WO2015111612A1 - 二次電池用添加剤、それを用いた電極及び電解液、リチウムイオン電池並びにリチウムイオンキャパシタ - Google Patents
二次電池用添加剤、それを用いた電極及び電解液、リチウムイオン電池並びにリチウムイオンキャパシタ Download PDFInfo
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- WO2015111612A1 WO2015111612A1 PCT/JP2015/051514 JP2015051514W WO2015111612A1 WO 2015111612 A1 WO2015111612 A1 WO 2015111612A1 JP 2015051514 W JP2015051514 W JP 2015051514W WO 2015111612 A1 WO2015111612 A1 WO 2015111612A1
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- Prior art keywords
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- additive
- compound
- carbon atoms
- lithium ion
- Prior art date
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- 239000000654 additive Substances 0.000 title claims abstract description 102
- 230000000996 additive effect Effects 0.000 title claims abstract description 99
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 88
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 88
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- 239000008151 electrolyte solution Substances 0.000 title claims description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 115
- 125000004432 carbon atom Chemical group C* 0.000 claims description 63
- 239000000126 substance Substances 0.000 claims description 43
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- 125000004429 atom Chemical group 0.000 claims description 17
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 8
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 8
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- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Classifications
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M10/42—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an additive useful for a nonaqueous electrolyte secondary battery, an electrode and an electrolyte using the same, a lithium ion battery, and a lithium ion capacitor.
- Non-aqueous electrolyte secondary batteries such as lithium ion batteries are characterized by high voltage and high energy density, so they are widely used in the field of portable information equipment, and the demand for them is rapidly expanding.
- a position as a standard battery for mobile information devices such as telephones and notebook computers has been established.
- higher performance for example, higher capacity and higher energy density
- various methods such as higher density by improving the filling rate of electrodes, improvement of the depth of use of current active materials (especially negative electrodes), development of new high-capacity active materials, etc. have been carried out. Yes.
- the capacity of the non-aqueous electrolyte secondary battery is reliably increased by these methods.
- a cobalt composite oxide which is an active material of a non-aqueous electrolyte secondary battery having an operating voltage of 4.2 V class, has a charge capacity of about 155 mAh / g when charged to 4.3 V based on the current Li standard.
- LiCoO 2 cobalt composite oxide
- the utilization rate of a positive electrode active material becomes large by the improvement of a charging voltage.
- Patent Document 1 Technology to treat battery materials with silane coupling agents as a method to solve problems such as deterioration of charge / discharge cycle characteristics in non-aqueous electrolyte secondary batteries, gas generation during high-temperature storage, and ignition accidents due to abnormal heating of batteries (See Patent Document 1), a technique for adding an ether compound (see Patent Documents 2 and 3), a technique for adding a sulfone compound having a triple bond (see Patent Document 4), and a phosphate ester as an electrolyte Techniques used (see Patent Documents 5 and 6) are disclosed.
- the use of the silane coupling agent described in Patent Document 1 has a certain gas generation suppression effect, the effect is not sufficient and there is a problem that the cycle characteristics deteriorate.
- the ether compounds described in Patent Documents 2 and 3 and the sulfone compound described in Patent Document 4 are added to the electrolytic solution, there is a problem that cycle characteristics deteriorate.
- the phosphate esters described in Patent Documents 5 and 6 are used in the electrolyte, safety is improved, but there is a problem that the ionic conductivity is lowered and the output characteristics are deteriorated.
- the present invention has been made in view of these problems. That is, the problem to be solved by the present invention is to suppress the gas generation of the nonaqueous electrolyte secondary battery and to improve the charge / discharge cycle characteristics and output characteristics.
- the present invention relates to an atomic group (X) and a triple bond (consisting of 2 to 4 atoms having 3 to 5 atoms, an electronegativity of 3 or more, and having at least one double bond ( a secondary battery additive containing the compound (A) having b); an electrode containing the secondary battery additive; an electrolyte containing the secondary battery additive; the electrode and / or the electrolysis A lithium ion battery having a liquid; a lithium ion capacitor having the electrode and / or the electrolyte.
- the electrode or electrolyte containing the secondary battery additive of the present invention By using the electrode or electrolyte containing the secondary battery additive of the present invention, it is possible to suppress the gas generation of the lithium ion battery or lithium ion capacitor and improve the charge / discharge cycle characteristics and output characteristics. it can. Moreover, safety can be improved by suppressing heat generation due to an abnormal reaction that occurs when the lithium ion battery becomes high temperature.
- the secondary battery additive of the present invention is also referred to as a secondary battery additive (B) of the present invention.
- the secondary battery additive (B) of the present invention comprises 3 to 5 atoms, has 2 to 4 atoms having an electronegativity of 3 or more, and has at least one double bond.
- a compound (A) having an atomic group (X) and a triple bond (b) is contained.
- the compound (A) may have two or more atomic groups (X) in one molecule. When the compound (A) has two or more atomic groups (X) in one molecule, they may all be the same or different.
- the compound (A) may have two or more triple bonds (b) in one molecule. When the compound (A) has two or more triple bonds (b) in one molecule, they may all be the same or different.
- the number of triple bonds (b) possessed by one molecule of compound (A) is preferably 1 to 4, more preferably 1 to 3.
- the atomic group (X) is composed of 3 to 5 atoms, has 2 to 4 atoms having an electronegativity of 3 or more, and has at least one double bond.
- Examples of the atoms constituting the atomic group (X) include typical elements. From the viewpoint of battery characteristics, a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a fluorine atom, a sulfur atom, a phosphorus atom, and a chlorine atom are preferable.
- a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom are more preferable, and a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom are still more preferable.
- the number of atoms constituting the atomic group (X) may be one, or two or more.
- the number of atoms constituting the atomic group (X) is usually 3 to 5, but is preferably 3 from the viewpoint of battery characteristics.
- Examples of the atom having an electronegativity of 3 or more in the atomic group (X) include an oxygen atom, a nitrogen atom, a fluorine atom and a chlorine atom, and among these, an oxygen atom and a nitrogen atom are preferable from the viewpoint of cycle characteristics.
- the number of atoms having an electronegativity of 3 or more is usually 2 to 4, but 2 is preferable from the viewpoint of battery characteristics and the like.
- Electronegativity represents the tendency of atoms to attract electrons. In the present invention, it means the electronegativity defined by Pauling, and the value of electronegativity defined by Pauling is L.P. It is described in "The Nature of the Chemical Bond” (1960) by Pauling. Since active materials used for non-aqueous electrolyte secondary batteries contain highly polar atoms such as oxygen atoms, there are portions where electrons are present in a biased manner.
- the compound (A) contained in the secondary battery additive (B) of the present invention has a high electronegativity atom (an atom having an electronegativity of 3 or more) and an active material in which electrons are biased. By doing so, it is considered that a high gas generation suppression effect and the like are exhibited by the secondary battery additive (B) of the present invention adsorbing to the active material.
- Examples of the double bond contained in the atomic group (X) include a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-nitrogen double bond, a sulfur-oxygen double bond, and a phosphorus-oxygen double bond.
- Preferred examples of the double bond include a carbon-oxygen double bond, a phosphorus-oxygen double bond, and a sulfur-oxygen double bond, and a carbon-oxygen double bond is more preferable.
- atomic group (X) examples include groups (bonds) represented by any of the following chemical formulas (1) to (5).
- the atomic group represented by the chemical formula (1) is included in an amide group, a urethane group, a urea group, an allophanate group, a biuret group, and the like.
- An amide group can be generated by a dehydration condensation reaction between a carboxyl group and an amino group
- a urethane group can be generated by an addition reaction between an isocyanate group and a hydroxyl group
- a urea group can be formed by a reaction between an isocyanate group and water.
- allophanate group can be generated by addition reaction of isocyanate group to urethane group
- biuret group has addition of isocyanate group to urea group It can produce
- the atomic group represented by the chemical formula (2) is contained in, for example, an ester group, and can be generated by a dehydration condensation reaction between a carboxyl group and a hydroxyl group, a ring-opening addition reaction of a hydroxyl group to an acid anhydride group, or the like.
- the atomic group represented by the chemical formula (3) can be generated by oxidizing the sulfide with an oxidizing agent.
- the atomic group represented by the chemical formula (4) can be generated by a dehydration condensation reaction between phosphoric acid and a hydroxyl group and a condensation reaction between a phosphate compound and a hydroxyl group.
- the atomic group represented by the chemical formula (5) can be generated by reacting a primary amine with phosgene.
- Each group represented by the chemical formulas (1) to (5) can be introduced into the compound (A) by, for example, the above reaction.
- a group represented by the chemical formula (1) is more preferable.
- the compound (A) in the present invention for example, a compound having at least one group represented by the chemical formula (1) and having a triple bond (b) is particularly preferable.
