ましくは0.1質量%以上、より好ましくは1質量%以上であり、また上限は、通常50質量%以下、好ましくは30質量%以下、より好ましくは15質量%以下含有するように用いられる。上記範囲であると、十分な導電性と電池容量を確保することができる。
正極活物質層の製造に用いる結着剤としては、特に限定されず、塗布法の場合は、電極製造時に用いる液体媒体に対して溶解又は分散される材料であればよいが、具体例としては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリイミド、芳香族ポリアミド、セルロース、ニトロセルロース等の樹脂系高分子;SBR(スチレン-ブタジエンゴム)、NBR(アクリロニトリル-ブタジエンゴム)、フッ素ゴム、イソプレンゴム、ブタジエンゴム、エチレン-プロピレンゴム等のゴム状高分子;スチレン・ブタジエン・スチレンブロック共重合体又はその水素添加物、EPDM(エチレン・プロピレン・ジエン三元共重合体)、スチレン・エチレン・ブタジエン・エチレン共重合体、スチレン・イソプレン・スチレンブロック共重合体又はその水素添加物等の熱可塑性エラストマー状高分子;シンジオタクチック-1,2-ポリブタジエン、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、プロピレン・α-オレフィン共重合体等の軟質樹脂状高分子;ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン、フッ素化ポリフッ化ビニリデン、ポリテトラフルオロエチレン・エチレン共重合体等のフッ素系高分子;アルカリ金属イオン(特にリチウムイオン)のイオン伝導性を有する高分子組成物等が挙げられる。なお、これらの物質は、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
スラリーを形成するための溶媒としては、正極活物質、導電材、結着剤、並びに必要に応じて使用される増粘剤を溶解又は分散することが可能な溶媒であれば、その種類に特に制限はなく、水系溶媒と有機系溶媒のどちらを用いてもよい。水系媒体としては、例えば、水、アルコールと水との混合媒等が挙げられる。有機系媒体としては、例えば、ヘキサン等の脂肪族炭化水素類;ベンゼン、トルエン、キシレン、メチルナフタレン等の芳香族炭化水素類;キノリン、ピリジン等の複素環化合物;アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類;酢酸メチル、アクリル酸メチル等のエステル類;ジエチレントリアミン、N,N-ジメチルアミノプロピルアミン等のアミン類;ジエチルエーテル、プロピレンオキシド、テトラヒドロフラン(THF)等のエーテル類;N-メチルピロリドン(NMP)、ジメチルホルムアミド、ジメチルアセトアミド等のアミド類;ヘキサメチルホスファルアミド、ジメチルスルホキシド等の非プロトン性極性溶媒等が挙げられる。
正極集電体の材質としては特に制限されず、公知のものを任意に用いることができる。具体例としては、アルミニウム、ステンレス鋼、ニッケルメッキ、チタン、タンタル等の金属材料;カーボンクロス、カーボンペーパー等の炭素材料が挙げられる。中でも金属材料、特にアルミニウムが好ましい。
集電体と正極活物質層の厚さの比は特には限定されないが、(電解液注液直前の片面の正極活物質層の厚さ)/(集電体の厚さ)の値が20以下であることが好ましく、より好ましくは15以下、最も好ましくは10以下であり、下限は、0.5以上が好ましく、より好ましくは0.8以上、最も好ましくは1以上の範囲である。この範囲を上回ると、高電流密度充放電時に集電体がジュール熱による発熱を生じる場合がある。上記範囲であると、高電流密度充放電時の集電体の発熱を抑制し、電池容量を確保することができる。
本発明の非水系電解液を用いる場合、高出力かつ高温時の安定性を高める観点から、正極活物質層の面積は、電池外装ケースの外表面積に対して大きくすることが好ましい。具体的には、二次電池の外装の表面積に対する正極の電極面積の総和が面積比で15倍以上とすることが好ましく、更に40倍以上とすることがより好ましい。外装ケースの外表面積とは、有底角型形状の場合には、端子の突起部分を除いた発電要素が充填されたケース部分の縦と横と厚さの寸法から計算で求める総面積をいう。有底円筒形状の場合には、端子の突起部分を除いた発電要素が充填されたケース部分を円筒として近似する幾何表面積である。正極の電極面積の総和とは、負極活物質を含む合材層に対向する正極合材層の幾何表面積であり、集電体箔を介して両面に正極合材層を形成してなる構造では、それぞれの面を別々に算出する面積の総和をいう。
