WO2022224629A1 - 非水電解液及び二次電池 - Google Patents
非水電解液及び二次電池 Download PDFInfo
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- WO2022224629A1 WO2022224629A1 PCT/JP2022/011333 JP2022011333W WO2022224629A1 WO 2022224629 A1 WO2022224629 A1 WO 2022224629A1 JP 2022011333 W JP2022011333 W JP 2022011333W WO 2022224629 A1 WO2022224629 A1 WO 2022224629A1
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- Prior art keywords
- compound
- general formula
- positive electrode
- aqueous electrolyte
- battery
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- XCXLEIPEAAEYTF-UHFFFAOYSA-M sodium fluorosulfate Chemical compound [Na+].[O-]S(F)(=O)=O XCXLEIPEAAEYTF-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to non-aqueous electrolytes and secondary batteries.
- Patent Literature 1 proposes a non-aqueous electrolytic solution containing an electrolyte containing a lithium-containing complex compound.
- a non-aqueous electrolytic solution containing a sulfonylimide compound such as lithium bis(fluorosulfonyl)imide as an electrolyte is excellent in high-temperature durability and charge-discharge cycle of lithium ion secondary batteries. It has been found to improve battery performance.
- Patent Document 1 does not discuss a non-aqueous electrolytic solution containing a sulfonylimide compound.
- the present disclosure has been made in view of such points, and an object of the present disclosure is to provide a non-aqueous electrolyte containing a sulfonylimide compound, which is capable of improving battery performance.
- An object of the present invention is to provide a secondary battery with an aqueous electrolyte.
- a battery using a nonaqueous electrolyte solution containing a sulfonylimide compound can be obtained by using a lithium compound other than a sulfonylimide compound (e.g., LiPF 6 , LiBF 4 , etc.) alone as an electrolyte.
- a lithium compound other than a sulfonylimide compound e.g., LiPF 6 , LiBF 4 , etc.
- Self-discharge from a fully charged state is large compared to batteries using a non-aqueous electrolyte containing such a solution, and it has been found that there is room for improvement in the storage characteristics of the battery.
- Patent Document 1 and other documents also describe batteries using a non-aqueous electrolyte containing a sulfonylimide compound (especially lithium bis(fluorosulfonyl)imide). No mention is made of self-discharge.
- a sulfonylimide compound especially lithium bis(fluorosulfonyl)imide.
- the non-aqueous electrolyte solution containing a sulfonylimide compound not only suppresses the self-discharge of the battery, which is a unique problem, but also improved charging characteristics.
- the present disclosure is specifically as follows.
- the non-aqueous electrolyte of the present disclosure is General formula ( 1 ): LiN( R1SO2 )( R2SO2 ) ( 1 ) (In Formula (1), R 1 and R 2 are the same or different and represent a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms.)
- the compound represented by the general formula (3) may contain at least one of (LiBF 3 ) 2 O and LiBF 3 OLi.
- the content of the compound represented by the general formula (3) may be 0.01% by mass or more and 20% by mass or less.
- the compound represented by the general formula (1) may contain LiN(FSO 2 ) 2 .
- the molar ratio of the concentration of the compound represented by the general formula (1) to the concentration of the compound represented by the general formula (2) is 1:25 or more and 5:1 or less, 1:120 or more and 1:25 or less, 5: It may be 1 or more and 12:1 or less, or 1:120 or more and 12:1 or less.
- the non-aqueous electrolyte may further contain a fluorine-containing carbonate compound.
- the secondary battery of the present disclosure uses the non-aqueous electrolyte.
- the secondary battery may include a separator coated with inorganic particles on at least one surface thereof.
- non-aqueous electrolyte containing a sulfonylimide compound which can improve battery performance
- a secondary battery including the non-aqueous electrolyte it is possible to provide a non-aqueous electrolyte containing a sulfonylimide compound, which can improve battery performance, and a secondary battery including the non-aqueous electrolyte.
- the non-aqueous electrolyte according to this embodiment contains compounds represented by general formulas (1) to (3). That is, this non-aqueous electrolyte contains the compounds represented by the general formulas (1) to (3) as essential components.
- the compound represented by the general formula (1) has the general formula (1): [Chemical 1] LiN( R1SO2 ) ( R2SO2 ) ( 1 )
- R 1 and R 2 are the same or different (independently) and represent a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms.
- alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group.
- alkyl groups having 1 to 6 carbon atoms linear or branched alkyl groups having 1 to 6 carbon atoms are preferred, and linear alkyl groups having 1 to 6 carbon atoms are more preferred.
- fluoroalkyl group having 1 to 6 carbon atoms examples include those in which some or all of the hydrogen atoms of an alkyl group having 1 to 6 carbon atoms are substituted with fluorine atoms.
- the fluoroalkyl group having 1 to 6 carbon atoms includes fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group and the like.
- the fluoroalkyl group may be a perfluoroalkyl group.
- the substituents R 1 and R 2 are preferably a fluorine atom and a perfluoroalkyl group (eg, a C 1-6 perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc.). , a fluorine atom, a trifluoromethyl group and a pentafluoroethyl group are more preferred, a fluorine atom and a trifluoromethyl group are still more preferred, and a fluorine atom is even more preferred.
- the substituents R 1 and R 2 may be the same or different.
- Examples of the sulfonylimide compound (1) include lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 , hereinafter also referred to as “LiFSI”), lithium bis(trifluoromethylsulfonyl)imide (LiN(CF 3 SO 2 ) 2 , hereinafter also referred to as “LiTFSI”), lithium (fluorosulfonyl) (methylsulfonyl) imide, lithium (fluorosulfonyl) (ethylsulfonyl) imide, lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide, lithium (fluorosulfonyl ) (pentafluoroethylsulfonyl)imide, lithium (fluorosulfonyl)(heptafluoropropylsulfonyl)imide, lithium bis(pentafluoroeth
- the sulfonylimide compound (1) preferably contains at least one of LiN(FSO 2 ) 2 and LiN(CF 3 SO 2 ) 2 , and LiN(FSO 2 ) 2 More preferred are those containing
- the sulfonylimide compound (1) may exist (contain) in the form of ions in the non-aqueous electrolyte.
- the compound represented by the general formula (2) has the general formula (2): [Chemical 2] LiPF a (C m F 2m+1 ) 6-a (2)
- a fluorophosphoric acid compound represented by hereinafter referred to as "fluorophosphoric acid compound (2)").
- Fluorophosphate compounds (2) include LiPF 6 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (C 3 F 7 ) 3 , LiPF 3 (C 4 F 9 ) 3 etc.
- the fluorophosphoric acid compound (2) may be used alone, or two or more of them may be used in combination.
- As the fluorophosphoric acid compound (2) a commercial product may be used, or one synthesized by a conventionally known method may be used.
- the fluorophosphate compound (2) may exist (contain) in the form of ions in the non-aqueous electrolyte.
- the compound represented by the general formula (3) has the general formula (3): [Chemical 3] (Li) m (A) n (UF x ) y (3) A complex compound represented by (hereinafter referred to as "complex compound (3)").
- A represents an oxygen atom (O), a sulfur atom (S), a phosphorus atom (P) or a nitrogen atom (N).