- the group represented by the chemical formula (1) is preferably a group represented by the following general formula (6).
- R is a hydrogen atom or an organic group having 1 to 12 carbon atoms.
- the organic group having 1 to 12 carbon atoms include an aliphatic hydrocarbon group having 1 to 12 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group).
- R is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrogen atom.
- the group represented by the general formula (6) is included in an amide group, a urethane group, a urea group, an allophanate group, a biuret group, and the like, and is selected from the group consisting of a urethane group, a urea group, an allophanate group, and a biuret group.
- the group is contained in at least one group selected from the group consisting of a urethane group (—OCONH—) and a urea group (—NHCONH—). preferable.
- the compound (A) in the present invention preferably has at least one selected from the group consisting of a urethane group, a urea group, an allophanate group and a biuret group, and more preferably has a urethane group or a urea group.
- the triple bond (b) possessed by the compound (A) is preferably a carbon-carbon triple bond and / or a carbon-nitrogen triple bond from the viewpoint of cycle characteristics and gas generation suppression.
- the compound (A) preferably has an alkyleneoxy group (d) from the viewpoint of battery output characteristics.
- the alkyleneoxy group (d) include alkyleneoxy groups having 2 to 4 carbon atoms (such as an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group). Among these, an ethyleneoxy group is preferable from the viewpoint of battery output characteristics.
- the alkyleneoxy group (d) may be composed of one alkyleneoxy group or may be composed of two or more alkyleneoxy groups bonded together, and from the viewpoint of battery output characteristics, Of alkyleneoxy groups or 2 to 40 alkyleneoxy groups are preferably bonded in succession, and 3 to 30 alkyleneoxy groups are preferably bonded in succession. preferable.
- the bonded alkyleneoxy groups When two or more alkyleneoxy groups are successively bonded, the bonded alkyleneoxy groups may be one type or two or more types. When two or more kinds of alkyleneoxy groups are continuously bonded, the bonding mode may be random, block, or a mixture thereof.
- the compound (A) preferably has a triple bond (b) and an alkyleneoxy group (d) as a structural unit represented by the following general formula (7) or (8).
- R 1 is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of R 1 s , they may be the same or different.
- R 1 include an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a tetramethylene group.
- an ethylene group is preferable from the viewpoint of battery characteristics.
- R 2 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and examples of R 2 include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexamethylene group. Among these, a methylene group and an ethylene group are preferable from the viewpoint of battery characteristics.
- R 3 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms in which the hydrogen atom may be substituted with a functional group containing a hetero atom, and R 3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms ( Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group
- aromatic hydrocarbon groups (benzyl group, phenyl group, methylphenyl group, biphenyl group, naphthyl group, etc.) and the like.
- a hydrogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferably used.
- R 3 is more preferably a hydrogen atom.
- the functional group containing a hetero atom include an amino group, an alkylamino group, a dialkylamino group, and an alkylthio group.
- h is an integer of 1 to 40, preferably 3 to 30, and more preferably 5 to 20.
- P 1 is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of P 1 s , P 1 may be the same or different. Examples of P 1 include the same as R 1 described above, and preferable ones are also the same.
- P 2 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and examples of P 2 include the same as those described above for R 2, and preferred ones are also the same.
- i is an integer of 1 to 40, preferably 3 to 30, and more preferably 5 to 20.
- the compound (A) preferably has the alkyleneoxy group (d) as a structural unit represented by the following general formula (9) from the viewpoint of battery output characteristics.
- W 1 is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of W 1 s , they may be the same or different. Examples of W 1 include the same as R 1 described above, and preferable ones are also the same.
- W 2 is a hydrocarbon group having 1 to 20 carbon atoms
- W 2 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1, 2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, heptyl group
- an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, an isopropyl group, and a 2-ethylhexyl group are more preferable.
- k is an integer of 1 to 40, preferably 3 to 30, and particularly preferably 5 to 20 from the viewpoint of output characteristics.
- the compound (A) preferably has a group represented by the following general formula (10).
- Q 1 is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of Q 1 s , Q 1 may be the same or different.
- Q 1 include the same as R 1 described above, and preferable examples are also the same.
- Q 2 is a divalent hydrocarbon group having 1 to 10 carbon atoms.
- examples of Q 2 include the same as R 2 described above, and preferable examples are also the same.
- M is a monovalent metal ion, and examples thereof include alkali metal ions such as lithium ion, sodium ion and potassium ion. Of these, lithium ions and sodium ions are preferable from the viewpoint of battery output characteristics and the like.
- A is —CO 2 — or —SO 3 — , and —SO 3 — is preferable from the viewpoint of battery output characteristics.
- j is an integer of 0 to 40, preferably 3 to 30, and particularly preferably 5 to 20, from the viewpoint of output characteristics.
- m is 0 or 1, preferably 1.
- Preferred examples of the compound (A) include those represented by the following general formulas (11) to (16). Each compound represented by the following general formulas (11) to (16) is suitable as a compound having the group represented by the above chemical formula (1) as the atomic group (X).
- R 4 is a hydrocarbon group having 1 to 20 carbon atoms having a carbon-carbon triple bond or a carbon-nitrogen triple bond.
- R 5 is a hydrocarbon group having 1 to 20 carbon atoms.
- X 1 represents an oxygen atom or an imino group.
- R 6 and R 8 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 6 and R 8 is a carbon-carbon triple bond or a carbon-nitrogen triple bond. Have a bond.
- R 7 is a divalent hydrocarbon group having 1 to 20 carbon atoms.
- X 2 and X 3 each independently represent an oxygen atom or an imino group.
- R 9 and R 15 are each independently a hydrocarbon group having 1 to 20 carbon atoms.
- R 10 to R 14 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 9 , R 11 , R 13 and R 15 is a carbon-carbon triple bond or carbon -It has a nitrogen triple bond.
- n is an integer of 0-20.
- X 4 , X 5 , X 6 , X 7 , X 8 and X 9 each independently represent an oxygen atom or an imino group. When a plurality of X 5 and X 6 are contained in the molecule, X 5 may be the same or different, and X 6 may be the same or different.
- R 16 , R 18 and R 20 are each independently a hydrocarbon group having 1 to 20 carbon atoms.
- R 17 and R 19 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 16 , R 18 and R 20 is a carbon-carbon triple bond or a carbon-nitrogen triple bond.
- X 10 , X 11 and X 12 each independently represent an oxygen atom or an imino group.
- R 21 , R 24 and R 26 are each independently a hydrocarbon group having 1 to 20 carbon atoms.
- R 22 , R 23 and R 25 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 21 , R 24 and R 26 is a carbon-carbon triple bond or carbon -It has a nitrogen triple bond.
- X 13 , X 14 and X 15 each independently represent an oxygen atom or an imino group.
- R 27 is an m + g-valent group obtained by removing an isocyanate group from a polyisocyanate compound.
- Y is a hydrocarbon group having 1 to 20 carbon atoms, and at least one is a hydrocarbon group having 1 to 20 carbon atoms having a carbon-carbon triple bond or a carbon-nitrogen triple bond. When a plurality of Y are contained in the molecule, Y may be the same or different.
- m is an integer of 1 to 7
- g is an integer of 0 to 6.
- X 16 represents an oxygen atom or an imino group. When a plurality of X 16 are contained in the molecule, each X 16 may be the same or different.
- R 4 in the general formulas (11) to (15) include 2-propynyl group, 3-hexynyl group, 4-hexynyl group, 2-phenyl-2-propynyl group, 3-phenyl-2 -Propynyl group, 2-cyanoethyl group, group represented by general formula (7), group represented by general formula (8), and the like.
- preferable R 5 include straight-chain hydrocarbon groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group), carbon An alicyclic hydrocarbon group having 1 to 10 carbon atoms (for example, a cyclohexyl group and a cyclopentyl group) and an aromatic hydrocarbon group having 6 to 10 carbon atoms (for example, a phenyl group, a methylphenyl group, a benzyl group, and a naphthyl group); Can be mentioned.
- straight-chain hydrocarbon groups having 1 to 10 carbon atoms for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group
- R 7 , R 10 , R 12 , R 14 , R 17 , R 19 , R 22 , R 23 and R 25 include divalent linear hydrocarbon groups having 1 to 20 carbon atoms, carbon Examples thereof include a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
- a residue obtained by removing two isocyanate groups from hexamethylene diisocyanate a residue obtained by removing two isocyanate groups from isophorone diisocyanate, a residue obtained by removing two isocyanate groups from dicyclohexylmethane diisocyanate, and two residues obtained from diphenylmethane diisocyanate.
- a residue excluding an isocyanate group is particularly preferably used.
- R 11 and R 13 include divalent linear hydrocarbon groups having 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
- An aromatic hydrocarbon group is mentioned.
