WO2016208607A1 - 導電性材料とその製造方法及び精製方法、並びにこの導電性材料を用いた非水電解液並びに帯電防止剤 - Google Patents
導電性材料とその製造方法及び精製方法、並びにこの導電性材料を用いた非水電解液並びに帯電防止剤 Download PDFInfo
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- WO2016208607A1 WO2016208607A1 PCT/JP2016/068460 JP2016068460W WO2016208607A1 WO 2016208607 A1 WO2016208607 A1 WO 2016208607A1 JP 2016068460 W JP2016068460 W JP 2016068460W WO 2016208607 A1 WO2016208607 A1 WO 2016208607A1
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- conductive material
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- mol
- turbidity
- carbonate
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- 125000004122 cyclic group Chemical group 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 description 1
- 125000006001 difluoroethyl group Chemical group 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
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- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005817 fluorobutyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229940074371 monofluorophosphate Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
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- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic 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
- H01G11/54—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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
-
- 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
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- 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 conductive material. More specifically, the present invention relates to a conductive material containing a fluorosulfonylimide salt, a production method and a purification method thereof, and a nonaqueous electrolytic solution and an antistatic agent using the conductive material.
- Fluorosulfonylimide salts and their derivatives are used in various applications such as electrolytes for various electricity storage devices, additives, selective electrophilic fluorinating agents, photoacid generators, thermal acid generators, near infrared absorbing dyes, etc. Is a useful compound.
- a disulfonylamine onium salt is subjected to a cation exchange reaction in an organic solvent, and then the obtained organic solvent solution of an alkali metal salt is filtered through a filter having a retention particle diameter of 0.1 to 10 ⁇ m, concentrated, A method of crystallizing to obtain a high purity disulfonylamine alkali metal salt is disclosed.
- the inventor has found that the solution of the fluorosulfonylimide salt may become turbid in the course of research, and this has the problem that the degree of turbidity increases as the concentration of the fluorosulfonylimide salt increases. did. Such turbidity may cause clogging of the separator when the solution is used in a non-aqueous electrolyte such as a lithium ion secondary battery, and the solution is used as an antistatic agent. In some cases, the color tone and appearance of the molded product using the antistatic agent may be changed.
- electrolyte solutions used for electricity storage devices such as lithium ion secondary batteries and antistatic applications are filtered using stainless steel mesh or polyolefin mesh such as polyethylene and polypropylene, and then used for various applications. Yes.
- the present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide a clear conductive material with reduced turbidity, a method for producing the same, and a method for purifying the same. Another object of the present invention is to provide a nonaqueous electrolytic solution and an antistatic agent containing the conductive material.
- the conductive material of the present invention that can achieve the above-mentioned object is selected from the group consisting of a fluorosulfonylimide salt represented by the following general formula (1), a carbonate series, an ester series, a ketone series, and an alcohol series. Containing at least one organic solvent, the concentration of the fluorosulfonylimide salt is 0.1 mol / L or more, and the turbidity when measured at 25 ° C. by a scattered light measurement method using a formazine standard solution is 50 NTU / mol -It is characterized by being below LiFSI.
- a fluorosulfonylimide salt represented by the following general formula (1)
- a carbonate series Containing at least one organic solvent
- the concentration of the fluorosulfonylimide salt is 0.1 mol / L or more
- the turbidity when measured at 25 ° C. by a scattered light measurement method using a formazine standard solution is 50 NTU
- X represents F or a fluoroalkyl group having 1 to 6 carbon atoms.
- the organic solvent preferably contains a carbonate solvent.
- the conductive material is at least one compound selected from the group consisting of a compound represented by the following general formula (2), a compound represented by the following general formula (3), and lithium hexafluoroarsenate. It is preferable that it contains. LiPF l (C m F 2m + 1 ) 6-l (0 ⁇ l ⁇ 6, 1 ⁇ m ⁇ 2) (2) LiBF n (C o F 2o + 1 ) 4-n (0 ⁇ n ⁇ 4, 1 ⁇ o ⁇ 2) (3)
- a nonaqueous electrolytic solution containing the conductive material and an antistatic agent containing the conductive material are one of the preferred embodiments of the present invention.
- the present invention includes a method for producing and refining the conductive material.
- the production method and purification method of the present invention include a fluorosulfonylimide salt represented by the general formula (1) and at least one organic solvent selected from the group consisting of carbonates, esters, ketones, and alcohols.
- a method for producing or purifying a conductive material comprising: a solution containing the fluorosulfonylimide salt, at least one selected from the group consisting of cellulose resins, polyester resins, silicon dioxide materials, and activated carbon It is characterized in that it is filtered using a filter medium containing the above materials.
- a clear conductive material with less turbidity can be provided.
- the conductive material of the present invention having a turbidity of 50 NTU / mol-LiFSI or less the non-aqueous electrolyte containing the conductive material of the present invention hardly causes defects when used in various power storage devices. It can be expected that the antistatic agent containing the conductive material of the present invention is less likely to cause poor appearance in a molded product.
- the conductive material of the present invention is a fluorosulfonylimide salt represented by the following general formula (1) (sometimes referred to as fluorosulfonylimide salt (1)), carbonate-based, ester-based, ketone And at least one organic solvent selected from the group consisting of alcohols, the concentration of the fluorosulfonylimide salt is 0.1 mol / L or more, and the turbidity is 50 NTU / mol-LiFSI or less. Has characteristics.
- X represents F or a fluoroalkyl group having 1 to 6 carbon atoms.
- the solution When the fluorosulfonylimide salt (1) is dissolved in an organic solvent, the solution may become turbid, and the turbidity may be caused by applying the solution to a non-aqueous electrolyte such as a lithium ion secondary battery as described above. When used, it may cause clogging of the separator, and when the solution is used as an antistatic agent, the color tone or appearance of the molded product using the antistatic agent may be changed. .
- the present inventor has further studied by paying attention to these problems. When the concentration of the fluorosulfonylimide salt in the solution containing the fluorosulfonylimide salt (1) is 0.1 mol / L or more, the turbidity is 50 NTU / mol. It has been found that the occurrence of the above problems can be suppressed if it is ⁇ LiFSI or less, and the present invention has been completed.
- Fluorosulfonylimide salt The conductive material of the present invention contains a fluorosulfonylimide salt represented by the following general formula (1).
- X represents a fluorine atom (F) or a fluoroalkyl group having 1 to 6 carbon atoms. Therefore, in the present invention, the term “fluorosulfonylimide” includes N- (fluorosulfonyl)-having a fluorosulfonyl group and a fluoroalkylsulfonyl group in addition to bis (fluorosulfonyl) imide having two fluorosulfonyl groups. N- (fluoroalkylsulfonyl) imide is included.
- the fluoroalkyl group having 1 to 6 carbon atoms is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 6 carbon atoms are substituted with fluorine.
- the fluoroalkyl group may be linear, branched, cyclic, or a combination of two or more of these.
- a linear or branched fluoroalkyl group is preferable, and a linear fluoroalkyl group is more preferable.
- fluoroalkyl group examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group, a fluoropropyl group, and a trifluoropropyl group.
- a fluorine atom and a fluoroalkyl group having 1 to 3 carbon atoms are preferable as X.