- O oxygen atom
- S sulfur atom
- P phosphorus atom
- N nitrogen atom
- an oxygen atom and a sulfur atom are preferable, and an oxygen atom is more preferable, from the viewpoint of stability of the lithium salt, solubility in a solvent, and the like.
- U represents a boron atom (B) or a phosphorus atom (P).
- a boron atom is preferable from the viewpoint of bondability with A (particularly an oxygen atom, a sulfur atom or a nitrogen atom).
- m and n are the same or different (independently of each other), preferably 1 ⁇ m ⁇ 3, more preferably 1 and 2; x is preferably 3 from the viewpoint of the solubility of the electrolyte in the solvent. From the viewpoint of bonding with A, y preferably satisfies 1 ⁇ m ⁇ 3.
- O—(BF 3 Li)(Li) [wherein O—(BF 3 Li) (Li) has a structure of Li—O(—BF 3 ⁇ Li + ). It is a complex with Compounds exemplified below are also complexes having structures similar to those described above. Hereinafter, it is described as "LiBF 3 OLi”. ], O—(BF 3 Li) 2 [hereinafter referred to as “(LiBF 3 ) 2 O”.
- the complex compound (3) may be used alone or in combination of two or more.
- a commercial product may be used, or one synthesized by a conventionally known method may be used.
- the complex compound ( 3 ) preferably contains at least one of LiBF3OLi and ( LiBF3 ) 2O .
- the concentration of the sulfonylimide compound (1) in the non-aqueous electrolyte is preferably 0.01 mol/L or more, more preferably 0.05 mol/L or more, and even more preferably 0, from the viewpoint of improving charging characteristics at low temperatures. .1 mol/L or more, more preferably 0.3 mol/L or more, and even more preferably 0.5 mol/L or more.
- the concentration is preferably 5 mol/L or less, more preferably 3 mol/L or less, and still more preferably from the viewpoint of suppressing deterioration of battery performance due to an increase in electrolyte viscosity and improving charging characteristics at low temperatures. It is 2 mol/L or less, more preferably 1.5 mol/L or less, and even more preferably 1 mol/L or less.
- the concentration of the fluorophosphate compound (2) in the non-aqueous electrolyte is preferably 0.1 mol/L or more, more preferably 0.2 mol/L or more, and still more preferably 0, from the viewpoint of improving charging characteristics at low temperatures. .3 mol/L or more, more preferably 0.5 mol/L or more. In addition, the concentration is preferably 1.5 mol/L or less, more preferably 1 mol/L or less, and still more preferably 0.8 mol/L or less from the viewpoint of improving charging characteristics at low temperatures.
- the total concentration of the sulfonylimide compound (1) and the fluorophosphoric acid compound (2) is preferably 0.8 mol/L or more, more preferably 1 mol/L or more, and still more preferably 1 mol/L or more, from the viewpoint of improving charging characteristics at low temperatures. is 1.1 mol/L or more, even more preferably 1.2 mol/L or more.
- the concentration is preferably 5 mol/L or less, more preferably 3 mol/L or less, and still more preferably from the viewpoint of suppressing deterioration of battery performance due to an increase in electrolyte viscosity and improving charging characteristics at low temperatures. It is 2.5 mol/L or less, more preferably 2.3 mol/L or less, even more preferably 2 mol/L or less, and particularly preferably 1.5 mol/L or less.
- the ratio of sulfonylimide compound (1):fluorophosphoric acid compound (2) is preferably 1:25 or more, more preferably 1: 10 or more, more preferably 1:8 or more, still more preferably 1:5 or more, even more preferably 1:2 or more, and particularly preferably 1:1 or more.
- the upper limit is preferably 5:1 or less, more preferably 4:1 or less, still more preferably 3:1 or less, and even more preferably 2:1 or less.
- the molar ratio is not limited to the above range, and the effect of improving the charge characteristics at low temperatures can be obtained even in a range wider than the above range.
- the sulfonylimide compound (1):fluorophosphoric acid compound (2) (molar ratio of the sulfonylimide compound (1) concentration and the fluorophosphoric acid compound (2) concentration) is 1:120 or more, 1: It may be 100 or more, 1:50 or more, 12:1 or less, 10:1 or less, or 8:1 or less.
- the molar ratio may be from 1:120 to 1:25 (less than), from 5:1 to (exceeding) 12:1, and in the broadest range from 1:120 to 12:1.
- the content (addition amount) of the complex compound (3) in the non-aqueous electrolyte is preferably 0.01 in 100% by mass of the non-aqueous electrolyte from the viewpoint of improving charging characteristics at low temperatures and suppressing self-discharge. % by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more.
- the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.
- the non-aqueous electrolyte according to the present embodiment contains the compounds (1) to (3), and the combination of specific three components improves the charging characteristics at low temperatures, and the sulfonylimide compound (1 ), which is a problem peculiar to non-aqueous electrolytes containing ), especially self-discharge after high-temperature storage is also suppressed.
- a battery using a non-aqueous electrolyte containing only the two components of the sulfonylimide compound (1) and the complex compound (3) without containing the fluorophosphoric acid compound (2) cannot be charged normally. cannot work. This finding was also found by the present inventors. In other words, in the non-aqueous electrolytic solution according to the present embodiment, by using the compounds (1) to (3) together, the above problems can be solved collectively, and a synergistic effect of improving charging characteristics and storage characteristics can be obtained.
- the non-aqueous electrolyte according to the present embodiment includes imide salts and non-imide salts generally used as electrolytes, and various characteristics of lithium ion secondary batteries. It may contain an additive or the like that
- imide salt examples include fluorine-containing sulfonylimide salts (hereinafter referred to as "other sulfonylimide compounds") different from the sulfonylimide compound (1).
- Other sulfonylimide compounds include non-lithium salts of fluorine-containing sulfonylimides listed as sulfonylimide compound (1) (for example, salts in which lithium (ion) is substituted with a cation other than lithium ion in sulfonylimide compound (1) ) and the like.
- Salts substituted with cations other than lithium ions include alkali metal salts such as sodium salts, potassium salts, rubidium salts and cesium salts; alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts and barium salts. aluminum salts; ammonium salts; phosphonium salts and the like.
- alkali metal salts such as sodium salts, potassium salts, rubidium salts and cesium salts
- alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts and barium salts. aluminum salts; ammonium salts; phosphonium salts and the like.
- Other sulfonylimide compounds may be used alone, respectively, or two or more of them may be used in combination.
- Other sulfonylimide compounds may be commercially available products or may be synthesized by conventionally known methods.
- Non-imide salts include salts of non-imide anions and cations (lithium ions and cations exemplified above).
- Examples of non-imide salts include LiBF 4 , LiBF(CF 3 ) 3 , LiBF(C 2 F 5 ) 3 , LiBF(C 3 F 7 ) 3 , lithium hexafluoroarsenate (LiAsF 6 ), LiSbF 6 , LiClO 4 , Lithium salts such as LiSCN , LiAlF4, CF3SO3Li , LiC[(CF3SO2)3 ] , LiN ( NO2), LiN[(CN) 2 ; , salts in which lithium (ion) is substituted with the cations exemplified above (e.g., NaBF 4 , NaPF 6 , NaPF 3 (CF 3 ) 3 , etc.)