- residues obtained by removing two hydroxyl groups from 2-butyne-1,4-diol and residues obtained by removing two hydroxyl groups from 3-hexyne-1,6-diol are particularly preferred.
- preferable R 5 include groups obtained by removing isocyanate groups from monoisocyanate compounds having 2 to 20 carbon atoms (for example, ethyl isocyanate, butyl isocyanate, octyl isocyanate, dodecyl isocyanate, etc.).
- preferable R 27 include diisocyanate compounds having 4 to 20 carbon atoms (for example, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, etc.) And triisocyanate compounds having 6 to 30 carbon atoms (eg, biuret-modified products of hexamethylene diisocyanate, isocyanurate-modified products of hexamethylene diisocyanate) and groups obtained by removing isocyanate groups from these modified products of polyisocyanate compounds.
- diisocyanate compounds having 4 to 20 carbon atoms for example, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diis
- preferred Y include, for example, methyl group, propyl group, butyl group, cyclohexyl group, 2-propynyl group, 3-hexynyl group, 4-hexynyl group, 2-phenyl-2-propynyl group, 3-phenyl- 2-propynyl group, 2-cyanoethyl group, group represented by general formula (7), group represented by general formula (8), group represented by general formula (9), represented by general formula (10) Group to be used.
- R 4 represents a 2-propynyl group, a 2-cyanoethyl group, a 3-hexynyl group, a 3-phenyl-2-propynyl group, a 2-phenyl-2-propynyl group, Or a group represented by the general formula (8), wherein X 1 is an oxygen atom or an imino group (preferably X 1 is an oxygen atom), and R 5 is a combination of a butyl group or a cyclohexyl group ;
- R 6 and R 8 are each independently a 2-propynyl group, 2-cyanoethyl group, 3-hexynyl group, a group represented by the general formula (9), or the general formula (10).
- R 6 and R 8 are a 2-propynyl group, a 2-cyanoethyl group or a 3-hexynyl group, and R 7 is obtained by removing two isocyanate groups from hexamethylene diisocyanate.
- R 9 and R 15 are a methyl group, 2-propynyl group, 2-cyanoethyl group, 3-hexynyl group, 3-phenyl-2-propynyl group or 2-phenyl-2-propynyl group.
- R 10 , R 12 and R 14 are residues obtained by removing two isocyanate groups from hexamethylene diisocyanate, residues obtained by removing two isocyanate groups from isophorone diisocyanate, or residues obtained by removing two isocyanate groups from dicyclohexylmethane diisocyanate
- R 11 and R 13 are residues obtained by removing two hydroxyl groups from 2-butyne-1,4-diol or residues obtained by removing two hydroxyl groups from 3-hexyne-1,6-diol, and 4 , a compound wherein X 5 , X 6 , X 7 , X 8 and X 9 are a combination of oxygen atoms;
- R 16 and R 20 are a 2-propynyl group, a 2-cyanoethyl group, a 3-hexynyl group, a 3-phenyl-2-propynyl group or a 2-phenyl-2
- R 22 , R 23 and R 25 are residues obtained by removing two isocyanate groups from hexamethylene diisocyanate, residues obtained by removing two isocyanate groups from isophorone diisocyanate, or residues obtained by removing two isocyanate groups from dicyclohexylmethane diisocyanate
- X 13 , X 14 and X 15 are a combination of oxygen atoms, etc .
- R 27 is a residue obtained by removing two isocyanate groups from isophorone diisocyanate or a residue obtained by removing two isocyanate groups from dicyclohexylmethane diisocyanate
- Y is a 2-propynyl group or a 2-cyanoethyl group.
- the compound (A1) in which the atomic group (X) is a group represented by the chemical formula (1) is a compound having an isocyanate group. It can be produced by a method of reacting (T1) with an active hydrogen compound (Z1) containing a triple bond (b).
- the compound (T1) having an isocyanate group a monoisocyanate compound having 2 to 20 carbon atoms (for example, ethyl isocyanate, butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, dodecyl isocyanate, etc.), a diisocyanate compound having 4 to 20 carbon atoms (for example, hexamethylene) Diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, etc.) and triisocyanate compounds having 6 to 30 carbon atoms (for example, biuret-modified products of hexamethylene diisocyanate, isocyanurate-modified products of hexamethylene diisocyanate, Allophanate modification of hexamethylene diiso
- Examples of the active hydrogen compound (Z1) having a triple bond (b) include 2-propyne-1-ol, 2-propyne-1-amine, 3-phenyl-1-propyne-1-amine, and 3-phenyl-2-propyne -1-amine, 3-butyn-2-ol, 4-diethylamino-2-butyn-1-ol, 3-butyn-2-amine, 3-butyn-1-ol, 3-butyn-1-amine, 4 -Pentyn-1-ol, 3-pentyn-1-ol, 5-hexyn-1-ol, 4-hexyn-1-ol, 3-hexyn-1-ol, 2-butyne-1,4-diol, 3 -Hexyne-1,6-diol, 3-hexyne-2,5-diol, 2-propargylpropane-1,3-diol, 2-cyanoethanol, cyanamide and 2-hydroxy-2-phenylacetoni Lil
- the compound (A2) in which the atomic group (X) is a group represented by the chemical formula (2) is acetyl chloride or phosgene. It can be produced by reacting with an active hydrogen compound (Z1) containing a triple bond (b).
- the compound (A3) in which the atomic group (X) is a group represented by the chemical formula (3) is a halogenated alkylsulfone, It can be produced by reacting with an active hydrogen compound (Z1) containing a triple bond (b).
- the compound (A4) in which the atomic group (X) is a group represented by the chemical formula (4) is phosphoryl chloride and triple bond It can manufacture by reacting with the active hydrogen compound (Z1) containing (b).
- the compound (A5) in which the atomic group (X) is a group represented by the chemical formula (5) is represented by the above formula (5). It can manufacture by reacting the compound (T5) which has two or more groups represented by this, and the active hydrogen compound (Z1) containing a triple bond (b).
- Specific examples of the compound (T5) having two or more groups represented by the chemical formula (5) include the diisocyanate compounds having 4 to 20 carbon atoms and the triisocyanate compounds having 6 to 30 carbon atoms.
- the compound (A6) further having an alkyleneoxy group is an alkyleneoxy group when the above (A1) to (A5) are produced.
- an active hydrogen compound (Z1) containing an alkyleneoxy group and a triple bond (b) is used, a compound (A) having an alkyleneoxy group can be obtained.
- Examples of the active hydrogen compound (Z1) containing an alkyleneoxy group and a triple bond (b) include 2- (2- (2-propyne-1-oxy) ethoxy) ethoxy) ethanol, 3- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) propanenitrile and the like.
- an active hydrogen compound not containing the triple bond (b) is used, if necessary, together with the active hydrogen compound (Z1) containing the triple bond (b). May be.
- an alkyleneoxy group may be introduced into the compound (A) by using an active hydrogen compound (Z2) having an alkyleneoxy group and no triple bond.
- the secondary battery additive (B) of the present invention may contain components other than the compound (A), such as vinylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, ethylene sulfite, propylene sulfite, propane sultone and ⁇ . -Bromo- ⁇ -butyrolactone and the like may be contained.
- the content of the compound (A) in the secondary battery additive (B) is preferably 10 to 100% by weight, more preferably 50%, based on the weight of the secondary battery additive (B). ⁇ 100% by weight.
- the compound (A) contained in the secondary battery additive (B) may be one type or two or more types.
- the secondary battery includes electrochemical devices such as a lithium ion battery, a lithium ion capacitor, an electric double layer capacitor, a lead storage battery, a nickel-cadmium battery, and a nickel metal hydride battery.
- the secondary battery additive (B) of the present invention is suitably used as an additive to be added to the electrode, electrolytic solution and the like of such a secondary battery.
- An electrode containing the secondary battery additive of the present invention is also encompassed by the present invention.
- a secondary battery additive (B), an active material (D), a binder (E) and, if necessary, a conductive additive (F) are dispersed in a solvent to obtain a slurry.
- the slurry can be applied on a current collector and the organic solvent dried.
- the secondary battery additive (B), the active material (D), the binder (E), the solvent, and the conductive additive (F) one or more of them can be used.
- the active material (D) may be any material that can be used as an active material for an electrode of a secondary battery, and examples thereof include a negative electrode active material (D1) and a positive electrode active material.
- a negative electrode for a lithium ion battery is obtained by using the negative electrode active material (D1), and a negative electrode for a lithium ion capacitor is obtained by doping lithium into the negative electrode active material (D1).
- the positive electrode active material (D2) for lithium ion batteries and the positive electrode active material (D3) for lithium ion capacitors are mentioned.