- fluorosulfonylimide salt (1) examples include lithium bis (fluorosulfonyl) imide, lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide, lithium (fluorosulfonyl) (pentafluoroethylsulfonyl) imide, lithium (Fluorosulfonyl) (heptafluoropropylsulfonyl) imide and the like.
- lithium bis (fluorosulfonyl) imide lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide, lithium (fluorosulfonyl) (pentafluoroethylsulfonyl) imide, lithium (fluorosulfonyl) (heptafluoropropylsulfonyl) imide More preferred are lithium bis (fluorosulfonyl) imide and lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide.
- the conductive material of the present invention may contain one kind of fluorosulfonylimide salt (1) alone or may contain two or more kinds of fluorosulfonylimide salts (1).
- fluorosulfonylimide salt (1) a commercially available product may be used, or a product synthesized by a conventionally known method may be used.
- the concentration of the fluorosulfonylimide salt (1) is 0.1 mol / L or more in the conductive material.
- it is 0.2 mol / L or more, more preferably 0.5 mol / L or more, still more preferably 1 mol / L or more, still more preferably 1.3 mol / L or more, particularly preferably 1.6 mol. / L or more, and most preferably 2 mol / L or more.
- It is preferably 6 mol / L or less, more preferably 5 mol / L or less, and still more preferably 4.5 mol / L or less.
- the concentration of the fluorosulfonylimide salt (1) is less than 0.1 mol / L, a significant increase in turbidity hardly occurs, and when the concentration of the fluorosulfonylimide salt (1) is too dilute, the conductive material It may be difficult to use. On the other hand, if the concentration of the fluorosulfonylimide salt (1) is too high, the fluorosulfonylimide salt (1) may remain undissolved during preparation of the conductive material, or the fluorosulfonylimide salt (1) may be precipitated.
- the conductive material of the present invention may contain an electrolyte salt different from the fluorosulfonylimide salt (1).
- electrolyte salt examples include trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorophosphate ion (PF 6 ⁇ ), perchlorate ion (ClO 4 ⁇ ), and tetrafluoroborate ion (BF 4 ⁇ ).
- LiPF l (C m F 2m + 1 ) 6-l (0 ⁇ l ⁇ 6, 1 ⁇ m ⁇ 2)
- LiAsF 6 hexafluoro arsenate lithium
- Examples of the electrolyte salt represented by the general formula (2) include LiPF 6 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , and LiPF.
- Preferred examples include 3 (C 3 F 7 ) 3 and LiPF 3 (C 4 F 9 ) 3 . More preferred are LiPF 6 and LiPF 3 (C 2 F 5 ) 3 , and more preferred is LiPF 6 .
- electrolyte salt (3) examples include LiBF 4 , LiBF (CF 3 ) 3 , LiBF (C 2 F 5 ) 3 , LiBF (C 3 F 7 ) 3 and the like are preferable, and LiBF 4 and LiBF (CF 3 ) 3 are more preferable, and LiBF 4 is more preferable.
- One of these other electrolyte salts may be used alone, or two or more thereof may be used in combination.
- LiPF 6 , LiPF 3 (C 2 F 5 ) 3 , LiBF 4 , and LiBF (CF 3 ) 3 are preferable, and LiPF 6 and LiPF 3 (C 2 F 5 ) 3 are more preferable. LiPF 6 is preferable.
- the concentration of the other electrolyte salt in the conductive material is preferably 0.1 mol / L or more, more preferably 0.2 mol / L or more, and further preferably 0.5 mol / L or more. It is preferably 0 mol / L or less, more preferably 1.8 mol / L or less, and still more preferably 1.5 mol / L or less. If the concentration of other electrolyte salt in the conductive material is too high, the viscosity of the conductive material may increase and the ionic conductivity may decrease. On the other hand, if the concentration of the other electrolyte salt is too low, it may be difficult to obtain desired ionic conductivity.
- the conductive material of the present invention preferably contains 5 mol% or more of fluorosulfonylimide salt (1) with respect to 100 mol% of the total amount of fluorosulfonylimide salt (1) and other electrolyte salt. More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more, It is preferable that it is 90 mol% or less, More preferably, it is 80 mol% or less, More preferably, it is 70 mol% or less. If the content of the fluorosulfonylimide salt (1) in the conductive material is too much or too little, it may be difficult to obtain desired characteristics.
- the total concentration of all electrolyte salts including the fluorosulfonylimide salt (1) and other electrolyte salts contained in the conductive material is 0.1 mol / L or more, 6 mol / L. It is preferable to use in the range which becomes L or less. More preferably, it is 0.2 mol / L or more, still more preferably 0.5 mol / L or more, more preferably 5 mol / L or less, still more preferably 4.5 mol / L or less, and further preferably 4 mol / L or less. 0.0 mol / L or less.
- Organic Solvent contains at least one organic solvent selected from the group consisting of carbonates, esters, ketones, and alcohols.
- organic solvents include chain carbonates such as dimethyl carbonate (dimethyl carbonate), ethyl methyl carbonate (ethyl methyl carbonate), diethyl carbonate (diethyl carbonate), diphenyl carbonate, and methyl phenyl carbonate; ethylene carbonate (ethylene carbonate) ), Cyclic carbonates such as propylene carbonate (propylene carbonate), 2,3-dimethylethylene carbonate, butylene carbonate, vinylene carbonate, and 2-vinylethylene carbonate.
- ester organic solvents include aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate; lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -valerolactone; trimethyl phosphate, phosphoric acid And phosphoric acid esters such as ethyldimethyl, diethylmethyl phosphate, and triethyl phosphate;
- the ketone-based organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
- alcohol organic solvent examples include ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methanol, ethanol, propan-1-ol, propan-2-ol, butan-2-ol, and the like. .
- the conductive material of the present invention preferably contains a carbonate organic solvent among the above organic solvents.
- a carbonate organic solvent among the above organic solvents.
- dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, and ethylene carbonate are more preferable.
- dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate are preferable because they are low in viscosity and easily dissolved.
- the combination is not particularly limited, and various combinations can be adopted.
- the mixed solvent contains a carbonate type organic solvent.
- a preferable combination includes a combination of a chain carbonate ester and a cyclic carbonate ester. More preferred is a combination of a chain carbonic acid ester and ethylene carbonate.
- a combination of dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate and ethylene carbonate is preferred because of its high versatility.
- the mixing ratio of the carbonate organic solvent and the other organic solvent is preferably 5:95 to 95: 5 (volume ratio). More preferably, it is 10:90 to 90:10, and still more preferably 20:80 to 80:20.
- the organic solvent is preferably contained in an amount of 20% by mass to 99% by mass in 100% by mass of the conductive material of the present invention. If the content of the organic solvent is too large, it may be difficult to obtain desired characteristics. On the other hand, if the content of the organic solvent is too small, the medium may be easily precipitated. More preferably, it is 30% by mass or more, still more preferably 40% by mass, further preferably 50% by mass or more, more preferably 90% by mass or less, and further preferably 80% by mass or less, Especially preferably, it is 70 mass% or less, Most preferably, it is 60 mass% or less.
- the conductive material of the present invention has various characteristics (for example, ionic conductivity, thermal stability, light stability, viscosity).