- Non-imide salts may be used alone, Two or more types may be used in combination.The non
- Additives include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenyl Carboxylic anhydride such as succinic anhydride; ethylene sulfite, 1,3-propanesultone, 1,4-butanesultone, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethylsulfone, tetramethylthiuram monosulfide, trimethylene sulfur-containing compounds such as glycol sulfate; 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide, etc
- nitrogen-containing compounds saturated hydrocarbon compounds such as heptane, octane, and cycloheptane; carbonate compounds such as phenylethylene carbonate and erythritan carbonate; fluoroethylene carbonate (FEC), 4,5-difluoroethylene carbonate, trifluoropropylene carbonate, Fluorine-containing carbonate compounds such as bis (trifluoromethyl) carbonate and ethyl (trifluoromethyl) carbonate; sulfamic acid (amidosulfuric acid, H 3 NSO 3 ); sulfamate (alkali metal salts such as lithium salt, sodium salt, potassium salt salts; alkaline earth metal salts such as calcium salts, strontium salts, barium salts; other metal salts such as manganese salts, copper salts, zinc salts, iron salts, cobalt salts, nickel salts; ammonium salts; guanidine salts, etc.); Fluorophosphate compounds such as lithium monoflu
- additives may be used alone or in combination of two or more.
- fluorine-containing carbonate compounds are preferable, and fluoroethylene carbonate (FEC) is more preferable, from the viewpoint of further improving the synergistic effect of the combination of the compounds (1) to (3).
- the content (addition amount) of the additive in the non-aqueous electrolyte is preferably 0.1% by mass or more and 25% by mass or less, more preferably 0.5% by mass or more and 15% by mass in 100% by mass of the non-aqueous electrolyte. Below, it is more preferably 3% by mass or more and 15% by mass or less, and still more preferably 5% by mass or more and 10% by mass or less.
- the amount of other additives used is too small, it may be difficult to obtain the effects derived from the other additives.
- the viscosity of the non-aqueous electrolyte increases, which may reduce the conductivity.
- the non-aqueous electrolyte according to this embodiment may contain an electrolyte solvent.
- the electrolyte solvent is not particularly limited as long as it can dissolve and disperse the above compounds (1) to (3) and other components.
- the electrolyte solvent non-aqueous solvents and electrolyte solvents are used instead. Examples include media such as polymers and polymer gels, and any solvent commonly used in batteries can be used.
- non-aqueous solvent a solvent having a large dielectric constant, a high solubility of the electrolyte salt, a boiling point of 60°C or higher, and a wide electrochemical stability range is suitable. More preferably, it is an organic solvent with a low water content.
- organic solvents examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran, crown ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, Ether solvents such as 1,4-dioxane and 1,3-dioxolane; Chain carbonate solvents such as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, diphenyl carbonate and methylphenyl carbonate; Ethylene carbonate and propylene carbonate , 2,3-dimethylethylene carbonate, 1,2-butylene carbonate and saturated cyclic carbonate solvents such as erythritan carbonate; vinylene carbonate, methylvinylene carbonate, ethylvinylene carbonate, 2-vinylethylene carbonate, phenylethylene carbonate and the
- Cyclic carbonate solvents having unsaturated bonds aliphatic carboxylic acid ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl acetate, and isopropyl propionate
- Aromatic carboxylic acid ester solvents such as methyl benzoate and ethyl benzoate
- Lactone solvents such as ⁇ -butyrolactone, ⁇ -valerolactone and ⁇ -valerolactone
- Trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate Phosphate ester solvents such as triethyl phosphate
- Nitrile solvents such as acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile,
- carbonate solvents such as linear carbonate solvents, cyclic carbonate solvents, lactone solvents, and ether solvents are preferable, and dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
- ⁇ -butyrolactone, ⁇ -valerolactone and the like are more preferable, and carbonate solvents such as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate are more preferable.
- a method in which a solution obtained by dissolving an electrolyte salt in a solvent is added dropwise to a polymer film formed by a conventionally known method to impregnate and support the electrolyte salt and a non-aqueous solvent A method of forming a film after melting and mixing a salt and impregnating the film with a solvent (above, gel electrolyte); A method of forming a film by a casting method or a coating method and volatilizing the organic solvent; A method of melting the polymer and electrolyte salt at a temperature above the melting point of the polymer, mixing and molding (intrinsic polymer electrolyte); .
- Polymers used instead of electrolyte solvents include polyethylene oxide (PEO), which is a homopolymer or copolymer of epoxy compounds (ethylene oxide, propylene oxide, butylene oxide, allyl glycidyl ether, etc.), and polyethers such as polypropylene oxide.
- system polymers methacrylic polymers such as polymethyl methacrylate (PMMA), nitrile polymers such as polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), fluorine-based polymers such as polyvinylidene fluoride-hexafluoropropylene, and their co- A polymer etc. are mentioned. These polymers may be used alone or in combination of two or more.
- the non-aqueous electrolytic solution configured as described above is used, for example, in batteries (batteries having a charging/discharging mechanism), electrical storage (electrochemical) devices (or ionic conductor materials constituting these), and the like.
- the electrolytic solution constitutes, for example, primary batteries, secondary batteries (e.g., lithium (ion) secondary batteries), fuel cells, electrolytic capacitors, electric double layer capacitors, solar cells, electrochromic display elements, and the like. It can be used as an electrolyte for A battery (particularly a secondary battery) will be described below as an example.
- a secondary battery according to this embodiment includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
- the non-aqueous electrolyte according to the present embodiment that is, the non-aqueous electrolyte containing the compounds (1) to (3) as essential components is used as the non-aqueous electrolyte.
- the positive electrode includes a positive electrode current collector and a positive electrode mixture layer, the positive electrode mixture layer is formed on the positive electrode current collector, and is usually formed into a sheet shape.
- Examples of metals used for positive electrode current collectors include iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, and platinum. Among these, aluminum is preferred.
- the shape and dimensions of the positive electrode current collector are not particularly limited.
- the positive electrode mixture layer is formed of a positive electrode mixture (positive electrode composition).
- the positive electrode mixture contains a positive electrode active material, a conductive aid, a binder, a solvent for dispersing these components, and the like.
- the positive electrode (positive electrode mixture) is preferably LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O Ternary cathode active materials such as LiNi0.6Co0.2Mn0.2O2 , LiNi0.8Co0.1Mn0.1O2 ; LiFePO4 , LiFe0.995Mn0 .
- An iron phosphate positive electrode active material having an olivine structure such as PO4 can be suitably used.
- Each of these positive electrode active materials may be used alone, or two or more of them may be used in combination.
- the positive electrode preferably contains at least one of the ternary positive electrode active material and the iron phosphate positive electrode active material described above, but may contain other positive electrode active materials.
- Other positive electrode active materials may be used as long as they can occlude and release various ions (lithium ions, sodium ions, etc.), such as conventionally known secondary batteries (lithium ion secondary batteries and sodium ion secondary batteries).
- the positive electrode active material used in can be used.
- a compound having an olivine fluoride structure; sulfur or the like can be used. Each of these may be used alone, or two or more of them may be used in combination.