正極板の厚さは特に限定されないが、高容量かつ高出力の観点から、芯材の金属箔厚さを差し引いた合材層の厚さは、集電体の片面に対して下限として、好ましくは10μm以上、より好ましくは20μm以上で、上限としては、好ましくは500μm以下、より好ましくは450μm以下である。
また、上記正極板の表面に、これとは異なる組成の物質が付着したものを用いてもよい。表面付着物質としては酸化アルミニウム、酸化ケイ素、酸化チタン、酸化ジルコニウム、酸化マグネシウム、酸化カルシウム、酸化ホウ素、酸化アンチモン、酸化ビスマス等の酸化物、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウム等の硫酸塩、炭酸リチウム、炭酸カルシウム、炭酸マグネシウム等の炭酸塩、炭素等が挙げられる。
正極と負極との間には、短絡を防止するために、通常はセパレータを介在させる。この場合、本発明の非水系電解液は、通常はこのセパレータに含浸させて用いる。
セパレータの材料や形状については特に制限されず、本発明の効果を著しく損なわない限り、公知のものを任意に採用することができる。中でも、本発明の非水系電解液に対し安定な材料で形成された、樹脂、ガラス繊維、無機物等が用いられ、保液性に優れた多孔性シート又は不織布状の形態の物等を用いるのが好ましい。
更に、セパレータとして多孔性シートや不織布等の多孔質のものを用いる場合、セパレータの空孔率は任意であるが、通常20%以上であり、35%以上が好ましく、45%以上が更に好ましく、また、通常90%以下であり、85%以下が好ましく、75%以下が更に好ましい。空孔率が、上記範囲であると、絶縁性及び機械的強度を確保できる一方、膜抵抗を抑え良好なレート特性を得ることができる。
<電極群>
電極群は、上記の正極板と負極板とを上記のセパレータを介してなる積層構造のもの、及び上記の正極板と負極板とを上記のセパレータを介して渦巻き状に捲回した構造のもののいずれでもよい。電極群の体積が電池内容積に占める割合(以下、電極群占有率と称する)は、通常40%以上であり、50%以上が好ましく、また、通常90%以下であり、80%以下が好ましい。電極群占有率が、上記範囲であると、電池容量を確保できるとともに内部圧力の上昇に伴う充放電繰り返し性能や高温保存等の特性低下を抑制し、更にはガス放出弁の作動を防止することができる。
集電構造は、特に制限されないが、本発明の非水系電解液による高電流密度の充放電特性の向上をより効果的に実現するには、配線部分や接合部分の抵抗を低減する構造にすることが好ましい。このように内部抵抗を低減させた場合、本発明の非水系電解液を使用した効果は特に良好に発揮される。
外装ケースの材質は用いられる非水系電解液に対して安定な物質であれば特に制限されない。具体的には、ニッケルめっき鋼板、ステンレス、アルミニウム又はアルミニウム合金、マグネシウム合金等の金属類、又は、樹脂とアルミ箔との積層フィルム(ラミネートフィルム)が用いられる。軽量化の観点から、アルミニウム又はアルミニウム合金の金属、ラミネートフィルムが好適に用いられる。
保護素子として、異常発熱や過大電流が流れた時に抵抗が増大するPTC(Positive temperature Coefficient)、温度ヒューズ、サーミスター、異常発熱時に電池内部圧力や内部温度の急激な上昇により回路に流れる電流を遮断する弁(電流遮断弁)等を使用することができる。上記保護素子は高電流の通常使用で作動しない条件のものを選択することが好ましく、保護素子がなくても異常発熱や熱暴走に至らない設計にすることがより好ましい。
<正極の作製>
正極活物質としてニッケルマンガンコバルト酸リチウム(LiNi1/3Mn1/3Co1/3O2)90質量部を用い、カーボンブラック7質量部とポリフッ化ビニリデン3質量部を混合し、N-メチル-2-ピロリドンを加えスラリー化し、これを厚さ15μmのアルミニウム箔の両面に均一に11.85mg・cm-2となるように塗布、乾燥した後、正極活物質層の密度が2.6g・cm-3になるようにプレスして正極とした。