- the negative electrode active material (D1) graphite, amorphous carbon, a polymer compound fired body (for example, those obtained by firing and carbonizing a phenol resin, a furan resin, etc.), cokes (for example, pitch coke, needle coke, and petroleum coke), And carbon fibers, conductive polymers (for example, polyacetylene and polypyrrole), tin, silicon, and metal alloys (for example, lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy). .
- Examples of the positive electrode active material (D2) for lithium ion batteries include composite oxides of lithium and transition metals (eg, LiCoO 2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 ), transition metal oxides (eg, MnO 2 and V 2 O). 5 ), transition metal sulfides (eg, MoS 2 and TiS 2 ), and conductive polymers (eg, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole).
- Examples of the positive electrode active material (D3) for the lithium ion capacitor include activated carbon, carbon fiber, and conductive polymer (for example, polyacetylene and polypyrrole).
- binder (E) examples include polymer compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, and polypropylene.
- the conductive auxiliary agent (F) as an optional component includes carbon blacks (for example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black) and metal powder (for example, aluminum powder and nickel powder) ), Conductive metal oxides (for example, zinc oxide and titanium oxide) and the like.
- carbon blacks for example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black
- metal powder for example, aluminum powder and nickel powder
- Conductive metal oxides for example, zinc oxide and titanium oxide
- Examples of the solvent used in preparing the electrode of the present invention include water, N-methylpyrrolidone (1-methyl-2-pyrrolidone), acetone and toluene.
- the content of the active material (D) in the electrode is preferably 70 based on the total weight of the active material (D), the binder (E) and the secondary battery additive (B) from the viewpoint of battery capacity. It is -98 weight%, More preferably, it is 90-98 weight%.
- the content of the binder (E) is preferably 0.00 based on the total weight of the active material (D), the binder (E) and the secondary battery additive (B) from the viewpoint of battery capacity. It is 5 to 29% by weight, and more preferably 1 to 10% by weight.
- the content of the secondary battery additive (B) is selected from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics.
- the active material (D), the binder (E), and the secondary battery additive (B) ) Is preferably 0.01 to 10% by weight, more preferably 0.05 to 1% by weight.
- the content of the conductive additive (F) is preferably 0 to from the viewpoint of battery output, based on the total weight of the active material (D), the binder (E) and the secondary battery additive (B). It is 29% by weight, more preferably 1 to 10% by weight.
- the electrolyte solution containing the secondary battery additive of the present invention is also included in the present invention.
- the electrolytic solution of the present invention preferably contains an additive for secondary batteries (B), an electrolyte (G), and a nonaqueous solvent (H).
- the secondary battery additive (B), the electrolyte (G), and the non-aqueous solvent (H) can be used alone or in combination of two or more.
- the electrolytic solution of the present invention can be obtained, for example, by dissolving the secondary battery additive (B) and the electrolyte (G) in a non-aqueous solvent (H).
- LiPF 6 LiBF 4, LiSbF 6, LiAsF 6
- LiClO 4 lithium salts of inorganic acids LiClO 4, etc.
- LiN (CF 3 Examples include lithium salts of organic acids such as SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 .
- LiPF 6 LiBF 4, LiSbF 6, LiAsF 6
- LiClO 4 lithium salts of inorganic acids
- LiN (CF 3 Examples include lithium salts of organic acids such as SO 2 ) 2 , Li
- non-aqueous solvent those used in ordinary electrolytes can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphoric acid Esters, nitrile compounds, amide compounds, sulfones, sulfolanes, and the like and mixtures thereof can be used.
- cyclic or chain carbonates are preferred from the viewpoint of battery output and charge / discharge cycle characteristics.
- cyclic carbonate include propylene carbonate, ethylene carbonate and butylene carbonate.
- chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
- the content of the secondary battery additive (B) is determined from the viewpoints of charge / discharge cycle characteristics, battery capacity, and high-temperature storage characteristics.
- Secondary battery additive (B), electrolyte (G), and nonaqueous solvent (H) Is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 1% by weight, based on the total weight.
- the content of the electrolyte (G) is preferably based on the total weight of the secondary battery additive (B), the electrolyte (G) and the nonaqueous solvent (H) from the viewpoint of battery output and charge / discharge cycle characteristics. It is 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight.
- the content of the nonaqueous solvent (H) is based on the total weight of the secondary battery additive (B), the electrolyte (G) and the nonaqueous solvent (H) from the viewpoint of battery output and charge / discharge cycle characteristics.
- the amount is preferably 60 to 99% by weight, and more preferably 85 to 95% by weight.
- the electrolytic solution of the present invention may further contain additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer.
- additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer.
- the overcharge inhibitor include biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, aromatic compounds such as cyclohexylbenzene, t-butylbenzene, and t-amylbenzene.
- the amount of the overcharge inhibitor used is usually 0 to 5% by weight, preferably 0.5 to 5%, based on the total weight of the secondary battery additive (B), electrolyte (G) and non-aqueous solvent (H). 3% by weight.
- dehydrating agent examples include zeolite, silica gel and calcium oxide.
- the amount of the dehydrating agent used is usually 0 to 5% by weight, preferably 0.5 to 3% by weight, based on the total weight of the secondary battery additive (B), electrolyte (G) and nonaqueous solvent (H). %.
- the capacity stabilizer examples include fluoroethylene carbonate, succinic anhydride, 1-methyl-2-piperidone, heptane and fluorobenzene.
- the amount of the capacity stabilizer used is usually 0 to 5% by weight, preferably 0.5 to 5% based on the total weight of the secondary battery additive (B), electrolyte (G) and nonaqueous solvent (H). 3% by weight.
- the electrode and the electrolytic solution of the present invention are preferably used for a secondary battery, but are particularly preferably used as an electrode and an electrolytic solution for a lithium ion battery and a lithium ion capacitor.
- Lithium ion batteries having the electrode and / or electrolyte of the present invention are also encompassed by the present invention.
- a lithium ion capacitor having the electrode and / or electrolyte of the present invention is also encompassed by the present invention.
- the lithium ion battery of the present invention is a method of using the electrode of the present invention as a positive electrode or a negative electrode when an electrolyte is injected into a battery can containing a positive electrode, a negative electrode, and a separator to seal the battery can. It can be obtained by the method using the electrolytic solution of the invention and the method using these together.
- separators examples include microporous films made of polyethylene or polypropylene films, multilayer films of porous polyethylene films and polypropylene, non-woven fabrics made of polyester fibers, aramid fibers, glass fibers, and the like, and silica, alumina, titania, etc. on their surfaces. The thing to which ceramic fine particles were made to adhere is mentioned.
- the battery can, metal materials such as stainless steel, iron, aluminum and nickel-plated steel can be used, but plastic materials can also be used depending on the battery application. Further, the battery can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape depending on the application.
- the lithium ion capacitor of the present invention can be obtained by replacing the positive electrode with a positive electrode for a lithium ion capacitor and replacing the battery can with a capacitor can in the basic configuration of the lithium ion battery of the present invention.
- Examples of the material and shape of the capacitor can include the same as those exemplified for the battery can.
- the number average molecular weight of the compound (A-7) was measured using GPC under the following conditions.
- Reference material Tosoh Co., Ltd. standard polystyrene (TSK standard POLY STYRENE) 5 points (Mw 500 1,050 2,800 5,970 9,100)
- Example 2 Synthesis of Compound (A-2) The procedure of Example 1 was repeated except that 3.4 parts of 2-propyne-1-ol was changed to 7.1 parts of 3-hexyn-1-ol. 13.5 parts of the compound (A-2) represented by The compound (A-2) was used as the secondary battery additive (B-2).
- Example 3 Synthesis of Compound (A-3) The procedure of Example 1 was repeated except that 3.4 parts of 2-propyn-1-ol was changed to 4.4 parts of 2-cyanoethanol, and represented by the following chemical formula (19). 10.2 parts of compound (A-3) were obtained. The compound (A-3) was used as the secondary battery additive (B-3).
- Example 4 Synthesis of Compound (A-4) The procedure of Example 1 was repeated except that 3.4 parts of 2-propyne-1-ol was changed to 8.0 parts of 3-phenyl-2-propyne-1-amine. 14.1 parts of the compound (A-4) represented by the chemical formula (20) were obtained. The compound (A-4) was used as an additive (B-4) for a secondary battery.
- Example 5 Synthesis of Compound (A-5) 3.4 parts of 2-propyn-1-ol and 6.5 parts of cyclohexyl isocyanate were added to Duranate (registered trademark) A201H (allophanate-modified hexamethylene diisocyanate) [Asahi Kasei Corporation 2) parts of compound (A-5) represented by the following chemical formula (21) were obtained in the same manner as in Example 1 except that the amount was changed to 22.5 parts. The compound (A-5) was used as an additive (B-5) for a secondary battery.