- positive electrode active materials used in sodium ion secondary batteries include NaNiO 2 , NaCoO 2 , NaMnO 2 , NaVO 2 , NaFeO 2 , Na(Ni X Mn 1-X )O 2 (0 ⁇ X ⁇ 1). , Na(Fe X Mn 1-X )O 2 (0 ⁇ X ⁇ 1), NaVPO 4 F, Na 2 FePO 4 F, Na 3 V 2 (PO 4 ) 3 and the like. Each of these may be used alone, or two or more of them may be used in combination.
- a positive electrode active material capable of intercalating and deintercalating lithium ions may be preferably used.
- Such a positive electrode active material is used, for example, in a lithium ion secondary battery using a non-aqueous electrolyte.
- Such non-aqueous systems generally have lower ionic conductivity than aqueous systems, but the present disclosure can efficiently improve the discharge capacity even in such cases.
- the content of the positive electrode active material (the total content when multiple positive electrode active materials are included) is 100% by mass of the total amount of components contained in the positive electrode mixture from the viewpoint of improving the output characteristics and electrical characteristics of the secondary battery. On the other hand, it is preferably 75% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 95% by mass or less. is.
- a conductive agent is used to improve the output of a lithium-ion secondary battery.
- Conductive carbon is mainly used as the conductive aid.
- Examples of conductive carbon include carbon black, fibrous carbon, and graphite. Conductive aids may be used alone, respectively, or two or more of them may be used in combination.
- carbon black is preferred. Examples of carbon black include ketjen black and acetylene black.
- the content of the conductive aid in the non-volatile content of the positive electrode mixture is preferably 1 to 20% by mass, more preferably 1.5 to 10% by mass, from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. is.
- Binders include fluorine-based resins such as polyvinylidene fluoride and polytetrafluoroethylene; synthetic rubbers such as styrene-butadiene rubber and nitrile-butadiene rubber; polyamide-based resins such as polyamideimide; polyolefin-based resins such as polyethylene and polypropylene.
- poly(meth)acrylic resins polyacrylic acid
- cellulose resins such as carboxymethyl cellulose
- the binders may be used alone or in combination of two or more. Further, the binder may be dissolved in the solvent or dispersed in the solvent when used.
- solvents examples include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, tetrahydrofuran, acetonitrile, acetone, ethanol, ethyl acetate, and water.
- NMP N-methyl-2-pyrrolidone
- dimethylformamide dimethylacetamide
- methyl ethyl ketone tetrahydrofuran
- acetonitrile acetone
- ethanol ethyl acetate
- water examples include water.
- the solvents may be used alone or in combination of two or more.
- the amount of the solvent to be used is not particularly limited, and may be determined as appropriate according to the manufacturing method and materials to be used.
- non-fluorine-based polymers such as (meth)acrylic polymers, nitrile-based polymers, and diene-based polymers, polymers such as fluorine-based polymers such as polytetrafluoroethylene, Emulsifiers such as anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers; dispersants such as polymer dispersants such as styrene-maleic acid copolymers and polyvinylpyrrolidone; ), a thickener such as an alkali-soluble (meth)acrylic acid-(meth)acrylic acid ester copolymer, a preservative, and the like.
- the content of other components in the nonvolatile matter of the positive electrode mixture is preferably 0 to 15% by mass, more preferably 0 to 10% by mass.
- the positive electrode mixture can be prepared, for example, by mixing a positive electrode active material, a conductive aid, a binder, a solvent, and optionally other components, and dispersing the mixture using a bead mill, a ball mill, an agitating mixer, or the like. .
- the method of forming the positive electrode is not particularly limited.
- the positive electrode mixture is applied (and dried) to the positive electrode current collector by a conventional coating method (for example, a doctor blade method, etc.).
- a conventional coating method for example, a doctor blade method, etc.
- Examples include a method of transferring to a current collector (positive electrode current collector) and using it as an electrode (positive electrode) without drying.
- the positive electrode mixture layer may be dried or pressurized (pressed) after being formed or coated (applied), if necessary.
- the negative electrode includes a negative electrode current collector and a negative electrode mixture layer, and the negative electrode mixture layer is formed on the negative electrode current collector and is usually formed into a sheet shape.
- Examples of metals used for negative electrode current collectors include iron, copper, aluminum, nickel, stainless steel (SUS), titanium, tantalum, gold, and platinum. Among these, copper is preferred.
- the shape and dimensions of the negative electrode current collector are not particularly limited.
- the negative electrode mixture layer is formed from a negative electrode mixture (negative electrode composition).
- the negative electrode mixture contains a negative electrode active material, a conductive aid, a binder, a solvent for dispersing these components, and the like.
- negative electrode active material conventionally known negative electrode active materials used in various batteries (e.g., lithium secondary batteries) can be used, and various ions (e.g., lithium ions) can be occluded and released. I wish I had.
- Specific negative electrode active materials include graphite materials such as artificial graphite and natural graphite, mesophase sintered bodies made from coal and petroleum pitch, carbon materials such as non-graphitizable carbon, Si, Si alloys, and SiO (silicon oxide). and the like, Sn-based negative electrode materials such as Sn alloys, lithium metals, and lithium alloys such as lithium-aluminum alloys.
- the negative electrode active materials may be used alone, or two or more of them may be used in combination. For example, a composite material of silicon oxide and graphite can be used.
- the negative electrode mixture may further contain a conductive aid (conductive material), a binder, a solvent, and the like.
- a conductive aid conductive material
- binder a binder
- solvent a solvent
- the same components as those described above can be used.
- usage ratio and the like are the same as those described above.
- the same method as the manufacturing method for the positive electrode may be adopted.
- the secondary battery may have a separator.
- a separator is arranged so as to separate the positive electrode and the negative electrode.
- the separator is not particularly limited, and any conventionally known separator can be used in the present disclosure.
- Specific separators include, for example, a porous sheet made of a polymer capable of absorbing and retaining an electrolytic solution (non-aqueous electrolytic solution) (for example, a polyolefin microporous separator, a cellulose separator, etc.), a non-woven fabric separator, and a porous sheet.
- an electrolytic solution non-aqueous electrolytic solution
- non-aqueous electrolytic solution for example, a polyolefin microporous separator, a cellulose separator, etc.
- non-woven fabric separator for example, a non-woven fabric separator, and a porous sheet.
- a metal object etc. are mentioned.
- Materials for the porous sheet include polyethylene, polypropylene, and laminates having a three-layer structure of polypropylene/polyethylene/polypropylene.
- non-woven fabric separator Materials for the non-woven fabric separator include, for example, cotton, rayon, acetate, nylon, polyester, polypropylene, polyethylene, polyimide, aramid, and glass. It may be used alone or in combination of two or more.
- a separator coated with inorganic particles on at least one side can be suitably used.
- a separator having an insulating layer containing inorganic particles on at least one surface is preferable.
- the synergistic effect of the combination of the compounds (1) to (3) is further improved.
- the surface having the insulating layer may be arranged on the positive electrode side or may be arranged on the negative electrode side.
- separators having an insulating layer on at least one side separators having insulating layers on both sides are preferred.
- the insulating layer is made of an insulating composite material.
- the insulating composite material contains inorganic particles, a binder, a solvent for dispersing these components, and the like.