黒鉛に、増粘剤としてカルボキシメチルセルロースナトリウムの水性ディスパージョン(カルボキシメチルセルロースナトリウムの濃度1質量%)と、バインダーとしてスチレン-ブタジエンゴムの水性ディスパージョン(スチレン-ブタジエンゴムの濃度50質量%)を加え、ディスパーザーで混合してスラリー化した。得られたスラリーを厚さ12μmの銅箔の片面に均一に6.0mg・cm-2となるように塗布して乾燥し、その後、負極活物質層の密度が1.36g・cm-3になるようにプレスして負極とした。用いた黒鉛は、d50値が10.9μmであり、比表面積が3.41m2/gであり、タップ密度が0.985g/cm3である。また、スラリーは乾燥後の負極において、黒鉛:カルボキシメチルセルロースナトリウム:スチレン-ブタジエンゴム=97.5:1.5:1の質量比となるように作成した。
上記の正極、負極、及びセパレータを、負極、セパレータ、正極の順に積層した。セパレータにはポリプロピレン製、厚み20μm、空孔率54%のものを用いた。こうして得られた電池要素を筒状のアルミニウムラミネートフィルムで包み込み、後述する電解液を注入した後で真空封止し、シート状の非水系電解液二次電池を作製した。更に、電極間の密着性を高めるために、ガラス板でシート状電池を挟んで加圧した。
<初期充放電試験>
25℃の恒温槽中、シート状の非水系電解液二次電池を0.05Cで10時間充電後、3時間休止させ、その後4.1Vまで0.2Cで定電流充電した。更に3時間の休止の後に、4.1Vまで0.2Cで定電流-定電圧充電し、次いで1/3Cで3.0Vまで定電流放電した。その後、4.1Vまでの1/3C定電流-定電圧充電と、これに続く3.0Vまでの1/3C定電流放電を1サイクルとする充放電サイクルを2サイクル行った。更に、4.1Vまで1/3Cで定電流-定電圧充電した後に、電池を60℃で12時間保管することで電池を安定させた。その後、25℃にて4.2Vまでの1/3C定電流-定電圧充電と、これに続く3.0Vまでの1/3C定電流放電の充放電サイクルを2サイクル行った。このときの最後の放電容量を初期容量とした。なお、1Cとは電池の全容量を1時間で放電させる場合の電流値のことである。
初期充放電を実施した電池を、60℃において、2Cの定電流法で4.2Vまで充電した後、2Cの定電流法で3.0Vまで放電する充放電を100サイクル行った。その後、25℃にて4.2Vまでの1/3C定電流-定電圧充電と、これに続く3.0Vまでの1/3C定電流放電の充放電サイクルを3サイクル行った。このときの最後の放電容量をサイクル後容量とし、初期容量に対するサイクル後容量をサイクル容量維持率(%)とした。
初期充放電を実施した電池を、4.2Vまで1/3C定電流-定電圧充電し、60℃で1週間静置した。その後、25℃にて4.2Vまでの1/3C定電流-定電圧充電と、これに続く3.0Vまでの1/3C定電流放電の充放電サイクルを3サイクル行った。このときの最後の放電容量を高温保存後容量とし、初期容量に対する高温保存後容量を高温保存容量維持率(%)とした。
初期及びサイクル後の電池を3.72Vに調整し、その状態から-30℃において種々の電流値で10秒間定電流放電する。種々の電流値に対して10秒後の電圧をプロットし、10秒後の電圧が3Vとなるような電流値を求める。このようにして求められた点と、初期値(開回路状態)の点を結んで得られる直線の傾きを低温抵抗特性(Ω)と定義した。
<合成例1:式(A)の化合物の合成>
50ml 三口フラスコにL-乳酸メチル4.28g(41mmol)を量りとり、メチルエチルケトン(MEK)10mlを加えて均一溶液とした。これを氷浴に浸し、3℃まで冷却後、トリエチルアミン4.16g(41mmol)を加えた。ここに、滴下ロートを用いて、1,3-ブタンジスルホン酸クロリド5.0g(20mmol)/MEK13ml溶液を、内温が10℃を超えないようにして、約1.5時間かけて滴下した。滴下終了後、内温5℃で2時間撹拌し、その後、反応溶液をろ過した。得られたろ液を揮発成分がなくなるまで濃縮し、薄黄色オイルを得た。得られたオイルをメタノール40mlに溶解し、ドライアイス/エタノールバスにて冷却しながら、内温-20℃にて30分撹拌した。目的物が白色粉末として析出した。これを吸引ろ過、メタノールで洗浄後、真空ポンプで真空乾燥(25℃、12時間)を行い、目的のジスルホン酸エステル4.87g(収率63.6%)を得た。GC分析から見積もられた純度は99.3%であった。
1H-NMR(CDCl3, 400MHz):δ5.15(q,J=7, 2H), 3.81(s,6H), 3.38-3.25(m,4H), 2.13-2.10(m,4H), 1.62(d,J=7, 6H). MS(DCI): m/z 391(M+H)+.