- Duranate registered trademark
- A201H allophanate-modified hexamethylene diisocyanate
- Example 7 In a flask equipped with a stirrer, thermometer, and condenser, 5.0 parts of 2-butyne-1,4-diol, 11.8 parts of hexamethylene diisocyanate, 200 parts of toluene and bismuth tris (2-ethylhexanoate) 0 .1 part was charged and heated at 80 ° C. for 8 hours. Thereafter, 3 parts of methanol was charged and heated for another 4 hours. Toluene was removed under reduced pressure (1.3 kPa) to obtain 16.2 parts of compound (A-7) represented by the following chemical formula (23). Compound (A-7) was used as an additive for secondary battery (B-7). The number average molecular weight of the compound (A-7) was 1,600. In the formula (23), n was about 4.
- Example 8 Example 1 was repeated except that 3.4 parts of 2-propyne-1-ol was changed to 11.5 parts of 2- (2- (2-propyne-1-oxy) ethoxy) ethoxy) ethanol. 17.3 parts of compound (A-8) represented by the following chemical formula (24) were obtained. The compound (A-8) was used as an additive (B-8) for a secondary battery.
- Example 9 Performed in the same manner as in Example 1 except that 3.4 parts of 2-propyn-1-ol was changed to 12.4 parts of 3- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) propanenitrile. 18.5 parts of the compound (A-9) represented by the chemical formula (25) were obtained. Compound (A-9) was used as an additive (B-9) for secondary batteries.
- Example 10 7.3 parts of cyclohexyl isocyanate was changed to 9.8 parts of hexamethylene diisocyanate, 3.4 parts of 2-propyne-1-ol was changed to 3.3 parts of 2-propyne-1-ol and 7.7 parts of lithium isethionate.
- Example 1 was carried out in the same manner as in Example 1 to obtain 19.2 parts of the compound (A-10) represented by the following chemical formula (26). Compound (A-10) was used as an additive for secondary batteries (B-10).
- Example 11 7.3 parts of cyclohexyl isocyanate to 9.8 parts of hexamethylene diisocyanate, 3.4 parts of 2-propyne-1-ol to 3.3 parts of 2-propyne-1-ol and lithium isethionate prepared in Preparation Example 1 Except having changed to 12.8 parts of ethylene oxide 2-mol adduct, it carried out like Example 1 and obtained 23.5 parts of compounds (A-11) shown by following Chemical formula (27). Compound (A-11) was used as an additive (B-11) for secondary batteries.
- Example 12 In a flask equipped with a stirrer, thermometer and condenser, 11.0 parts of 2- (2- (2- (2-propyne-1-oxy) ethoxy) ethoxy) ethanol, 4.6 parts of acetyl chloride, triethylammonium 5.8 parts and 100 parts of tetrahydrofuran were added and reacted at 60 ° C. for 8 hours. Next, tetrahydrofuran was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 4.6 parts of a compound (A-12) represented by the following chemical formula (28). The compound (A-12) was used as an additive (B-12) for a secondary battery.
- Example 13 To a flask equipped with a stirrer, thermometer and condenser, 11.0 parts of 2- (2- (2-propyne-1-oxy) ethoxy) ethoxy) ethanol, 10.7 parts of 2-bromoethylmethylsulfone Part, 2.3 parts of sodium hydroxide and 100 parts of tetrahydrofuran were added and reacted at 60 ° C. for 8 hours. Next, tetrahydrofuran was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 8.6 parts of a compound (A-13) represented by the following chemical formula (29). Compound (A-13) was used as the secondary battery additive (B-13).
- Example 14 In a flask equipped with a stirrer, thermometer and condenser, 11.0 parts of 2- (2- (2- (2-propyne-1-oxy) ethoxy) ethoxy) ethanol, 2.9 parts of phosphoryl chloride, triethylamine 5 8 parts and 100 parts of tetrahydrofuran were added and reacted at 60 ° C. for 8 hours. Next, tetrahydrofuran was removed under reduced pressure, and purification was performed by silica gel column chromatography to obtain 4.5 parts of a compound (A-14) represented by the following chemical formula (30). The compound (A-14) was used as an additive (B-14) for a secondary battery.
- Example 15 To a flask equipped with a stirrer, thermometer and condenser, 13.0 parts of isophorone diisocyanate, 4.1 parts of 2-cyanoethanol, 0.1 part of dibutyltin laurate and 100 parts of toluene were added and reacted at 80 ° C. for 6 hours. . Next, toluene was removed under reduced pressure to obtain 17.0 parts of a compound (A-15) represented by the following chemical formula (31). Compound (A-15) was used as an additive for secondary battery (B-15). The compound (A-15) has a group represented by the chemical formula (1) and a group represented by the chemical formula (5).
- Example 16 In a flask equipped with a stirrer, thermometer and condenser, 9.8 parts of hexamethylene diisocyanate, 3.3 parts of 2-propyn-1-ol, 14.7 parts of an EO5 molar adduct of methanol, 0.1% of dibutyltin laurate And 100 parts of toluene were added and reacted at 80 ° C. for 6 hours. Next, toluene was removed under reduced pressure to obtain 17.0 parts of a compound (A-16) represented by the following chemical formula (32). The compound (A-16) was used as an additive (B-16) for a secondary battery.
- Tributyl phosphate was used as a comparative compound (A′-5) and a comparative additive (B′-5).
- Table 1 summarizes the secondary battery additive (B) of the example and the comparative additive (B ') of the comparative example.
- pre-proliferative / absence of alkyleneoxy group and “presence / absence of group represented by general formula (10)”, “ ⁇ ” is indicated when the compound has these groups, and “ ⁇ ” is indicated when the compound does not exist. Shown respectively.
- Examples 17 to 33 and Comparative Examples 7 to 13 Evaluation of Lithium Ion Battery and Electrode
- a lithium ion battery electrode containing the above secondary battery additive (B) or comparative additive (B ′) in the number of parts shown in Table 2 was prepared by the following method. Using the electrode, a lithium ion battery was produced by the following method. Table 2 shows the results of evaluating the high voltage charge / discharge cycle characteristics, output characteristics, and gas generation characteristics of the manufactured lithium ion batteries by the following method.
- the obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 ⁇ m using a wire bar in the air, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. After drying for 2 hours and punching out to 15.95 mm ⁇ , positive electrodes for lithium ion batteries of Examples 17 to 33 and Comparative Examples 7 to 13 were produced.
- Capacity maintenance rate during 1 C discharge (%) (1 C discharge capacity / 0.1 C discharge capacity) ⁇ 100 Tables 2 and 3 show the capacity retention rate (%) during 1 C discharge as output characteristics (%).
- the lithium ion battery was charged to a voltage of 4.5 V with a current of 0.1 C, and after a pause of 10 minutes, 0.1 C of The cycle of discharging to a voltage of 3.5 V with current was repeated three times. Further, the battery was charged to a voltage of 4.5 V with a current of 0.1 C, and stored at 60 ° C. for 7 days while maintaining the voltage. Thereafter, the cell thickness was measured (thickness after measurement).
- the thickness increase rate gas generation characteristics
- Thickness increase rate (%) (Thickness after measurement / Initial thickness) ⁇ 100
- a slurry was obtained by thoroughly mixing 92.5 parts of graphite powder having an average particle size of about 8 to 12 ⁇ m, 7.5 parts of polyvinylidene fluoride and 200 parts of 1-methyl-2-pyrrolidone in a mortar. The obtained slurry was applied to one side of a 20 ⁇ m-thick copper foil in the air using a wire bar, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. for 2 hours. It was dried, punched to 16.15 mm ⁇ , and made 3 ⁇ m thick with a press machine to produce a graphite-based negative electrode for lithium ion batteries.
- the positive electrode and the negative electrode were arranged at both ends in a 2032 type coin cell so that the respective coated surfaces face each other, and a separator (polypropylene nonwoven fabric) was inserted between the electrodes to produce a lithium ion battery cell.
- the electrolytes of Examples 34 to 48 and Comparative Examples 14 to 20 were poured into the prepared lithium ion battery cells and sealed to prepare secondary batteries (lithium ion batteries).
- Thickness increase rate (Thickness after measurement / Initial thickness) ⁇ 100-100
- the obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 ⁇ m using a wire bar in the air, dried at 80 ° C. for 1 hour, and further under reduced pressure (1.3 kPa) at 80 ° C. It was dried for 2 hours and punched out to 15.95 mm ⁇ to produce a positive electrode for a lithium ion capacitor.
- the obtained electrode and lithium metal foil are sandwiched between separators (polypropylene nonwoven fabric) and set in a beaker cell, and about 75% of the negative electrode theoretical capacity of lithium ions is occluded in the negative electrode over about 10 hours.
- a negative electrode was prepared.