- inorganic particles include alumina, silica, magnesia, titania, zirconia, LiNbO 3 , LIPON (Li 3+y PO 4-x N x ), a group called LISICON (Lithium-Super-Ion-Conductor), Thio-LISICON (for example, Li 3.25Ge0.25P0.75S4 ), Li2S alone , Li2SP2S5 , Li2S - SiS2 , Li2S - GeS2 , Li2S - B2 Ceramic particles such as S 5 , Li 2 S—Al 2 S 5 , Li 2 O—Al 2 O 3 —TiO 2 —P 2 O 5 (LATP).
- LATP Li 3+y PO 4-x N x
- LISICON Lithium-Super-Ion-Conductor
- Thio-LISICON for example, Li 3.25Ge0.25P0.75S4
- Li2S alone Li2SP2S5 , Li2S
- the same component as the binder described above can be used, and examples include polymer compounds such as polyvinylidene fluoride (PVdF).
- Solvents used in positive and negative electrodes can be used, such as N-methyl-2-pyrrolidone (NMP).
- the same method as the method of forming the positive electrode (coating method) described above can be adopted.
- the insulating layer may be formed on one or both sides of the separator by replacing the positive electrode mixture with the insulating mixture and the positive electrode current collector with the separator.
- a battery element comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte (and a separator) is usually housed in a battery outer packaging material to protect the battery element from external impact, environmental degradation, and the like during battery use.
- the material of the battery exterior material is not particularly limited, and any conventionally known exterior material can be used.
- Expanded metals, fuses, overcurrent protection elements such as PTC elements, lead plates, etc. may be included in the battery exterior material as necessary to prevent pressure increases inside the battery and overcharge/discharge.
- the shape of the battery is not particularly limited. can also be used.
- a high voltage power source severe tens of volts to several hundreds of volts
- a battery module configured by connecting individual batteries in series can also be used. .
- the rated charging voltage of the secondary battery is not particularly limited, but when the secondary battery has a positive electrode containing the above-described ternary positive electrode active material as a main component, it is 3.6 V or more, preferably It may be 4.0 V or higher, more preferably 4.1 V or higher, and even more preferably 4.2 V or higher. Although the higher the rated charging voltage, the higher the energy density, the rated charging voltage may be 4.6 V or less (for example, 4.5 V or less) from the viewpoint of safety.
- the positive electrode and the negative electrode are laminated (via a separator as necessary), the obtained laminate is placed in the battery outer packaging material, and the non-aqueous electrolyte is placed in the battery outer packaging material. can be easily manufactured by injecting and sealing.
- the non-aqueous electrolytic solution according to the present embodiment contains three specific components: a sulfonylimide compound (1), a fluorophosphoric acid compound (2), and a complex compound (3).
- the non-aqueous electrolytic solution according to the present embodiment can further improve the above effects by using four specific components that further include a fluorine-containing carbonate compound.
- a battery provided with a separator having an insulating layer containing inorganic particles on at least one surface together with the non-aqueous electrolyte according to the present embodiment can further improve the above effects.
- Example 1 series> (Production example 1) Under an argon atmosphere, 10 mL of diethyl ether and 0.75 g of lithium oxide were added to a 100 mL Erlenmeyer flask to prepare a mixed liquid, which was then cooled to 0° C. while stirring. While stirring, 10.5 g of boron trifluoride diethyl ether complex was added to the mixed solution over 30 minutes to prepare a reaction solution, which was then kept at 25° C. and stirred for 16 hours. Subsequently, the reaction solution was filtered to obtain a crude lithium oxide/2BF 3 complex.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC) 3:7 (volume ratio) as a solvent for the electrolytic solution (manufactured by Kishida Chemical Co., Ltd., hereinafter the same). (manufactured by Nippon Shokubai Co., Ltd., the same applies hereinafter) and LiPF 6 (manufactured by Stella Chemifa Co., Ltd., the same applies hereinafter) as the fluorophosphate compound (2). 1-1 and the concentrations shown in Table 1-2.
- electrolytic solution (LiBF 3 ) 2 O obtained in Production Example 1 as the complex compound (3) was added so as to have the content shown in Tables 1-1 and 1-2.
- electrolytic solution a non-aqueous electrolytic solution (hereinafter simply referred to as electrolytic solution) was prepared.
- Comparative Example 1-1 A non-aqueous electrolytic solution was prepared in the same manner as in each example except that (LiBF 3 ) 2 O was not added to the solution obtained above. That is, in Comparative Example 1-1, the solution obtained above was used as the non-aqueous electrolyte.
- LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Umicore, product number: MX7h), which is a ternary positive electrode active material, acetylene black (AB, manufactured by Denka Co., Ltd., product name: Denka Black (registered trademark) )), graphite (manufactured by Nippon Graphite Industry Co., Ltd., product number: SP270), and polyvinylidene fluoride (PVdF, manufactured by Kureha Co., Ltd., product number: KF1120) are dispersed in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- the resulting negative electrode mixture slurry was applied to a copper foil (negative electrode current collector, manufactured by Fukuda Metal Foil & Powder Co., Ltd., thickness 15 ⁇ m) with a coating weight of 9.8 mg/cm 2 after drying.
- a copper foil negative electrode current collector, manufactured by Fukuda Metal Foil & Powder Co., Ltd., thickness 15 ⁇ m
- One side was coated with an applicator so as to have a uniform thickness, and dried on a hot plate at 80° C. for 10 minutes. Furthermore, it was dried in a vacuum drying oven at 100° C. for 12 hours. After that, a sheet-like negative electrode (thickness: 113 ⁇ m) was obtained by pressure molding with a roll press until the density reached 1.3 g/cm 3 .
- the battery was pre-charged at 0.2 C (6 mA) for 2 hours in an unsealed state. After that, the battery was vacuum-sealed and left at room temperature for 3 days. After 3 days, charge at 0.5C (15mA), 4.2V, 5 hours, then charge and discharge at 0.2C (6mA), 2.75V final charge and discharge, tear one piece of laminate, and vacuum the battery again. Degassing was performed by sealing. After degassing, the battery was charged and discharged under the following conditions, and this operation was defined as a conditioning step. As described above, a laminate battery (cell) having a capacity of 4.2 V and a capacity of 30 mAh was produced. (conditioning conditions) Charge: 0.5C (15mA), 4.2V for 5 hours (25°C) ⁇ Discharge: 1C (30mA), 2.75V cut off (25°C).
- Example 2 series (Examples 2-1 to 2-56, Comparative Examples 2-1 to 2-3) A non-aqueous electrolytic solution was prepared in the same manner as in the Example 1 series, except that LiBF 3 OLi obtained in Production Example 2 was used as the complex compound (3) instead of (LiBF 3 ) 2 O.
- the LiFSI concentration, LiPF 6 concentration, and LiBF 3 OLi content are shown in Tables 2-1 and 2-2.
- a laminate battery (cell) was produced in the same manner as in the Example 1 series, and the battery was evaluated. The results are shown in Tables 2-1 and 2-2.
- Example 3 Series (Examples 3-1 to 3-10, Comparative Examples 3-1 to 3-5) [Preparation of non-aqueous electrolyte]
- Non-aqueous electrolytes were prepared in the same manner as in Examples 1 and 2 series.