100ml三口フラスコに、L-乳酸メチル1.79g(17.2mmol)及び1,5-ペンタンジスルホン酸クロリド2.10g(7.8mmol)、テトラヒドロフラン(THF)20mlを仕込み、均一な溶液とした後、内温2℃まで氷冷した。窒素フロー下、トリエチルアミン1.92g(18.9mmol)のTHF(5ml)溶液を、滴下ロートにて内温2~5℃で滴下した。滴下終了後、氷冷下で2時間撹拌し、水を投入した後、酢酸エチルにて抽出し、有機層を無水硫酸マグネシウムにて乾燥後濃縮し、オイル状物を得た。ここにメタノール5mlを添加し、ドライアイス/エタノールバスにて冷却しながら内温-20℃にて30分撹拌した。析出した白色粉末をろ別し、真空乾燥(40℃、5時間)を行い、目的のジスルホン酸エステル1.8g(4.4mmol)(収率57%)を得た。GC分析から見積もられた純度は99.8%であった。
1H-NMR(CDCl3, 400MHz):δ5.14(q,J=8, 2H), 3.81(s,6H), 3.33-3.18(m,4H), 2.03-1.92(m,4H), 1.61-1.58(m,2H), 1.62(d,J=8, 6H). MS(DCI): m/z 405(M+H)+.
100ml三口フラスコに、L-乳酸メチル2.03g(19.5mmol)及び1,6-ヘキサンビス(スルホニルクロリド) 2.50g(8.8mmol)、THF20mlを仕込み、均一な溶液とした後、内温2℃まで氷冷した。窒素フロー下、トリエチルアミン2.23g(22.0mmol)のTHF(5ml)溶液を、滴下ロートにて内温2~5℃で滴下した。滴下終了後氷冷下2h撹拌し、水を投入した後、酢酸エチルにて抽出し、有機層を無水硫酸マグネシウムにて乾燥後濃縮した。得られたオイル状粗体にメタノール5mlを添加し、ドライアイス/エタノールバスにて冷却しながら内温-20℃にて撹拌したが固化しなかった。シリカゲルカラム(酢酸エチル/ヘキサン=3/7→2/3)にて精製を行い、オイル状の目的物を得た。メタノールを除去後、真空乾燥を行い、目的のジスルホン酸エステル1.1g(2.6mmol)、収率30%で得た。
1H-NMR(CDCl3):δ5.14(q,J=8, 2H), 3.80(s,6H), 3.30-3.16(m,4H), 2.01-1.88(br,4H), 1.62(d,J=8, 6H), 1.56-1.49(m,4H). MS(DCI): m/z 419(M+H)+.