- An additive for the purpose of improving characteristics such as characteristics and workability may be included. Examples of such additives include antioxidants, anti-aging agents, light stabilizers, lubricants, reinforcing agents, fillers, and the like.
- the content of the additive is 100% by mass in 100% by mass of the conductive material of the present invention (fluorosulfonylimide salt (1), organic solvent, other electrolyte salt optionally used, and additive). ), Preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and more preferably 20% by mass or less. More preferably, it is 10 mass% or less. If the content of the additive is too large, the original physical properties of the conductive material may be impaired. On the other hand, if the content of the additive is too small, the desired effect may not be obtained.
- the conductive material of the present invention has a turbidity of 50 NTU / mol-LiFSI or less.
- the turbidity is a value indicating the degree of turbidity of the conductive material, and the smaller the value, the less turbidity and the clearer the conductive material.
- the turbidity is measured by a scattered light measurement method (neferometry measurement method) in accordance with ISO 7027. More specifically, a turbidimeter (for example, a turbidity tester (2100P manufactured by HACK) was used and calibrated with a formazine standard solution according to ISO 7027, and then the turbidity of the sample solution was measured to obtain a concentration of 1 mol / L.
- the value converted into the value is the turbidity of the sample solution, where the conductive material is a fluorosulfonylimide salt (1) other than LiFSI, an electrolyte salt (2), (3), lithium hexafluoroarsenate, etc.
- the turbidity per LiFSI concentration of 1 mol / L may be determined in the same manner as described above, and the turbidity is preferably measured within 2 hours after the preparation of the sample solution.
- the conductive material of the present invention preferably has a turbidity of 40 NTU / mol-LiFSI or less, more preferably 30 NTU / mol-LiFSI or less, and even more preferably 25 NTU / mol-LiFSI or less. If the turbidity is too high, when the conductive material is used for a non-aqueous electrolyte or an antistatic agent, the separator may be clogged or the appearance of the molded product may be easily deteriorated. The lower the turbidity, the better. However, in order to achieve low turbidity, it is usually necessary to carry out excessive purification, which may complicate the production process and is not economically preferable.
- the ionic conductivity (25 ° C.) of the conductive material is preferably 1 ⁇ 10 ⁇ 6 S / cm or more. More preferably, it is 1 ⁇ 10 ⁇ 5 S / cm or more, and further preferably 1 ⁇ 10 ⁇ 4 S / cm or more.
- the ionic conductivity is within the above range, desired characteristics are easily obtained both when the conductive material is used as a non-aqueous electrolyte described later and when used as an antistatic agent.
- the ion conductivity can be measured by, for example, a complex impedance method using an impedance analyzer HP4294A (trade name, manufactured by Toyo Technica) using an SUS electrode or an impedance analyzer SI1260 (trade name, manufactured by Solartron).
- HP4294A trade name, manufactured by Toyo Technica
- SI1260 trade name, manufactured by Solartron
- the viscosity (25 ° C.) of the conductive material is preferably 500 mPa ⁇ s or less. More preferably, it is 100 mPa * s or less, More preferably, it is 50 mPa * s or less.
- the lower limit of the viscosity of the conductive material is not particularly limited, but is preferably 1 mPa ⁇ s or more. If the viscosity of the conductive material is within the above range, the filterability is improved, which is preferable.
- the viscosity can be measured, for example, by a rheometer manufactured by Brookfield (DV-III type, cone: CPE).
- a solution containing a fluorosulfonylimide salt (1) (that is, the conductive material, hereinafter may be referred to as a fluorosulfonylimide salt (1) solution) is a cellulose resin. It is characterized in that it is filtered using a filter medium (filter) containing at least one material selected from the group consisting of polyester resin, glass material, silica material, and activated carbon.
- the timing of filtration is not particularly limited, and a solution containing a fluorosulfonylimide salt (1) by mixing a preliminarily synthesized fluorosulfonylimide salt (1), an organic solvent and other optional components (conductivity).
- the composition containing the fluorosulfonylimide salt (1) may be continuously filtered as it is after the preparation of the active material composition). Filtration may be performed before use as a non-aqueous electrolyte or an antistatic agent described below.
- the former is referred to as a conductive material manufacturing method, and the latter is referred to as a conductive material purification method.
- any one of the production method and the purification method of the present invention may be carried out alone.
- the obtained conductive material is purified by the present invention. It may be purified by a method.
- a filter medium (filter) containing at least one material selected from the group consisting of a cellulose-based resin, a polyester-based resin, a silicon dioxide-based material, and activated carbon is used. Since water becomes an impurity in non-aqueous electrolytes, stainless steel mesh or the like is often used instead of the filter medium that can adsorb water. However, in the present invention, since the turbidity of the conductive material after filtration is remarkably improved, at least one polarity selected from the group consisting of a cellulose resin, a polyester resin, a silicon dioxide material, and activated carbon is used. The filter medium (filter) containing the material which has is used.
- the polar filter medium adsorbs suspended substances that cause turbidity.
- the cellulose-based resin include cellulose acetate, absorbent cotton, paper and cloth using cellulose as a raw material, and the like.
- the polyester resin include polyethylene terephthalate and polybutylene terephthalate.
- the silicon dioxide-based material include glass-based materials (such as silicate materials), silica, diatomaceous earth, and unglazed plates.
- the activated carbon include gas activated charcoal and zinc chloride activated charcoal.
- the shape of the material is not particularly limited, and is fibrous, powdery, granular, block-like, columnar, cylindrical, weight-like, or film-like (thickness is not particularly limited, and includes sheets and foils. The same applies hereinafter. ) And the like.
- cellulose fiber polyester fiber, glass fiber, silica fiber, activated carbon (granular, powdery or fibrous), silica (granular or powdery), and diatomaceous earth (granular or powdery). It is preferred to use a filter medium comprising at least one selected material.
- the shape and form of the filter medium according to the present invention are not particularly limited as long as it includes at least one of the above materials.
- the above-mentioned material formed into a woven fabric, non-woven fabric, film, or plate, filled with any of the above materials into an arbitrary container, or previously formed into an arbitrary shape (filter material) into any container Any of those filled can be used in the present invention. More specifically, a flat filter paper, a cylindrical filter paper, a cartridge filter, a capsule filter, a membrane filter, a hollow fiber membrane filter, a pleated membrane filter, a woven fabric, a nonwoven fabric, a filter plate, and the like can be given.
- the filter medium used in the production method of the present invention has a retained particle size of preferably 0.05 ⁇ m to 200 ⁇ m, more preferably 0.05 ⁇ m to 5 ⁇ m, and even more preferably 0.05 ⁇ m to 1 ⁇ m. If the retained particle diameter of the filter medium is within the above range, fine impurities can also be removed by filtration. If the retained particle diameter is too small, the filter medium tends to be clogged, whereas if the retained particle diameter is too large, the ability to remove fine impurities tends to be reduced.
- the retained particle diameter of the filter medium is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, and particularly preferably 7 ⁇ m or more.
- the retention particle size is the natural particle filtration of barium sulfate specified in JIS P 3801, and then the efficiency is calculated by the number of particles of barium sulfate in the stock solution and the filtrate. Called the diameter.