- Table 3 shows the LiFSI concentration, the LiPF 6 concentration, and the type and content of the complex compound (3).
- the alumina-coated polyethylene separator was produced by the following method. First, 80 parts by mass of alumina powder having an average particle size of 0.5 ⁇ m as inorganic particles and 20 parts by mass of polyvinylidene fluoride (PVdF) as a binder are mixed and diluted with N-methyl-2-pyrrolidone (NMP). to prepare a mixture. A 20 ⁇ m thick polyethylene sheet was immersed in the resulting mixture, the film thickness was controlled with a gravure roller, and then the sheet was passed through a drier at 120° C. to remove the solvent. An alumina-coated polyethylene separator coated with a porous membrane was produced.
- PVdF polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Table 4 shows the concentration of LiFSI, the concentration of LiPF6 , the type and content of complex compound (3), and the content of FEC.
- a laminate battery (cell) was produced in the same manner as in the Example 1 series, and the battery was evaluated. Table 4 shows the results.
- Example 5 series (Examples 5-1 to 5-56, Comparative Examples 5-1 to 5-3) [Preparation of non-aqueous electrolyte]
- a non-aqueous electrolyte was prepared in the same manner as in the Example 1 series.
- Tables 5-1 and 5-2 show the concentration of LiFSI, the concentration of LiPF 6 , and the content of (LiBF 3 ) 2 O obtained in Production Example 1 as the complex compound (3).
- LiNi 0.8 Co 0.1 Mn 0.1 O 2 (manufactured by Beijing Toben), which is a ternary positive electrode active material, acetylene black (AB, manufactured by Denka Co., Ltd., product name: Denka Black (registered trademark)) , graphite (manufactured by Nippon Graphite Industry Co., Ltd., product number: SP270), and polyvinylidene fluoride (PVdF, manufactured by Kureha Co., Ltd., product number: KF1120) were dispersed in N-methyl-2-pyrrolidone (NMP) to form a positive electrode.
- NMP N-methyl-2-pyrrolidone
- a laminate battery (cell) having a capacity of 4.2 V and a capacity of 30 mAh was produced in the same manner as in Example 1 series, except that the positive electrode and negative electrode obtained above were used, and the battery was evaluated. The results are shown in Tables 5-1 and 5-2.
- Example 6 series (Examples 6-1 to 6-56, Comparative Examples 6-1 to 6-3) A non-aqueous electrolytic solution was prepared in the same manner as in the Example 1 series, except that LiBF 3 OLi obtained in Production Example 2 was used as the complex compound (3) instead of (LiBF 3 ) 2 O.
- the LiFSI concentration, LiPF 6 concentration, and LiBF 3 OLi content are shown in Tables 6-1 and 6-2.
- a laminate battery (cell) was produced in the same manner as in the Example 5 series, and the battery was evaluated. The results are shown in Tables 6-1 and 6-2.
- the present disclosure is suitable for nonaqueous electrolytes used in lithium ion secondary batteries.
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Abstract
Description
一般式(1):LiN(R1SO2)(R2SO2) (1)
(式(1)中、R1及びR2は同一又は異なってフッ素原子、炭素数1~6のアルキル基又は炭素数1~6のフルオロアルキル基を示す。)
で表される化合物と、
一般式(2):LiPFa(CmF2m+1)6-a (2)
(式(2)中、a:0≦a≦6、m:1≦m≦4を示す。)
で表される化合物と、
一般式(3):(Li)m(A)n(UFx)y (3)
(式(3)中、Aは酸素原子、硫黄原子、リン原子又は窒素原子を示し、Uはホウ素原子又はリン原子を示す。m:1≦m≦6、n:1≦m≦6、x:3又は5、y:1≦y≦6を示す。)
で表される化合物とを含む。前記非水電解液では、前記一般式(3)で表される化合物が(LiBF3)2O及びLiBF3OLiの少なくとも一種を含んでいてもよい。前記一般式(3)で表される化合物の含有量が0.01質量%以上20質量%以下であってもよい。前記一般式(1)で表される化合物がLiN(FSO2)2を含んでいてもよい。前記一般式(1)で表される化合物濃度と前記一般式(2)で表される化合物濃度とのモル比率が1:25以上5:1以下、1:120以上1:25以下、5:1以上12:1以下又は1:120以上12:1以下であってもよい。前記非水電解液は、フッ素含有カーボネート化合物をさらに含んでいてもよい。
本実施形態に係る非水電解液は、一般式(1)~(3)で表される化合物を含む。即ち、この非水電解液は、一般式(1)~(3)で表される化合物を必須成分とするものである。