- a positive electrode and a negative electrode of Examples 49 to 65 and Comparative Examples 21 to 27 are arranged in a storage case made of polypropylene aluminum laminate film so that the coated surfaces face each other, and a separator (polypropylene nonwoven fabric) is placed between the electrodes.
- the capacitor cell was prepared by inserting.
- a lithium ion capacitor was manufactured by injecting and sealing a cell prepared with an electrolytic solution in which LiPF 6 was dissolved in propylene carbonate (PC) at a ratio of 12% by weight.
- PC propylene carbonate
- Capacity maintenance rate during 10C discharge (%) (10C discharge capacity / 1C discharge capacity) ⁇ 100 Tables 4 and 5 show the capacity retention rate (%) during 10 C discharge as output characteristics (%).
- the thickness of the laminate cell (lithium ion capacitor) produced by the above method was measured (initial thickness).
- the lithium ion capacitor is charged to a voltage of 3.8 V with a current of 1 C, and after a pause of 10 minutes, a voltage of 2
- the battery was discharged to 0 V and the capacity was measured (initial battery capacity).
- the battery was further charged to a voltage of 3.8 V with a current of 1 C, and stored at 60 ° C. for 7 days while maintaining the voltage. Thereafter, the cell thickness was measured (thickness after measurement).
- the positive electrode active material activated carbon having a specific surface area of about 2200 m 2 / g obtained by an alkali activation method was used. Activated carbon powder, acetylene black, and polyvinylidene fluoride are mixed in a weight ratio of 80:10:10, and this mixture is added to 1-methyl-2-pyrrolidone as a solvent and mixed by stirring. To obtain a slurry. This slurry was applied onto an aluminum foil having a thickness of 30 ⁇ m by a doctor blade method, temporarily dried, and then cut so that the electrode size was 20 mm ⁇ 30 mm. The electrode thickness was about 50 ⁇ m. Before assembling the cell, the electrode was dried in a vacuum at 120 ° C. for 10 hours to produce a positive electrode for a lithium ion capacitor.
- the obtained electrode and lithium metal foil are sandwiched between separators (polypropylene nonwoven fabric) and set in a beaker cell, and about 75% of the negative electrode theoretical capacity of lithium ions is occluded in the negative electrode over about 10 hours.
- a negative electrode was prepared.
- a separator polypropylene nonwoven fabric
- a separator is inserted between the positive electrode and the negative electrode, impregnated with the electrolytes of Examples 66 to 80 and Comparative Examples 28 to 34, and placed in a storage case made of a polypropylene aluminum laminate film. Sealed to produce a lithium ion capacitor cell.
- the positive electrode is placed in an LVC pan (pressure pan) under an argon atmosphere, 12 wt% of LiPF 6 in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1).
- EC ethylene carbonate
- DEC diethyl carbonate
- About 2 mg of the electrolytic solution dissolved at a rate of% was put to prepare a measurement sample.
- DSC differential scanning calorimeter
- the temperature was raised from 25 ° C. to 320 ° C. at a rate of 5 ° C./min, and the calorific value and the exothermic peak temperature were measured.
- the lithium ion battery and lithium ion capacitor produced using the additive for secondary battery (B) of the present invention are excellent in charge / discharge cycle performance and gas generation characteristics from the results of the above Examples and Comparative Examples, and further suppress the heat generation. It was found that it also has.
- the reason why the charge / discharge cycle performance is improved is considered to be that an atomic group having an electronegativity of 3 or more is adsorbed on the surface of the active material and suppresses the decomposition reaction of the electrolyte. Moreover, it is considered that the cause of the effective suppression of gas generation is that the triple bond reacted with the active material.
- the compounds having the group represented by the chemical formula (2) or the alkyleneoxy group (d) in the molecule showed particularly excellent effects in output characteristics. . This is considered because these additives have high lithium ion conductivity. Although the detailed mechanism of the heat generation suppression effect is unknown, it is thought that the additive adsorbed on the positive electrode surface suppressed the action of oxygen released from the active material surface at high temperatures.
- the electrode and electrolyte using the secondary battery additive (B) of the present invention are useful for electrochemical devices such as lithium ion batteries and thium ion capacitors, and particularly for lithium ion batteries and lithium ion capacitors for electric vehicles. Is preferred. Moreover, it is applicable also to electrochemical devices (electric double layer capacitor, nickel metal hydride battery, nickel cadmium battery, air battery, alkaline battery, etc.) other than those disclosed in the present invention.