- the retained particle diameter may be referred to the manufacturer's nominal value or measured according to the above method.
- Specific filter media that can be used in the present invention include “1034-2” manufactured by ADVANTEC Co., Ltd. 1-No. 7, “NA-17” (including cellulose fiber and diatomaceous earth), etc. Kiriyama Roto (registered trademark) filter paper No. 3, No. 4, no. 5A, no. 5B, no. 5C, No. 6, no. 7 etc .; As a filter medium containing polyester, “TRG940B2K” manufactured by Nakao Filter Industry Co., Ltd .; As a filter medium containing glass (fiber), “SS-47” manufactured by Kiriyama Seisakusho, “GA-55” manufactured by ADVANTEC Co., Ltd.
- one type of filter medium may be used alone, or two or more types of filter medium may be used in combination.
- one or more filter media containing one kind of material are used (for example, use of two or more glass fiber filter papers, combined use of glass fiber filter papers and cellulose fiber filter papers);
- a mode in which one or two or more filter media containing the above materials are used for example, a filter plate made of cellulose fiber and diatomaceous earth; or a mode in which these are combined is included.
- the method of the solution containing the fluorosulfonylimide salt (1) is not particularly limited, and a conventionally known method can be adopted.
- a conventionally known method can be adopted.
- natural filtration, vacuum filtration, pressure filtration, centrifugal filtration and the like can be mentioned as filtration methods.
- Vacuum filtration is preferable because sufficient turbidity can be achieved in a shorter time than natural filtration.
- Nonaqueous Electrolytic Solution The conductive material can be used as a nonaqueous electrolytic solution provided in an electricity storage device such as an electric double layer capacitor, a lithium ion capacitor, or a lithium ion secondary battery. Since the electroconductive material of the present invention has a turbidity of 50 NTU / mol-LiFSI or less, the non-aqueous electrolyte containing this electro-conductive material is clogged with the separator and the suspended components in the non-aqueous electrolyte are unevenly distributed during long-term use. This makes it difficult to cause defects such as performance degradation.
- the non-aqueous electrolyte of the present invention contains the above conductive material. That is, the configuration of the nonaqueous electrolytic solution of the present invention is not particularly limited as long as it contains the conductive material. Therefore, in the present invention, the conductive material may be used as a non-aqueous electrolyte as it is, or if necessary, other than conductive materials such as organic solvents and various additives used in non-aqueous electrolytes of conventional power storage devices. May be included.
- Organic solvent for non-aqueous electrolyte As an organic solvent that can be used for the non-aqueous electrolyte of the present invention, in addition to the above-mentioned carbonate-based, ester-based, ketone-based, and alcohol-based organic solvents, ether-based, sulfur compound-based, Other organic solvents are mentioned.
- the nonaqueous electrolytic solution of the present invention may contain a medium such as a polymer and a polymer gel used in place of the solvent in various power storage devices.
- ether organic solvents 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, 1 , 4-dioxane, 1,3-dioxolane, etc .; sulfur organic solvents include dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane, etc .; , 3-Dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazoly Non, and the like.
- carbonate esters such as chain carbonate esters and cyclic carbonate esters, lactones, and ethers are preferable.
- Dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ⁇ -Butyrolactone, ⁇ -valerolactone, and the like are more preferable, and carbonate solvents such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate are more preferable.
- the said non-aqueous solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the following method may be employed. That is, a method in which a conductive material of the present invention or a solution obtained by dissolving a conductive material in the above-mentioned organic solvent is dropped onto a polymer formed by a conventionally known method to impregnate and carry the conductive material and the organic solvent.
- a method in which a polymer and a conductive material are melted and mixed at a temperature equal to or higher than the melting point of the polymer, and then formed into a film and impregnated with a non-aqueous solvent examples include a method of mixing a dissolved nonaqueous electrolytic solution and a polymer, then forming a film by casting or coating, and volatilizing an organic solvent.
- Polymers used in place of organic solvents include polyethers such as polyethylene oxide (PEO) and polypropylene oxide, which are homopolymers or copolymers of epoxy compounds (ethylene oxide, propylene oxide, butylene oxide, allyl glycidyl ether, etc.)
- Polymers methacrylic polymers such as polymethylmethacrylate (PMMA), nitrile polymers such as polyacrylonitrile (PAN), fluoropolymers such as polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene, and their co-polymers Examples include coalescence.
- PMMA polymethylmethacrylate
- PAN polyacrylonitrile
- PVdF polyvinylidene fluoride
- PVdF polyvinylidene fluoride-hexafluoropropylene
- the nonaqueous electrolyte of the present invention may contain an additive for the purpose of improving various characteristics of the electricity storage device.
- cyclic carbonates having unsaturated bonds such as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), methyl vinylene carbonate (MVC), ethyl vinylene carbonate (EVC); fluoroethylene carbonate, trifluoropropylene carbonate, Carbonate compounds such as phenylethylene carbonate and erythritan carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetra Carboxylic anhydrides such as carboxylic dianhydride and phenyl succinic anhydride; ethylene sulfite, 1,3-propylene carbonate; ethylene sulfite, 1,3
- the additive is preferably used in a concentration of 0.1% by mass to 10% by mass in the non-aqueous electrolyte of the present invention (more preferably 0.2% by mass to 8% by mass, and still more preferably 0%). 3% by mass to 5% by mass, and the total of the conductive material and optionally used organic solvent and additives is 100% by mass).
- the amount of the additive used is too small, it may be difficult to obtain an effect derived from the additive.On the other hand, even if another additive is used in a large amount, it is difficult to obtain an effect commensurate with the added amount. There is a possibility that the viscosity of the non-aqueous electrolyte increases and the conductivity decreases.
- the nonaqueous electrolytic solution of the present invention can be suitably used as a nonaqueous electrolytic solution for, for example, an electric double layer capacitor, a lithium ion capacitor, a lithium ion secondary battery, and the like.
- the conductive material of the present invention also functions as an antistatic agent that imparts antistatic performance to a polymer material. Since the conductive material of the present invention has a turbidity of 50 NTU / mol-LiFSI or less, for example, when the conductive material is kneaded and molded with a polymer material or the like to obtain a molded product, the intended color tone is changed to the molded product. It can be faithfully reproduced, and even when an antistatic layer is formed on a molded product with a coating solution containing the antistatic agent of the present invention, it is difficult to change the design of the coated surface and the molded product is less likely to have a poor appearance. .
- the antistatic agent of the present invention contains the above conductive material. That is, as long as the antistatic agent of this invention contains the said electroconductive material, the structure is not specifically limited. Therefore, in the present invention, the conductive material may be used as an antistatic agent as it is, and if necessary, it has various characteristics such as electrical conductivity, thermal stability, and wettability used in conventional antistatic agents. Components other than the conductive material such as an additive for the purpose of improvement may be included.
- Additives for antistatic agents include dyes, pigments, fillers, silane coupling agents, adhesion improvers, stabilizers, leveling agents, antifoaming agents, antisettling agents, A lubricant, a rust preventive agent, etc. are mentioned.
- the additive is preferably used in the range where the concentration in the antistatic agent of the present invention is 0.01% by mass to 50% by mass. More preferably, the content is 0.1% by mass to 20% by mass, and further preferably 0.5% by mass to 10% by mass (the total of the conductive material and the optional additives is 100% by mass). ).