一般式(1)で表される化合物は、一般式(1):
[化1]
LiN(R1SO2)(R2SO2) (1)
で表されるスルホニルイミド化合物(以下「スルホニルイミド化合物(1)」という、フッ素含有スルホニルイミド塩)をいう。
一般式(2)で表される化合物は、一般式(2):
[化2]
LiPFa(CmF2m+1)6-a (2)
で表されるフルオロリン酸化合物(以下「フルオロリン酸化合物(2)」という)をいう。
一般式(3)で表される化合物は、一般式(3):
[化3]
(Li)m(A)n(UFx)y (3)
で表される錯体化合物(以下「錯体化合物(3)」という)をいう。
本実施形態に係る非水電解液は、前記化合物(1)~(3)以外に、電解質として一般に使用されるイミド塩、非イミド塩や、リチウムイオン二次電池の各種特性の向上を目的とする添加剤等を含んでいてもよい。
本実施形態に係る非水電解液は電解液溶媒を含んでいてもよい。電解液溶媒は、前記した化合物(1)~(3)やその他の成分を溶解、分散できるものであれば特に限定されない、電解液溶媒としては、非水系溶媒、電解液溶媒に代えて用いられるポリマー及びポリマーゲル等の媒体等が挙げられ、電池に一般に使用される溶媒はいずれも使用できる。
本実施形態に係る二次電池は、正極、負極及び非水電解液を備えている。この二次電池では、非水電解液として、本実施形態に係る非水電解液、つまり前記化合物(1)~(3)を必須成分として含む非水電解液が用いられる。
正極は、正極集電体及び正極合材層を含み、正極合材層が正極集電体上に形成され、通常、シート状に成形されている。
負極は、負極集電体及び負極合材層を含み、負極合材層が負極集電体上に形成され、通常、シート状に成形されている。
二次電池はセパレータを備えていてもよい。セパレータは正極と負極とを隔てるように配置されるものである。セパレータには、特に制限がなく、本開示では、従来公知のセパレータのいずれも使用できる。具体的なセパレータとしては、例えば、電解液(非水電解液)を吸収・保持し得るポリマーからなる多孔性シート(例えば、ポリオレフィン系微多孔質セパレータやセルロース系セパレータ等)、不織布セパレータ、多孔質金属体等が挙げられる。
正極、負極及び非水電解液(さらにはセパレータ)を備えた電池素子は、通常、電池使用時の外部からの衝撃、環境劣化等から電池素子を保護するため電池外装材に収容される。電池外装材の素材は特に限定されず従来公知の外装材はいずれも使用できる。
本実施形態に係る二次電池は、例えば、正極と負極とを(必要に応じてセパレータを介して)重ね合わせ、得られた積層体を電池外装材に入れ、電池外装材に非水電解液を注液して封口することにより、容易に製造できる。
本実施形態に係る非水電解液及び二次電池によれば、以下の効果を得ることができる。
・本実施形態に係る非水電解液は、スルホニルイミド化合物(1)、フルオロリン酸化合物(2)及び錯体化合物(3)という特定の3成分を含む。これにより、当該非水電解液が用いられた電池は、低温での充電特性を改善できるとともに、スルホニルイミド化合物(1)を含む非水電解液特有の課題である自己放電、特に高温保存後の自己放電を抑制できる。
・本実施形態に係る非水電解液は、フッ素含有カーボネート化合物をさらに含む特定の4成分とすることで、前記した効果をさらに改善できる。
・本実施形態に係る非水電解液と共に、少なくとも一面に無機物粒子を含む絶縁層を有するセパレータを備える電池は、前記した効果をさらに改善できる。
(製造例1)
アルゴン雰囲気下で、100mLの三角フラスコに、10mLのジエチルエーテル及び0.75gの酸化リチウムを加えて混合液を調製した後、撹拌しながら0℃に冷却した。撹拌しながら、当該混合液に、10.5gの三フッ化ホウ素ジエチルエーテル錯体を30分かけて加えて反応液を調製した後、25℃に保ち、16時間撹拌した。続いて、反応液をろ過し、酸化リチウム/2BF3錯体の粗体を得た。得られた酸化リチウム/2BF3錯体の粗体を10mLのジブチルエーテルを用いて3回洗浄し、過剰の三フッ化ホウ素ジエチルエーテル錯体を除去した。得られた固形物を110℃の雰囲気下で10時間減圧乾燥することにより、酸化リチウムと2BF3錯体である「(LiBF3)2O」4.04gを得た。
10.5gの三フッ化ホウ素ジエチルエーテル錯体の代わりに、3.55gの三フッ化ホウ素ジエチルエーテル錯体を使用した以外は製造例1と同様にして、酸化リチウム/BF3錯体である「LiBF3OLi」2.24gを得た。
[非水電解液の調製]
電解液溶媒としてエチレンカーボネート(EC):エチルメチルカーボネート(EMC)=3:7(体積比)組成の混合溶媒(キシダ化学(株)製、以下同じ。)に、スルホニルイミド化合物(1)としてLiFSI((株)日本触媒製、以下同じ)と、フルオロリン酸化合物(2)としてLiPF6(ステラケミファ(株)製、以下同じ。)とを含む混合塩組成の電解質塩の電解質塩をそれぞれ表1-1及び表1-2に示す濃度となるように溶解した。前記で得られた溶液に、錯体化合物(3)として製造例1で得られた(LiBF3)2Oを表1-1及び表1-2に示す含有量となるように添加し、一日攪拌することにより、非水電解液(以下単に電解液ともいう)を調製した。
前記で得られた溶液に(LiBF3)2Oを添加しなかったこと以外は、各実施例と同様にして非水電解液を調製した。つまり、比較例1-1では、前記で得られた溶液を非水電解液として用いた。
LiPF6のみを含む単体塩組成の電解質塩を用いたこと以外は、各実施例と同様にして非水電解液を調製した。
LiFSIのみを含む単体塩組成の電解質塩を用いたこと以外は、各実施例と同様にして非水電解液を調製した。
(正極の作製)
三元系正極活物質であるLiNi1/3Co1/3Mn1/3O2(ユミコア製、品番:MX7h)、アセチレンブラック(AB、デンカ(株)製、製品名:デンカブラック(登録商標))、グラファイト(日本黒鉛工業(株)製、品番:SP270)、及びポリフッ化ビニリデン(PVdF、(株)クレハ製、品番:KF1120)をN-メチル-2-ピロリドン(NMP)中に分散させて正極合材スラリー(正極活物質:AB:グラファイト:PVdF=93:2:2:3(固形分質量比))を作製した。続いて、得られた正極合材スラリーをアルミニウム箔(正極集電体、日本製箔(株)製、厚み15μm)に対して、乾燥後の塗工重量が19.4mg/cm2となるようにアプリケーターで片面塗工し、110℃のホットプレート上で10分間乾燥させた。さらに、110℃の真空乾燥炉で12時間乾燥させた。その後、ロールプレス機により密度3.1g/cm3となるまで加圧成形することにより、シート状(厚み83μm)の正極を得た。
負極活物質としてグラファイト(天然黒鉛(日立化成(株)製、品番:SMG):人造黒鉛(TIMCAL製、品番:SFG15)=85:15(固形分質量比))、スチレン-ブタジエンゴム(SBR、結着剤)及びカルボキシメチルセルロース(CMC、結着剤)を、超純水中に分散させて、負極合材スラリー(負極活物質:SBR:CMC=97.3:1.5:1.2(固形分質量比))を作製した。続いて、得られた負極合材スラリーを銅箔(負極集電体、福田金属箔粉工業(株)製、厚み15μm)に対して、乾燥後の塗工重量が9.8mg/cm2となるようにアプリケーターで片面塗工し、80℃のホットプレート上で10分間乾燥させた。さらに、100℃の真空乾燥炉で12時間乾燥させた。その後、ロールプレス機により密度1.3g/cm3となるまで加圧成形することにより、シート状(厚み113μm)の負極を得た。
得られた正極及び負極をそれぞれカットし、極性導出リードを超音波で溶接し、20μmのポリエチレン(PE)セパレータを介して該正極及び負極を対向させ、ラミネート外装で3方を封止することにより、未注液電池を作製した。続いて、未注液電池の未封止の1方より、表1-1及び表1-2に示す各電解液を700μL添加した。
(コンディショニング条件)
充電:0.5C(15mA)、4.2Vで5時間(25℃)⇒放電:1C(30mA)、2.75V終止(25℃)。
コンディショニング工程後のセルを用い、低温での充電時間と高温保存後の自己放電を評価した。その結果を表1-1及び表1-2に示す。
コンディショニング工程後のセルを-20℃にて4.2V、1C(30mA)で定電流充電したときの充電時間(分)を求めた。なお、充電時間が長いほど、充電特性に優れることを意味する。