窒素雰囲気下、50ml三口フラスコに、グリセロールカーボネート 1.94g (0.016 mol)、THF10mlを仕込み、均一な溶液とした。次いで、撹拌しながらトリエチルアミン1.75g(0.017 mol)を加え、氷浴で内温3℃まで冷却した。ここに、1,4-ブタンジスルホン酸クロリド2.0g(0.008mol) /THF6mlを、内温が10℃を超えないようにゆっくりと滴下した。その後、更に内温5℃で2時間撹拌した。氷浴を外して室温(27.2℃)に戻し、水20ml、酢酸エチル30mlを添加後、析出した固体をろ取した。この固体をアセトン:メタノール混合溶媒(体積比で1:3)に溶解させ、5℃で30分間した。目的物が白色粉末として析出した。これを吸引ろ過、メタノールで洗浄後、真空ポンプで真空乾燥(25℃、12時間)する事で、目的のジスルホン酸エステル2.76g(収率:90.2%)を得た。本化合物は沸点が高くGC分析では検出できなかったが、1H NMRより不純物なく目的のジスルホン酸エステルが得られることを確認した。
1H-NMR(CDCl3, 400MHz):δ5.12-5.07(m, 2H), 4.60(t, J=9, 2H), 4.51-4.42(m,4H), 4.30-4.26(dd, J=6, 2H), 3.51-3.47(m,4H), 1.88-1.81(m, 4H). MS(DCI): m/z 419(M+H)+.
薄黄色オイルを得るまでは実施例1と同様の方法にて製造を行った。得られたオイルを、そのままドライアイス/エタノールバスにて、内温-20℃まで冷却したが、目的物の固体は得られなかった。この薄黄色オイルについて真空ポンプで真空乾燥(25℃, 12時間)し、目的物を薄黄色オイル9.27g (収率:121.1%)を得た。GC分析から見積もられた純度は66.5%であった。
得られた薄黄色オイルをメタノールに溶解するまでは実施例1(スケール5分の3)と同様の方法にて製造を行った。得られたメタノール溶液を室温(27℃)で撹拌したが、目的物の固体は得られなかった。また、このメタノール溶液を再び水浴30℃にて濃縮することで、目的物を薄黄色オイル4.99g (収率:108.7%)として得た。GC分析から見積もられた純度は87.8%であった。
乾燥アルゴン雰囲気下、エチレンカーボネートとジメチルカーボネートとエチルメチルカーボネートとの混合物(容量比3:3:4)に、十分に乾燥したLiPF6を非水電解液全量で1mol/Lとなるように溶解させた(この電解液を「基準電解液」と称する場合がある)。基準電解液に上記合成例1で得られた式(A)で表される化合物を非水系電解液100質量%中、0.73質量%となるように加えて、非水系電解液を調製した。この電解液を用いて上述の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
実施例1の非水系電解液に、更にビニレンカーボネート(以下、VC)を非水系電解液100質量%中、0.5質量%となるように加えたこと以外は、実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)の化合物の代わりに、合成例2の式(B)の化合物を非水系電解液に対して1.03質量%となるように加えたこと以外は、実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)の化合物の代わりに、合成例3の式(C)の化合物を非水系電解液に対して1.07質量%となるように加えたこと以外は、実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)の化合物の代わりに、合成例4の式(D)の化合物を非水系電解液に対して0.78質量%となるように加えたこと以外は、実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)で表される化合物の代わりに、下記式(E)で表される化合物を非水系電解液100質量%中、0.70質量%となるように加えた以外は実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。このようにして得られた結果を表2に示す。
参考例1の非水系電解液に、更にVCを非水系電解液100質量%中、0.5質量%となるように加えた以外は、参考例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
構造式(A)の化合物の代わりに、下記式(F)の化合物を非水系電解液に対して0.51質量%となるように加えた以外は実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
構造式(A)の化合物の代わりに、下記式(G)の化合物を非水系電解液に対して0.71質量%となるように加えた以外は実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)で表される化合物の代わりに、VCを非水系電解液100質量%中、0.50質量%となるように加えた以外は実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