- the amount of the additive used is too small, it may be difficult to obtain the effect derived from the additive. On the other hand, even if a large amount of other additive is used, it is difficult to obtain an effect commensurate with the added amount.
- Antistatic agent-containing composition and molded article imparted with antistatic properties An antistatic agent-containing composition can be obtained by mixing the antistatic agent with a polymer material or a solvent.
- the polymer material include a thermoplastic resin, a thermosetting resin, and rubber.
- thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene and polystyrene and compositions thereof; polyacetals, polyacrylates, acrylic resins and compositions thereof; polyphenylene ether (PPE), PPE / polystyrene, PPE / polyamide (PA ), Polyphenylene ether resins such as PPE / polybutylene terephthalate (PBT) and compositions thereof; polyester resins such as polyether ketone, polyethylene terephthalate (PET), PBT / ABS and compositions thereof; polycarbonate (PC), PC / ABS, PC / PET, PC / PBT, and other polycarbonate resins and compositions thereof; polyurethane and compositions thereof; polyvinyl chloride, polyvinylidene chloride; polyimide, polyetherimide, polyester Amideimide; polyphenylene sulfide resin and its composition; polysulfone, and the like, it is preferable to use one or more of
- thermosetting resin examples include phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, epoxy resin, silicon resin, polyurethane resin, etc., and one or more of these are used. It is preferable to do.
- the rubber examples include urethane rubber, acrylic rubber, acrylonitrile-butadiene rubber, epichlorohydrin rubber, epichlorohydrin-ethylene oxide copolymer rubber, silicon rubber, fluoroolefin vinyl ether copolymer urethane rubber, styrene butadiene copolymer rubber and the like.
- a foam etc. are mentioned, It is preferable to use these 1 type, or 2 or more types.
- the blending amount of the antistatic agent may be appropriately determined according to the use, but for example, it is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the polymer material. More preferably, it is 1 mass part or more, More preferably, it is 5 mass parts or more, More preferably, it is 20 mass parts or less, More preferably, it is 10 mass parts or less. If the amount of the antistatic agent is too large, the antistatic agent may bleed. On the other hand, if the amount of the antistatic agent is too small, the desired antistatic performance may not be obtained.
- the antistatic agent of the present invention includes, for example, a conductive sheet; a PCT (Pressure Cooker Test) element; a charging member such as an electrophotographic printer or a copying machine; a cleaning member; a developing member; a transfer member; ⁇ Housing products such as OA equipment, game equipment and office equipment, various plastic containers such as IC (Integrated Circuit) trays, various packaging films, flooring sheets, artificial turf, mats, and various moldings such as automobile parts Body: It can be suitably used as an antistatic agent such as a resin material having antistatic properties.
- the turbidity was measured by a scattered light measurement method (neferometry measurement method) in accordance with ISO 7027. More specifically, calibration was performed with a formazine standard solution in accordance with ISO7027 using a turbidity tester (HACK 2100P). Next, lithium bis (fluorosulfonyl) imide solutions (fluorosulfonylimide salt (1) concentration 1 mol / L, before filtration) and conductive materials (fluorosulfonylimide salt (1) concentration 1 mol / L) obtained in the following Examples and Comparative Examples were used. L, after filtration), the scattered light measurement method (neferometry measurement method) was measured at a temperature of 25 ° C., and the turbidity was determined from the obtained value and a calibration curve prepared in advance.
- Lithium bis (fluorosulfonyl) imide (manufactured by Nippon Shokubai Co., Ltd., hereinafter referred to as “LiFSI”) is dissolved in diethyl carbonate (DEC) (manufactured by Kishida Chemical Co., Ltd., LBG grade) so as to have a concentration of 1 mol / L.
- DEC diethyl carbonate
- the turbidity of this lithium bis (fluorosulfonyl) imide solution was measured and found to be 80 NTU / mol-LiFSI.
- a cellulose fiber filter paper (“1034-2” manufactured by ADVANTEC Co., Ltd., retained particle diameter of 1 ⁇ m) was placed as a filter medium on the eye plate portion of the filter holder KGS-47 (effective filtration area 9.6 cm 2 ) manufactured by ADVANTEC. This was set in a filter bell and pressure reduction was started with a vacuum pump. After the filter medium was moistened with a portion of 100 ml of the lithium bis (fluorosulfonyl) imide solution, the remaining lithium bis (fluorosulfonyl) imide solution was poured and filtered under reduced pressure. 1 was obtained. The filtration time at this time was 10 seconds. Conductive material No. obtained according to the above measuring method. A turbidity of 1 was measured. The results are shown in Table 1.
- Example 2 The conductive material No. 1 was the same as in Example 1 except that glass fiber filter paper (“SS-47” manufactured by Kiriyama Seisakusho, retained particle diameter 0.5 ⁇ m) was used as the filter medium. 2 was prepared and its turbidity was measured. The results are shown in Table 1.
- glass fiber filter paper (“SS-47” manufactured by Kiriyama Seisakusho, retained particle diameter 0.5 ⁇ m) was used as the filter medium. 2 was prepared and its turbidity was measured. The results are shown in Table 1.
- Example 3 The conductive material No. 1 was the same as Example 1 except that the vacuum pump was not used. 3 was prepared and its turbidity was measured (natural filtration). The filtration time at this time was 60 seconds. The results are shown in Table 1.
- Example 4 Conductive material No. 1 was used in the same manner as in Example 1 except that filter paper made of polyester fiber (“TRG940B2K” manufactured by Nakao Filter Industry Co., Ltd.) was used as the filter medium. 4 was prepared and its turbidity was measured. The filtration time at this time was 30 seconds. The results are shown in Table 1.
- Example 5 Conductive material No. 1 was used in the same manner as in Example 1 except that a filter plate made of cellulose fiber (“1034-2” manufactured by ADVANTEC) was used as the filter medium. 5 was prepared and its turbidity was measured. The filtration time at this time was 8 seconds. The results are shown in Table 1.
- Example 6 Conductive material No. 1 was used in the same manner as in Example 1 except that filter paper made of cellulose fiber and diatomaceous earth (“NA-17” manufactured by ADVANTEC, retention particle size: 0.3 ⁇ m) was used as the filter medium. 6 was prepared and its turbidity was measured. The filtration time at this time was 25 seconds. The results are shown in Table 1.
- Comparative Example 1 In the same manner as in Example 1 except that a commercially available stainless steel mesh (800 mesh, mesh opening 16 ⁇ m, retention particle size (converted value) 16 ⁇ m) was used, the conductive material No. 7 was prepared and its turbidity was measured. The filtration time at this time was 5 seconds. The results are shown in Table 1.
- Comparative Example 2 Conductivity in the same manner as in Example 1 except that hydrophilic PTFE filter paper “H010A047” (manufactured by ADVANTEC, hydrophilized product, pore size 0.1 ⁇ m, retention particle size (converted value) 0.1 ⁇ m) was used as the filter medium. Material No. 8 was prepared and its turbidity was measured. The filtration time at this time was 8 seconds. The results are shown in Table 1.