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Abstract
Description
本発明はこれらの課題を鑑みてなされたものである。
すなわち本発明の解決しようとする課題は、非水電解液二次電池のガス発生を抑制し、かつ充放電のサイクル特性と出力特性を改善することである。
本発明の二次電池用添加剤(B)は、3~5個の原子で構成され、電気陰性度が3以上である原子を2~4個有し、少なくとも1個の二重結合を有する原子団(X)及び三重結合(b)を有する化合物(A)を含有する。
化合物(A)は、1分子中に原子団(X)を2以上有していてもよい。化合物(A)が1分子中に原子団(X)を2以上有する場合、それらは全て同じであってもよく、異なっていてもよい。
また、化合物(A)は、1分子中に三重結合(b)を2以上有していてもよい。化合物(A)が1分子中に三重結合(b)を2以上有する場合、それらは全て同じであってもよく、異なっていてもよい。化合物(A)1分子が有する三重結合(b)は、1~4個が好ましく、1~3個がより好ましい。
原子団(X)を構成する原子としては、典型元素が挙げられ、電池特性の観点から、水素原子、炭素原子、酸素原子、窒素原子、フッ素原子、硫黄原子、リン原子及び塩素原子が好ましく、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子及びリン原子がより好ましく、水素原子、炭素原子、酸素原子及び窒素原子が更に好ましい。原子団(X)を構成する原子は、1種であってもよく、2種以上であってもよい。
非水電解液二次電池に用いられる活物質には酸素原子等の極性の高い原子が含まれているため、電子が偏って存在している部分が存在する。本発明の二次電池用添加剤(B)に含まれる化合物(A)が有する電気陰性度の大きい原子(電気陰性度が3以上の原子)と活物質の電子が偏った部分とが相互作用することで本発明の二次電池用添加剤(B)が活物質へ吸着することによって高いガス発生抑制効果等が発現すると考えられる。
アミド基はカルボキシルキ基とアミノ基との脱水縮合反応により生成することができ、ウレタン基はイソシアネート基と水酸基との付加反応により生成することができ、ウレア基はイソシアネート基と水との反応及びイソシアネート基とアミノ基又はイミノ基との反応によって生成することができ、アロファネート基はウレタン基に更にイソシアネート基が付加反応することで生成することができ、ビウレット基はウレア基に更にイソシアネート基が付加反応することで生成することができる。
化学式(1)~(5)で表される各基は、例えば上記の反応により、化合物(A)に導入することができる。
炭素数1~12の有機基としては、炭素数1~12の脂肪族炭化水素基(メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、1-メチルプロピル基、イソブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、1-メチルブチル基、2-メチルブチル基、1,1-ジメチルプロピル基、2,2-ジメチルプロピル基、1,2-ジメチルプロピル基、1-エチルプロピル基、n-ヘキシル基、イソヘキシル基、3-メチルペンチル基、2-メチルペンチル基、1-メチルペンチル基、1,1-ジメチルブチル基、2,2-ジメチルブチル基、1,1,2-トリメチルプロピル基、1-エチル-1-メチルプロピル基、ヘプチル基、オクチル基、イソオクチル基、2-エチルヘキシル基、ノニル基、デシル基及びドデシル基等)、炭素数1~12の脂環式炭化水素基(シクロヘキシル基及びシクロペンチル基等)、炭素数6~12の芳香族炭化水素基(ベンジル基、フェニル基、メチルフェニル基、ビフェニル基及びナフチル基等)及びこれらの水素原子がヘテロ原子を含む官能基(アミノ基、アルキルアミノ基、ジアルキルアミノ基及びアルキルチオ基等)により置換された基等が挙げられる。
これらのうち、電池出力特性の観点から、Rとしては水素原子及び炭素数1~12の脂肪族炭化水素基が好ましく、水素原子が更に好ましい。
アルキレンオキシ基(d)は1個のアルキレンオキシ基で構成されていても、2個以上のアルキレンオキシ基が連続して結合して構成されていてもよく、電池出力特性の観点から、1個のアルキレンオキシ基又は2~40個のアルキレンオキシ基が連続して結合して構成されていることが好ましく、3~30個のアルキレンオキシ基が連続して結合して構成されていることが更に好ましい。
2個以上のアルキレンオキシ基が連続して結合している場合、結合しているアルキレンオキシ基は1種であっても、2種以上であってもよい。2種以上のアルキレンオキシ基が連続して結合している場合の結合様式は、ランダム、ブロック又はその混合のいずれであってもよい。
hは1~40の整数であり、好ましくは3~30、更に好ましくは5~20である。
P2は炭素数1~10の2価の炭化水素基であり、P2としては前記のR2と同じものが挙げられ、好ましいものも同じである。
iは1~40の整数であり、好ましくは3~30、更に好ましくは5~20である。
Q2は炭素数1~10の2価の炭化水素基である。Q2としては前記のR2と同じものが挙げられ、好ましいものも同じである。
Mは1価の金属イオンであり、リチウムイオン、ナトリウムイオン及びカリウムイオン等のアルカリ金属イオン等が挙げられる。これらのうち、電池出力特性等の観点から、リチウムイオン及びナトリウムイオンが好ましい。
Aは-CO2 -又は-SO3 -であり、電池出力特性の観点から-SO3 -が好ましい。
jは0~40の整数であり、出力特性の観点から3~30が好ましく、5~20が特に好ましい。mは0又は1であり、好ましくは1である。
一般式(11)~(15)中、R6、R8、R9、R15、R16、R18、R20、R21、R24及びR26として好ましいものの具体例としては、メチル基、プロピル基、ブチル基、シクロヘキシル基、2-プロピニル基、3-ヘキシニル基、4-ヘキシニル基、2-フェニル-2-プロピニル基、3-フェニル-2-プロピニル基、2-シアノエチル基、一般式(7)で表される基、一般式(8)で表される基、一般式(9)で表される基、一般式(10)で表される基等が挙げられる。R5として好ましいものの具体例としては、炭素数1~10の直鎖炭化水素基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基)、炭素数1~10の脂環式炭化水素基(例えば、シクロヘキシル基及びシクロペンチル基)及び炭素数6~10の芳香族炭化水素基(例えば、フェニル基、メチルフェニル基、ベンジル基及びナフチル基等)が挙げられる。
Yの好ましいものの具体例として、例えば、メチル基、プロピル基、ブチル基、シクロヘキシル基、2-プロピニル基、3-ヘキシニル基、4-ヘキシニル基、2-フェニル-2-プロピニル基、3-フェニル-2-プロピニル基、2-シアノエチル基、一般式(7)で表される基、一般式(8)で表される基、一般式(9)で表される基、一般式(10)で表される基が挙げられる。
一般式(11)において、R4が2-プロピニル基、2-シアノエチル基、3-ヘキシニル基、3-フェニル-2-プロピニル基、2-フェニル-2-プロピニル基、上記一般式(7)で表される又は一般式(8)で表される基であり、X1が酸素原子又はイミノ基(好ましくはX1は酸素原子)であり、R5がブチル基又はシクロヘキシル基の組み合わせである化合物;
一般式(12)において、R6及びR8が、それぞれ独立して2-プロピニル基、2-シアノエチル基、3-ヘキシニル基、一般式(9)で表される基又は一般式(10)で表される基であり、かつR6及びR8のうち少なくとも1つは2-プロピニル基、2-シアノエチル基又は3-ヘキシニル基であり、R7がヘキサメチレンジイソシアネートから2つのイソシアネート基を除いた残基、イソホロンジイソシアネートから2つのイソシアネート基を除いた残基又はジシクロヘキシルメタンジイソシアネートから2つのイソシアネート基を除いた残基であり、X2及びX3が酸素原子の組み合わせである化合物;
一般式(13)において、R9及びR15がメチル基、2-プロピニル基、2-シアノエチル基、3-ヘキシニル基、3-フェニル-2-プロピニル基又は2-フェニル-2-プロピニル基であり、R10、R12及びR14がヘキサメチレンジイソシアネートから2つのイソシアネート基を除いた残基、イソホロンジイソシアネートから2つのイソシアネート基を除いた残基又はジシクロヘキシルメタンジイソシアネートから2つのイソシアネート基を除いた残基であり、R11及びR13が2-ブチン-1,4-ジオールから2つの水酸基を除いた残基又は3-ヘキシン-1,6-ジオールから2つの水酸基を除いた残基であり、X4、X5、X6、X7、X8及びX9が酸素原子の組み合わせである化合物;
一般式(14)において、R16及びR20が2-プロピニル基、2-シアノエチル基、3-ヘキシニル基、3-フェニル-2-プロピニル基又は2-フェニル-2-プロピニル基であり、R18がプロピル基(好ましくはイソプロピル基)、2-プロピニル基、2-シアノエチル基、3-ヘキシニル基、3-フェニル-2-プロピニル基又は2-フェニル-2-プロピニル基であり、R17及びR19がヘキサメチレンジイソシアネートから2つのイソシアネート基を除いた残基、イソホロンジイソシアネートから2つのイソシアネート基を除いた残基又はジシクロヘキシルメタンジイソシアネートから2つのイソシアネート基を除いた残基であり、X10、X11及びX12が酸素原子の組み合わせである化合物;
一般式(15)において、R21、R24及びR26が2-プロピニル基、3-ヘキシニル基、2-シアノエチル基、3-フェニル-2-プロピニル基又は2-フェニル-2-プロピニル基であり、R22、R23及びR25がヘキサメチレンジイソシアネートから2つのイソシアネート基を除いた残基、イソホロンジイソシアネートから2つのイソシアネート基を除いた残基又はジシクロヘキシルメタンジイソシアネートから2つのイソシアネート基を除いた残基であり、X13、X14及びX15が酸素原子の組み合わせである化合物等;
一般式(16)において、R27がイソホロンジイソシアネートから2つのイソシアネート基を除いた残基又はジシクロヘキシルメタンジイソシアネートから2つのイソシアネート基を除いた残基であり、Yが2-プロピニル基又は2-シアノエチル基であり、X16が酸素原子であり、gが0~1であり、mが1~2の組み合わせである化合物等。
上記化学式(5)で表される基を2つ以上有する化合物(T5)の具体例としては前記の炭素数4~20のジイソシアネート化合物及び炭素数6~30のトリイソシアネート化合物等が挙げられる。