コンディショニング工程後のセルを、常温にて1C(30mA)、4.2Vで0.02C(0.6mA)終止の定電流定電圧充電を行い、満充電状態(SOC100%)とした。満充電状態のセルを60℃で4週間保存した。保存後のセルを常温で3時間冷却した後、常温でセルの開路電圧(OCV:Open Circuit Voltage)を測定し、この測定値を「保存後OCV」とした。なお、「保存後OCV」の値が大きいほど、満充電状態からの自己放電が小さい、即ち電池の自己放電が抑制されていることを意味する。
(実施例2-1~2-56、比較例2-1~2-3)
錯体化合物(3)として(LiBF3)2Oの代わりに、製造例2で得られたLiBF3OLiを用いたこと以外は、実施例1シリーズと同様にして非水電解液を調製した。LiFSIの濃度、LiPF6の濃度、及びLiBF3OLiの含有量を表2-1及び表2-2に示す。得られた各非水電解液を用い、実施例1シリーズと同様にして、ラミネート電池(セル)の作製し、電池の評価を行った。その結果を表2-1及び表2-2に示す。
(実施例3-1~3-10、比較例3-1~3-5)
[非水電解液の調製]
実施例1及び2シリーズと同様にして非水電解液を調製した。LiFSIの濃度、LiPF6の濃度、並びに錯体化合物(3)の種類及び含有量を表3に示す。
20μmのポリエチレン(PE)セパレータの代わりに、当該ポリエチレンセパレータの両面にアルミナ粒子が塗布されたアルミナコートポリエチレンセパレータを用いたこと以外は、実施例1及び2シリーズと同様にして、4.2V、容量30mAhのラミネート電池(セル)を作製し、電池の評価を行った。その結果を表3に示す。
非水電解液に、添加剤としてフルオロエチレンカーボネート(FEC)を表4に示す含有量となるようにさらに添加したこと以外は、実施例1及び2シリーズと同様にして非水電解液を調製した。LiFSIの濃度、LiPF6の濃度、錯体化合物(3)の種類及び含有量、並びにFECの含有量を表4に示す。得られた各非水電解液を用い、実施例1シリーズと同様にして、ラミネート電池(セル)の作製し、電池の評価を行った。その結果を表4に示す。
(実施例5-1~5-56、比較例5-1~5-3)
[非水電解液の調製]
実施例1シリーズと同様にして非水電解液を調製した。LiFSIの濃度、LiPF6の濃度、及び錯体化合物(3)として製造例1で得られた(LiBF3)2Oの含有量を表5-1及び表5-2に示す。
(正極の作製)
三元系正極活物質であるLiNi0.8Co0.1Mn0.1O2(北京当弁製)、アセチレンブラック(AB、デンカ(株)製、製品名:デンカブラック(登録商標))、グラファイト(日本黒鉛工業(株)製、品番:SP270)、及びポリフッ化ビニリデン(PVdF、(株)クレハ製、品番:KF1120)をN-メチル-2-ピロリドン(NMP)中に分散させて正極合材スラリー(正極活物質:AB:グラファイト:PVdF=93:3:3:3(固形分質量比))を作製した。続いて、得られた正極合材スラリーをアルミニウム箔(正極集電体、日本製箔(株)製、厚み15μm)に対して、乾燥後の塗工重量が19.4mg/cm2となるようにアプリケーターで片面塗工し、110℃のホットプレート上で10分間乾燥させた。さらに、110℃の真空乾燥炉で12時間乾燥させた。その後、ロールプレス機により密度3.1g/cm3となるまで加圧成形することにより、シート状(厚み78μm)の正極を得た。
負極活物質として酸化ケイ素(SiO)/黒鉛複合材料(BTR製、品番:BSO-600)、導電助剤(昭和電工(株)製、品番:VGCF-H(登録商標)および(イメリス製、品番:Super-P(登録商標)、スチレン-ブタジエンゴム(SBR、結着剤)及びカルボキシメチルセルロース(CMC、結着剤)を、超純水中に分散させて、負極合材スラリー(負極活物質:VGCF:Super-P:SBR:CMC=90:2:3:3:2(固形分質量比))を作製した。続いて、得られた負極合材スラリーを銅箔(負極集電体、福田金属箔粉工業(株)製、厚み15μm)に対して、乾燥後の塗工重量が6.8mg/cm2となるようにアプリケーターで片面塗工し、80℃のホットプレート上で10分間乾燥させた。さらに、100℃の真空乾燥炉で12時間乾燥させた。その後、ロールプレス機により密度1.3g/cm3となるまで加圧成形することにより、シート状(厚み64μm)の負極を得た。
前記で得られた正極及び負極を用いたこと以外は、実施例1シリーズと同様にして、4.2V、容量30mAhのラミネート電池(セル)を作製し、電池の評価を行った。その結果を表5-1及び表5-2に示す。
(実施例6-1~6-56、比較例6-1~6-3)
錯体化合物(3)として(LiBF3)2Oの代わりに、製造例2で得られたLiBF3OLiを用いたこと以外は、実施例1シリーズと同様にして非水電解液を調製した。LiFSIの濃度、LiPF6の濃度、及びLiBF3OLiの含有量を表6-1及び表6-2に示す。得られた各非水電解液を用い、実施例5シリーズと同様にして、ラミネート電池(セル)の作製し、電池の評価を行った。その結果を表6-1及び表6-2に示す。
Claims (11)
- 一般式(1)~(3)で表される化合物を含む、非水電解液。
LiN(R1SO2)(R2SO2) (R1及びR2は同一又は異なってフッ素原子、炭素数1~6のアルキル基又は炭素数1~6のフルオロアルキル基を示す。) (1)
LiPFa(CmF2m+1)6-a (a:0≦a≦6、m:1≦m≦4) (2)
(Li)m(A)n(UFx)y (Aは酸素原子、硫黄原子、リン原子又は窒素原子を示し、Uはホウ素原子又はリン原子を示す。m:1≦m≦6、n:1≦m≦6、x:3又は5、y:1≦y≦6) (3) - 前記一般式(3)で表される化合物が(LiBF3)2O及びLiBF3OLiの少なくとも一種を含む、請求項1に記載の非水電解液。
- 前記一般式(3)で表される化合物の含有量が0.01質量%以上20質量%以下である、請求項1又は2に記載の非水電解液。
- 前記一般式(1)で表される化合物がLiN(FSO2)2を含む、請求項1~3のいずれか一項に記載の非水電解液。
- 前記一般式(1)で表される化合物濃度と前記一般式(2)で表される化合物濃度とのモル比率が1:25以上5:1以下である、請求項1~4のいずれか一項に記載の非水電解液。
- 前記一般式(1)で表される化合物濃度と前記一般式(2)で表される化合物濃度とのモル比率が1:120以上1:25以下である、請求項1~4のいずれか一項に記載の非水電解液。
- 前記一般式(1)で表される化合物濃度と前記一般式(2)で表される化合物濃度とのモル比率が5:1以上12:1以下である、請求項1~4のいずれか一項に記載の非水電解液。
- 前記一般式(1)で表される化合物濃度と前記一般式(2)で表される化合物濃度とのモル比率が1:120以上12:1以下である、請求項1~4のいずれか一項に記載の非水電解液。
- フッ素含有カーボネート化合物をさらに含む、請求項1~8のいずれか一項に記載の非水電解液。
- 請求項1~9のいずれか一項に記載の非水電解液が用いられてなる、二次電池。
- 少なくとも一面に無機物粒子を塗布してなるセパレータを備える、請求項10に記載の二次電池。
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JPH0922706A (ja) * | 1995-07-07 | 1997-01-21 | Yuasa Corp | 電池用電解質および電池 |
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JP2020004598A (ja) * | 2018-06-28 | 2020-01-09 | 株式会社日立製作所 | 電池 |
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JPH0922706A (ja) * | 1995-07-07 | 1997-01-21 | Yuasa Corp | 電池用電解質および電池 |
JP2019169302A (ja) * | 2018-03-22 | 2019-10-03 | 富山薬品工業株式会社 | 蓄電デバイス用電解質及び非水電解液 |
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