- Comparative Example 3 Lithium bis (fluorosulfonyl) imide in the same manner as in Example 1 except that a hydrophobic PTFE filter paper “T010A047” (manufactured by ADVANTEC, pore size 0.1 ⁇ m, retention particle size (converted value) 0.1 ⁇ m) was used as the filter medium.
- a hydrophobic PTFE filter paper “T010A047” manufactured by ADVANTEC, pore size 0.1 ⁇ m, retention particle size (converted value) 0.1 ⁇ m
- the turbidity of the fluorosulfonylimide (1) solution could not be reduced, but a specific material was used. It can be seen that the fluorosulfonylimide (1) solution of the example filtered using the filter medium containing the turbidity after filtration is less than 50 NTU / mol-LiFSI, and the solution is clear. Further, from the results of Examples 2 and 4 and Comparative Examples 1 to 3, not only the retained particle diameter of the filter medium but also the constituent materials of the filter medium greatly affect the turbidity reduction of the fluorosulfonylimide (1) solution. Recognize.
- Example 7 LiFSI was dissolved in diethyl carbonate (DEC) to a concentration of 3.3 mol / L to prepare a LiFSI solution. The turbidity of this LiFSI solution was measured and found to be 65 NTU / mol-LiFSI.
- DEC diethyl carbonate
- filter paper manufactured by Kiriyama Mfg. Co., Ltd., Kiriyama Roto (registered trademark) filter paper No. 5A, retained particle diameter 7 ⁇ m
- ADVANTEC's pressure filtration holder KST-47 effective filtration area 12.5 cm 2
- the LiFSI solution was subjected to pressure filtration at a pressure of 0.5 MPa, and the conductive material No. 10 was obtained. The filtration time at this time was 134 seconds.
- Conductive material No. obtained according to the above measuring method. A turbidity of 10 was measured. The results are shown in Table 2.
- Example 8 The filter paper used was manufactured by Kiriyama Mfg. Co., Ltd., Kiriyama Roto (registered trademark) filter paper No. 3 (retained particle diameter: 5 ⁇ m), except that the conductive material No. 11 was prepared and turbidity was measured. The results are shown in Table 2.
- Example 9 The conductive material No. 1 was changed in the same manner as in Example 8 except that the concentration of the DEC solution of LiFSI was changed to 2.2 mol / L. 12 was prepared and the turbidity was measured. The results are shown in Table 2.
- Example 10 The conductive material No. 1 was changed in the same manner as in Example 7 except that the solvent was changed from diethyl carbonate (DEC) to ethylene carbonate (EC). 13 was prepared and the turbidity was measured. The results are shown in Table 2.
- Example 11 The conductive material No. 1 was changed in the same manner as in Example 9 except that the solvent was changed from diethyl carbonate (DEC) to ethylene carbonate (EC). 14 was prepared and the turbidity was measured. The results are shown in Table 2.
- the non-aqueous electrolyte containing the conductive material of the present invention is less likely to cause defects when used in various power storage devices, and the antistatic agent containing the conductive material of the present invention is less likely to cause poor appearance in molded products. Can be expected.
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Abstract
Description
特許文献1には、有機溶媒中でジスルホニルアミンオニウム塩をカチオン交換反応させた後、得られたアルカリ金属塩の有機溶媒溶液を保留粒子径0.1~10μmのフィルターでろ過し、濃縮、晶析させて高純度のジスルホニルアミンアルカリ金属塩を得る方法が開示されている。
LiPFl(CmF2m+1)6-l(0≦l≦6、1≦m≦2) (2)
LiBFn(CoF2o+1)4-n(0≦n≦4、1≦o≦2) (3)
本発明の導電性材料とは、下記一般式(1)で表されるフルオロスルホニルイミド塩(フルオロスルホニルイミド塩(1)と称する場合がある。)と、カーボネート系、エステル系、ケトン系、アルコール系よりなる群から選択される少なくとも1種の有機溶媒を含み、上記フルオロスルホニルイミド塩の濃度が0.1mol/L以上であり、濁度が50NTU/mol-LiFSI以下であるところに特徴を有する。
本発明の導電性材料は、下記一般式(1)で表されるフルオロスルホニルイミド塩を含む。
一般式(1)中、Xはフッ素原子(F)、又は炭素数1~6のフルオロアルキル基を表す。したがって、本発明において「フルオロスルホニルイミド」との文言には、フルオロスルホニル基を2つ有するビス(フルオロスルホニル)イミドの他、フルオロスルホニル基とフルオロアルキルスルホニル基とを有するN-(フルオロスルホニル)-N-(フルオロアルキルスルホニル)イミドが含まれる。
無機カチオンとしてはアルカリ金属カチオン及びアルカリ土類金属カチオンが好ましく、有機カチオンとしてはオニウムカチオンが好ましい。
本発明の導電性材料は、カーボネート系、エステル系、ケトン系、アルコール系よりなる群から選択される少なくとも1種の有機溶媒を含む。