式(A)の化合物を用いなかった以外は、実施例1と同様の方法で電池を作成し、サイクル容量維持率、高温保存試験及び低温抵抗特性を測定した。結果を表2に示す。
参考例1~2に示した通り、式(1)におけるZの炭素数が3のスルホン酸エステルを用いた場合では、サイクル容量維持率を向上させることはできたが、低温抵抗特性は、式(1)におけるZが炭素数4以上である実施例1~2の方が優れる結果が得られた。
参考例3、4より、式(1)におけるXが酸素原子を有していない化合物を用いた場合には、サイクル容量維持率と低温抵抗特性に改善効果は見られなかった。
具体例としては、ノート型パソコン、タブレット型パソコン、電子ブックプレーヤー、携帯電話、スマートフォン、ポータブルCD/DVD/BDプレイヤー、ポータブル液晶テレビ、ハンディークリーナー、トランシーバー、電子手帳、電卓、メモリーカード、ラジオ、バックアップ電源、モーター、自動車、バイク、原動機付自転車、自転車、照明器具、玩具、ゲーム機器、時計、電動工具、カメラ、負荷平準化用電源、自然エネルギー貯蔵電源等が挙げられる。
Claims (19)
- 前記Xが、カルボニル基を含む有機基である、請求項1に記載の非水系電解液。
- 前記Yが、硫黄原子である、請求項1又は2に記載の非水系電解液。
- 前記Zが、炭素数4~6のアルキレン基である、請求項1乃至3のいずれか1項に記載の非水系電解液。
- 前記式(1)で表される化合物の少なくとも1種を、非水系電解液100質量%中、0.01~5質量%含有する、請求項1乃至4のいずれか1項に記載の非水系電解液。
- 更に不飽和結合を有する環状カーボネートを含有する、請求項1乃至5のいずれか1項に記載の非水系電解液。
- 金属イオンを吸蔵・放出可能な負極及び正極、並びに請求項1乃至6のいずれか1項に記載の非水系電解液を含むことを特徴とする非水系電解液二次電池。
- 金属イオンを吸蔵及び放出可能な正極が、少なくとも1種以上の層状遷移金属酸化物を含む、請求項7に記載の非水系電解液二次電池。
- 金属イオンを吸蔵及び放出可能な負極が、少なくとも1種以上の炭素化合物を含む、請求項7に記載の非水系電解液二次電池。
- 式(10):
式中、
Wは、ヘテロ原子を含む有機基であって、前記ヘテロ原子として少なくとも1個の酸素原子を有する有機基を表し、
mは、2~4の整数を表し、
Zは、炭素数4~12のヘテロ原子を有していてもよい有機基を表す
で表されるスルホン酸エステルの製造方法であって、
式(11):
式中、Z及びmは、式(10)と同義である
で表されるスルホン酸クロリドと、式(12):
W-OH (12)
式中、Wは、式(10)と同義である
で表されるアルコール性水酸基を有する化合物を反応させる工程、及び
晶析により式(10)で表されるスルホン酸エステルを固体として取り出す工程を含むことを特徴とするスルホン酸エステルの製造方法。 - 晶析を、式(10)で表されるスルホン酸エステルを含む溶液の温度を下げることによって行う、請求項11記載のスルホン酸エステルの製造方法。
- 式(10)で表されるスルホン酸エステルを含む溶液が、メタノール溶液である、請求項11記載のスルホン酸エステルの製造方法。
- 晶析を20℃以下の温度条件で行う、請求項10~12のいずれか1項記載のスルホン酸エステルの製造方法。
- 式(10)におけるZが直鎖構造の有機基である、請求項10~13のいずれか1項記載のスルホン酸エステルの製造方法。
- 式(12)で表されるアルコール性水酸基を有する化合物が、グリセロールカーボネートである、請求項10~16のいずれか1項記載のスルホン酸エステルの製造方法。
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US20230155178A1 (en) | 2023-05-18 |
EP3561937A1 (en) | 2019-10-30 |
US20200263516A1 (en) | 2020-08-20 |
JP6540514B2 (ja) | 2019-07-10 |
EP3086398A4 (en) | 2016-10-26 |
JPWO2015093580A1 (ja) | 2017-03-23 |
US20210207452A2 (en) | 2021-07-08 |
EP3086398B1 (en) | 2019-08-21 |
US10734680B2 (en) | 2020-08-04 |
US20160294008A1 (en) | 2016-10-06 |
KR20160100970A (ko) | 2016-08-24 |
CN105830272A (zh) | 2016-08-03 |
US11695155B2 (en) | 2023-07-04 |
EP3086398A1 (en) | 2016-10-26 |
CN105830272B (zh) | 2019-08-06 |
EP3561937B1 (en) | 2020-08-19 |
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