カーボネート系の有機溶媒としては、炭酸ジメチル(ジメチルカーボネート)、炭酸エチルメチル(エチルメチルカーボネート)、炭酸ジエチル(ジエチルカーボネート)、炭酸ジフェニル、炭酸メチルフェニル等の鎖状炭酸エステル類;炭酸エチレン(エチレンカーボネート)、炭酸プロピレン(プロピレンカーボネート)、2,3-ジメチル炭酸エチレン、炭酸ブチレン、炭酸ビニレン、2-ビニル炭酸エチレン等の環状炭酸エステル類;が挙げられる。
ケトン系の有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等が挙げられる。
アルコール系の有機溶媒としては、エチレングリコール、プロピレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メタノール、エタノール、プロパン-1-オール、プロパン-2-オール、ブタン-2-オール等が挙げられる。
本発明の導電性材料は、上記フルオロスルホニルイミド塩(1)、有機溶媒、及び任意で用いられる電解質塩以外に、各種特性(例えば、イオン伝導度、熱安定性、光安定性、粘度特性、作業性等の特性)の向上を目的とする添加剤を含んでいてもよい。このような添加剤としては、例えば酸化防止剤、老化防止剤、光安定剤、滑剤、補強剤、充填剤等が挙げられる。
本発明の導電性材料は濁度が50NTU/mol-LiFSI以下である。濁度とは導電性材料の濁りの程度を指標する値であって、その値が小さいほど濁りが少なく導電性材料が清澄であることを意味する。本発明ではISO7027に準拠して、散乱光測定法(ネフェロメトリー測定法)により濁度を測定する。より詳細には、濁度計(例えば濁度試験機(HACK社製2100P)を用い、ISO7027に従って、ホルマジン標準液により校正を行った後、試料溶液の濁度を測定して濃度1mol/Lの値に換算した値を、その試料溶液の濁度とする。なお、導電性材料がLiFSI以外のフルオロスルホニルイミド塩(1)や、電解質塩(2)、(3)又は六フッ化砒酸リチウム等の化合物を含む場合も、上記と同じようにして、LiFSI濃度1mol/Lあたりの濁度を求めればよい。濁度の測定は、試料溶液の調製後2時間以内に実施するのが好ましい。
次に本発明の導電性材料の製造方法及び精製方法について説明する。本発明の製造方法及び精製方法とは、フルオロスルホニルイミド塩(1)を含む溶液(すなわち上記導電性材料。以下、フルオロスルホニルイミド塩(1)溶液と称する場合がある。)を、セルロース系樹脂、ポリエステル系樹脂、ガラス系材料、シリカ系材料、及び活性炭よりなる群から選択される少なくとも1種の材料を含む濾材(フィルター)を使用して濾過するところに特徴を有する。
なお、本発明の製造方法、精製方法は何れか1種を単独で実施してもよく、また本発明の製造方法により導電性材料を得た後、得られた導電性材料を本発明の精製方法で精製してもよい。
非水電解液では水分は不純物となるため、通常は、水を吸着する可能性のある上記濾材ではなく、ステンレス鋼のメッシュ等が使われることが多かった。しかし、本発明では、濾過後の導電性材料の濁度が著しく改善されることから、セルロース系樹脂、ポリエステル系樹脂、二酸化ケイ素系材料及び活性炭よりなる群から選択される少なくとも1種の極性を有する材料を含む濾材(フィルター)を用いる。これらを用いることで導電性材料の濁度が改善されるのは、極性を有する濾材が濁りの原因となる懸濁物質を吸着してためであると推察される。
セルロース系樹脂としては、セルロースアセテート、脱脂綿、セルロースを原料とする紙及び布等挙げられる。ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。二酸化ケイ素系材料としては、ガラス系材料(ケイ酸塩材料等)、シリカ、珪藻土、素焼板等が挙げられる。活性炭としては、ガス賦活炭、塩化亜鉛賦活炭等が挙げられる。
なお、保留粒子径とはJIS P 3801で規定された硫酸バリウムを自然濾過した後、原液と濾液の硫酸バリウムの粒子数により効率を算出し、約99%以上分離している粒子径を保留粒子径と称する。保留粒子径は、製造業者の公称値を参考にしてもよく、上記方法に従って測定してもよい。
上記導電性材料は、電気二重層キャパシタ、リチウムイオンキャパシタ、リチウムイオン二次電池などの蓄電デバイスに備えられる非水電解液として使用することができる。本発明の導電性材料は濁度が50NTU/mol-LiFSI以下なので、この導電性材料を含む非水電解液はセパレーターの目詰まりや、長期使用時に非水電解液中の懸濁成分が偏在することによる性能の低下といった不良を生じ難いものとなる。
本発明の非水電解液に使用できる有機溶媒としては、上述したカーボネート系、エステル系、ケトン系、及びアルコール系の有機溶媒の他、エーテル系、硫黄化合物系、その他有機溶媒が挙げられる。また、本発明の非水電解液は、各種蓄電デバイスにおいて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を含んでいてもよい。
本発明の非水電解液は、蓄電デバイスの各種特性の向上を目的とする添加剤を含んでいてもよい。
添加剤としては、ビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、メチルビニレンカーボネート(MVC)、エチルビニレンカーボネート(EVC)等の不飽和結合を有する環状カーボネート;フルオロエチレンカーボネート、トリフルオロプロピレンカーボネート、フェニルエチレンカーボネート及びエリスリタン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、シクロペンタンテトラカルボン酸二無水物、フェニルコハク酸無水物等のカルボン酸無水物;エチレンサルファイト、1,3-プロパンスルトン、1,4-ブタンスルトン、メタンスルホン酸メチル、ブサルファン、スルホラン、スルホレン、ジメチルスルホン、テトラメチルチウラムモノスルフィド、トリメチレングリコール硫酸エステル等の含硫黄化合物;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、N-メチルスクシンイミド等の含窒素化合物;モノフルオロリン酸塩、ジフルオロリン酸塩等のリン酸塩;ヘプタン、オクタン、シクロヘプタン等の飽和炭化水素化合物;等が挙げられる。
本発明の導電性材料は、高分子材料に帯電防止性能を付与する帯電防止剤としても機能する。本発明の導電性材料は濁度が50NTU/mol-LiFSI以下であるので、例えば導電性材料を高分子材料等と混練、成形して成形品とする場合には、意図した色調を成形品に忠実に再現でき、また、本発明の帯電防止剤を含む塗布液により成形品に帯電防止層を形成する場合にも、被塗布面の意匠に変化を与え難く、成形品に外観不良を起こし難い。
本発明の帯電防止剤に使用できる添加剤としては染料、顔料、充填剤、シランカップリング剤、接着性改良剤、安定剤、レベリング剤、消泡剤、沈降防止剤、潤滑剤、及び防錆剤等が挙げられる。
添加剤は、本発明の帯電防止剤中の濃度が0.01質量%~50質量%となる範囲で用いるのが好ましい。より好ましくは0.1質量%~20質量%であり、さらに好ましくは0.5質量%~10質量%である(導電性材料と、任意で用いられる添加剤の合計を100質量%とする。)。添加剤の使用量が少なすぎるときには、添加剤に由来する効果が得られ難い場合があり、一方、多量に他の添加剤を使用しても、添加量に見合う効果は得られ難くなる。
上記帯電防止剤を高分子材料や溶媒等と混合すれば、帯電防止剤含有組成物が得られる。
高分子材料としては、例えば熱可塑性樹脂、熱硬化性樹脂及びゴム等が挙げられる。熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン等のポリオレフィン系樹脂及びその組成物;ポリアセタール、ポリアクリレート、アクリル樹脂及びその組成物;ポリフェニレンエーテル(PPE)、PPE/ポリスチレン、PPE/ポリアミド(PA)、PPE/ポリブチレンテレフタレート(PBT)等のポリフェニレンエーテル系樹脂及びその組成物;ポリエーテルケトン、ポリエチレンテレフタレート(PET)、PBT/ABS等のポリエステル系樹脂及びその組成物;ポリカーボネート(PC)、PC/ABS、PC/PET、PC/PBT等のポリカーボネート系樹脂及びその組成物;ポリウレタン及びその組成物;ポリ塩化ビニル、ポリ塩化ビニリデン;ポリイミド、ポリエーテルイミド、ポリアミドイミド;ポリフェニレンサルファイド系樹脂及びその組成物;ポリサルホン等が挙げられ、これらの1種又は2種以上を使用することが好ましい。これらの中でも、導電性に優れる点から、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリ塩化ビニル樹脂、エポキシ樹脂がより好ましく、上記高分子材料として、これらの樹脂の少なくとも1種を用いることが好適である。
上記ゴムとしては、例えば、ウレタンゴム、アクリルゴム、アクリロニトリル-ブタジエンゴム、エピクロルヒドリンゴム、エピクロルヒドリン-エチレンオキサイド共重合ゴム、シリコンゴム、フルオロオレフィンビニルエーテル共重合体ウレタンゴム、スチレンブタジエン共重合体ゴム及びそれらの発泡体等が挙げられ、これらの1種又は2種以上を使用することが好ましい。
本発明ではISO7027に準拠して、散乱光測定法(ネフェロメトリー測定法)により濁度を測定した。より詳細には、濁度試験機(HACK社製2100P)を用い、ISO7027に従って、ホルマジン標準液により校正を行った。次いで下記実施例及び比較例で得られたリチウムビス(フルオロスルホニル)イミド溶液(フルオロスルホニルイミド塩(1)濃度1mol/L、濾過前)と導電性材料(フルオロスルホニルイミド塩(1)濃度1mol/L、濾過後)について、温度25℃で散乱光測定法(ネフェロメトリー測定法)の測定を行い、得られた値と予め作成しておいた検量線より濁度を求めた。
ジエチルカーボネート(DEC)(キシダ化学株式会社製、LBGグレード)に、濃度が1mol/Lとなるようにリチウムビス(フルオロスルホニル)イミド(株式会社日本触媒製。以下「LiFSI」と称する。)を溶解させてリチウムビス(フルオロスルホニル)イミド溶液を調製した。このリチウムビス(フルオロスルホニル)イミド溶液について濁度を測定したところ80NTU/mol-LiFSIであった。
濾材としてガラス繊維濾紙(桐山製作所製「SS-47」、保留粒子径0.5μm)を使用したこと以外は実施例1と同様にして導電性材料No.2を調製し、その濁度を測定した。結果を表1に示す。
真空ポンプを用いなかったこと以外は実施例1と同様にして導電性材料No.3を調製し、その濁度を測定した(自然濾過)。このときの濾過時間は60秒間であった。結果を表1に示す。
濾材としてポリエステル繊維からなる濾紙(中尾フィルター工業株式会社製「TRG940B2K」)を使用したこと以外は実施例1と同様にして導電性材料No.4を調製し、その濁度を測定した。このときの濾過時間は30秒間であった。結果を表1に示す。
濾材としてセルロース繊維からなる濾過板(ADVANTEC社製「1034-2」)を使用したこと以外は実施例1と同様にして導電性材料No.5を調製し、その濁度を測定した。このときの濾過時間は8秒間であった。結果を表1に示す。
濾材としてセルロース繊維と珪藻土からなる濾紙(ADVANTEC社製「NA-17」、保留粒子径0.3μm)を使用したこと以外は実施例1と同様にして導電性材料No.6を調製し、その濁度を測定した。このときの濾過時間は25秒間であった。結果を表1に示す。
市販のステンレス鋼製メッシュ(800メッシュ、目開き16μm、保留粒子径(換算値)16μm)を使用したこと以外は実施例1と同様にして導電性材料No.7を調製し、その濁度を測定した。このときの濾過時間は5秒間であった。結果を表1に示す。
濾材として親水性PTFE濾紙「H010A047」(ADVANTEC社製、親水処理化品、ポアサイズ0.1μm、保留粒子径(換算値)0.1μm)を使用したこと以外は実施例1と同様にして導電性材料No.8を調製し、その濁度を測定した。このときの濾過時間は8秒間であった。結果を表1に示す。
濾材として疎水性PTFE濾紙「T010A047」(ADVANTEC社製、ポアサイズ0.1μm、保留粒子径(換算値)0.1μm)を使用したこと以外は実施例1と同様にしてリチウムビス(フルオロスルホニル)イミド溶液の吸引濾過を行おうとしたところ、濾材がリチウムビス(フルオロスルホニル)イミド溶液をはじいてしまい濾過をすることができなかった。
ジエチルカーボネート(DEC)に、濃度が3.3mol/LとなるようにLiFSIを溶解させてLiFSI溶液を調製した。このLiFSI溶液について濁度を測定したところ、65NTU/mol-LiFSIであった。
用いた濾紙を、桐山製作所製、桐山ロート(登録商標)用濾紙No.3(保留粒子径5μm)に変えた以外は、実施例7と同様にして導電性材料No.11を調製し、濁度を測定した。結果を表2に示す。
LiFSIのDEC溶液の濃度を2.2mol/Lに変えた以外は、実施例8と同様にして導電性材料No.12を調製し、濁度を測定した。結果を表2に示す。
溶媒をジエチルカーボネート(DEC)からエチレンカーボネート(EC)に変えた以外は、実施例7と同様にして導電性材料No.13を調製し、濁度を測定した。結果を表2に示す。
溶媒をジエチルカーボネート(DEC)からエチレンカーボネート(EC)に変えた以外は、実施例9と同様にして導電性材料No.14を調製し、濁度を測定した。結果を表2に示す。
Claims (7)
- 上記有機溶媒が、カーボネート系溶媒を含む請求項1に記載の導電性材料。
- 上記導電性材料が、下記一般式(2)で表される化合物、下記一般式(3)で表される化合物、及び六フッ化砒酸リチウムよりなる群から選択される少なくとも1種の化合物を含む請求項1又は2に記載の導電性材料。
LiPFl(CmF2m+1)6-l(0≦l≦6、1≦m≦2) (2)
LiBFn(CoF2o+1)4-n(0≦n≦4、1≦o≦2) (3) - 請求項1~3のいずれかに記載の導電性材料を含むことを特徴とする非水電解液。
- 請求項1~3のいずれかに記載の導電性材料を含むことを特徴とする帯電防止剤。
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KR1020177033905A KR102542990B1 (ko) | 2015-06-23 | 2016-06-22 | 도전성 재료와 그 제조방법 및 정제방법, 및 이 도전성 재료를 사용한 비수전해액 및 대전방지제 |
JP2017524935A JP6246983B2 (ja) | 2015-06-23 | 2016-06-22 | 導電性材料とその製造方法及び精製方法、並びにこの導電性材料を用いた非水電解液並びに帯電防止剤 |
US15/565,759 US10461365B2 (en) | 2015-06-23 | 2016-06-22 | Conductive material and manufacturing method and purification method for same, and non aqueous electrolyte solution and antistatic agent using said conductive material |
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CN201680036268.8A CN107710492A (zh) | 2015-06-23 | 2016-06-22 | 导电性材料及其制备方法和精制方法,以及使用了该导电性材料的非水电解液和抗静电剂 |
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US10926190B2 (en) * | 2018-11-16 | 2021-02-23 | Ses Holdings Pte. Ltd. | Purified lithium bis(fluorosulfonyl)imide (LiFSI) products, methods of purifying crude LiFSI, and uses of purified LiFSI products |
CN113262566B (zh) * | 2021-05-21 | 2022-11-25 | 苏州克劳丝纳米科技有限公司 | 一种基于碳纳米纤维的防静电纳米纤维过滤材料及其制备方法 |
EP4332054A1 (en) | 2022-11-24 | 2024-03-06 | Specialty Operations France | Composition comprising an alkali metal salt of bis(fluoro sulfonyl)imide |
EP4332055A1 (en) | 2022-11-24 | 2024-03-06 | Specialty Operations France | Composition comprising an alkali metal salt of bis(fluoro sulfonyl)imide |
EP4332056A1 (en) | 2022-11-24 | 2024-03-06 | Specialty Operations France | Composition comprising an alkali metal salt of bis(fluoro sulfonyl)imide |
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KR20180020135A (ko) | 2018-02-27 |
JP6452786B2 (ja) | 2019-01-16 |
KR102542990B1 (ko) | 2023-06-12 |
JPWO2016208607A1 (ja) | 2017-12-07 |
US20180123172A1 (en) | 2018-05-03 |
US10461365B2 (en) | 2019-10-29 |
CN107710492A (zh) | 2018-02-16 |
EP3316381A1 (en) | 2018-05-02 |
JP6246983B2 (ja) | 2017-12-13 |
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