二次電池用添加剤(B)中における化合物(A)の含有量は、二次電池用添加剤(B)の重量を基準として、10~100重量%であることが好ましく、更に好ましくは50~100重量%である。二次電池用添加剤(B)に含まれる化合物(A)は1種であってもよく、2種以上であってもよい。
負極活物質(D1)としては、黒鉛、アモルファス炭素、高分子化合物焼成体(例えばフェノール樹脂及びフラン樹脂等を焼成し炭素化したもの)、コークス類(例えばピッチコークス、ニードルコークス及び石油コークス)、炭素繊維、導電性高分子(例えばポリアセチレン及びポリピロール)、スズ、シリコン、及び金属合金(例えばリチウム-スズ合金、リチウム-シリコン合金、リチウム-アルミニウム合金及びリチウム-アルミニウム-マンガン合金等)等が挙げられる。
リチウムイオン電池用正極活物質(D2)としてはリチウムと遷移金属との複合酸化物(例えばLiCoO2、LiNiO2、LiMnO2及びLiMn2O4)、遷移金属酸化物(例えばMnO2及びV2O5)、遷移金属硫化物(例えばMoS2及びTiS2)、及び導電性高分子(例えばポリアニリン、ポリフッ化ビニリデン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリ-p-フェニレン及びポリカルバゾール)等が挙げられる。
リチウムイオンキャパシタ用正極活物質(D3)としては活性炭、炭素繊維及び導電性高分子(例えばポリアセチレン及びポリピロール)等が挙げられる。
結着剤(E)の含有量は、電池容量の観点から、活物質(D)、結着剤(E)及び二次電池用添加剤(B)の合計重量に基づいて、好ましくは0.5~29重量%であり、更に好ましくは1~10重量%である。
二次電池用添加剤(B)の含有量は、充放電サイクル特性、電池容量及び高温貯蔵特性の観点から、活物質(D)、結着剤(E)及び二次電池用添加剤(B)の合計重量に基づいて、好ましくは0.01~10重量%、更に好ましくは0.05~1重量%である。
導電助剤(F)の含有量は、電池出力の観点から、活物質(D)、結着剤(E)及び二次電池用添加剤(B)の合計重量に基づいて、好ましくは0~29重量%であり、更に好ましくは1~10重量%である。
本発明の電解液は、例えば、二次電池用添加剤(B)及び電解質(G)を非水溶媒(H)に溶解させることにより得ることができる。
環状炭酸エステルとしては、プロピレンカーボネート、エチレンカーボネート及びブチレンカーボネート等が挙げられる。
鎖状炭酸エステルとしては、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、メチル-n-プロピルカーボネート、エチル-n-プロピルカーボネート及びジ-n-プロピルカーボネート等が挙げられる。
電解質(G)の含有量は、電池出力及び充放電サイクル特性の観点から、二次電池用添加剤(B)、電解質(G)及び非水溶媒(H)の合計重量に基づいて、好ましくは0.1~30重量%であり、更に好ましくは0.5~20重量%である。
非水溶媒(H)の含有量は、電池出力及び充放電サイクル特性の観点から、二次電池用添加剤(B)、電解質(G)及び非水溶媒(H)の合計重量に基づいて、好ましくは60~99重量%であり、更に好ましくは85~95重量%である。
過充電防止剤としては、ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、t-ブチルベンゼン及びt-アミルベンゼン等の芳香族化合物等が挙げられる。過充電防止剤の使用量は、二次電池用添加剤(B)、電解質(G)及び非水溶媒(H)の合計重量に基づいて、通常0~5重量%、好ましくは0.5~3重量%である。
本発明の電極及び/又は電解液を有するリチウムイオン電池も本発明に包含される。本発明の電極及び/又は電解液を有するリチウムイオンキャパシタも本発明に包含される。
装置(一例) : 東ソー(株)製 HLC-8120
カラム(一例): TSK GEL GMH6 2本 〔東ソー(株)製〕
測定温度 : 40℃
試料溶液 : 0.25重量%のTHF溶液
溶液注入量 : 100μL
検出装置 : 屈折率検出器
基準物質 : 東ソー(株)製 標準ポリスチレン(TSKstandard POLY STYRENE)5点(Mw 500 1,050 2,800 5,970 9,100)
温度計、加熱冷却装置、撹拌機及び滴下ボンベを備えた耐圧反応容器に、イセチオン酸リチウム132部及び水酸化カリウム1.3部を投入し、窒素置換後密閉し100℃に昇温した後、0.5kPaまで減圧し1時間攪拌した。ついで150℃まで昇温し、圧力が0.5MPaG(ゲージ圧)以下になるように調整しながらエチレンオキサイド88部を5時間かけて滴下後同温度で3時間熟成し、イセチオン酸リチウムのエチレンオキサイド2モル付加物を得た。
化合物(A-1)の合成
撹拌機、温度計及び冷却管を取り付けたフラスコに、2-プロピン-1-オール3.4部、シクロヘキシルイソシアネート7.3部、トルエン200部及びトリス(2-エチルヘキサン酸)ビスマス0.1部を仕込み80℃で8時間加熱した。トルエンを減圧(1.3kPa)下に除去し、下記化学式(17)で示される化合物(A-1)10.1部を得た。化合物(A-1)を二次電池用添加剤(B-1)とした。
化合物(A-2)の合成
2-プロピン-1-オール3.4部を3-ヘキシン-1-オール7.1部に変更したこと以外は実施例1と同様にして行い下記化学式(18)で示される化合物(A-2)13.5部を得た。化合物(A-2)を二次電池用添加剤(B-2)とした。
化合物(A-3)の合成
2-プロピン-1-オール3.4部を2-シアノエタノール4.4部に変更したこと以外は実施例1と同様にして行い下記化学式(19)で示される化合物(A-3)10.2部を得た。化合物(A-3)を二次電池用添加剤(B-3)とした。
化合物(A-4)の合成
2-プロピン-1-オール3.4部を3-フェニル-2-プロピン-1-アミン8.0部に変更したこと以外は実施例1と同様にして行い下記化学式(20)で示される化合物(A-4)14.1部を得た。化合物(A-4)を二次電池用添加剤(B-4)とした。
化合物(A-5)の合成
2-プロピン-1-オール3.4部を6.5部に、シクロヘキシルイソシアネート7.3部をデュラネート(登録商標)A201H(アロファネート変性ヘキサメチレンジイソシアネート)[旭化成(株)製]22.5部に変更したこと以外は実施例1と同様にして行い下記化学式(21)で示される化合物(A-5)25.7部を得た。化合物(A-5)を二次電池用添加剤(B-5)とした。
化合物(A-6)の合成
2-プロピン-1-オール3.4部を9.8部に、シクロヘキシルイソシアネート7.3部をデュラネート24A-100(ビウレット変性ヘキサメチレンジイソシアネート)[旭化成(株)製]29.4部に変更したこと以外は実施例1と同様にして行い下記化学式(22)で示される化合物(A-6)37.1部を得た。化合物(A-6)を二次電池用添加剤(B-6)とした。
撹拌機、温度計及び冷却管を取り付けたフラスコに、2-ブチン-1,4-ジオール5.0部、ヘキサメチレンジイソシアネート11.8部、トルエン200部及びトリス(2-エチルヘキサン酸)ビスマス0.1部を仕込み80℃で8時間加熱した。その後メタノール3部を仕込み更に4時間加熱した。トルエンを減圧(1.3kPa)下に除去し、下記化学式(23)で示される化合物(A-7)16.2部を得た。化合物(A-7)を二次電池用添加剤(B-7)とした。化合物(A-7)の数平均分子量は1,600であった。式(23)中、nは4程度であった。
2-プロピン-1-オール3.4部を2-(2-(2-(2-プロピン-1-オキシ)エトキシ)エトキシ)エタノール11.5部に変更した以外は実施例1と同様にして行い下記化学式(24)で示される化合物(A-8)17.3部を得た。化合物(A-8)を二次電池用添加剤(B-8)とした。
2-プロピン-1-オール3.4部を3-(2-(2-(2-ヒドロキシエトキシ)エトキシ)エトキシ)プロパンニトリル12.4部に変更した以外は実施例1と同様にして行い下記化学式(25)で示される化合物(A-9)18.5部を得た。化合物(A-9)を二次電池用添加剤(B-9)とした。
シクロヘキシルイソシアネート7.3部をヘキサメチレンジイソシアネート9.8部に、2-プロピン-1-オール3.4部を2-プロピン-1-オール3.3部及びイセチオン酸リチウム7.7部に変更した以外は実施例1と同様にして行い下記化学式(26)で示される化合物(A-10)19.2部を得た。化合物(A-10)を二次電池用添加剤(B-10)とした。
シクロヘキシルイソシアネート7.3部をヘキサメチレンジイソシアネート9.8部に、2-プロピン-1-オール3.4部を2-プロピン-1-オール3.3部及び製造例1で製造したイセチオン酸リチウムのエチレンオキサイド2モル付加物12.8部に変更した以外は実施例1と同様にして行い下記化学式(27)で示される化合物(A-11)23.5部を得た。化合物(A-11)を二次電池用添加剤(B-11)とした。
撹拌機、温度計及び冷却管を取り付けたフラスコに、2-(2-(2-(2-プロピン-1-オキシ)エトキシ)エトキシ)エタノール11.0部、塩化アセチル4.6部、トリエチルアンモニウム5.8部及びテトラヒドロフラン100部を加え、60℃で8時間反応させた。次にテトラヒドロフランを減圧下で除き、シリカゲルカラムクロマトグラフィーで精製することにより、下記化学式(28)で示される化合物(A-12)4.6部を得た。化合物(A-12)を二次電池用添加剤(B-12)とした。
撹拌機、温度計及び冷却管を取り付けたフラスコに、2-(2-(2-(2-プロピン-1-オキシ)エトキシ)エトキシ)エタノール11.0部、2-ブロモエチルメチルスルホン10.7部、水酸化ナトリウム2.3部及びテトラヒドロフラン100部を加え、60℃で8時間反応させた。次にテトラヒドロフランを減圧下で除き、シリカゲルカラムクロマトグラフィーで精製することにより、下記化学式(29)で示される化合物(A-13)8.6部を得た。化合物(A-13)を二次電池用添加剤(B-13)とした。
撹拌機、温度計及び冷却管を取り付けたフラスコに、2-(2-(2-(2-プロピン-1-オキシ)エトキシ)エトキシ)エタノール11.0部、塩化ホスホリル2.9部、トリエチルアミン5.8部及びテトラヒドロフラン100部を加え、60℃で8時間反応させた。次にテトラヒドロフランを減圧下で除き、シリカゲルカラムクロマトグラフィーで精製することにより、下記化学式(30)で示される化合物(A-14)4.5部を得た。化合物(A-14)を二次電池用添加剤(B-14)とした。
撹拌機、温度計及び冷却管を取り付けたフラスコにイソホロンジイソシアネート13.0部、2-シアノエタノール4.1部、ジブチルスズラウリレート0.1部及びトルエン100部を加え80℃で6時間反応させた。次にトルエンを減圧下で除き、下記化学式(31)で示される化合物(A-15)17.0部を得た。化合物(A-15)を二次電池用添加剤(B-15)とした。化合物(A-15)は、上記化学式(1)で表される基及び化学式(5)で表される基を有する。
撹拌機、温度計及び冷却管を取り付けたフラスコにヘキサメチレンジイソシアネート9.8部、2-プロピン-1-オール3.3部、メタノールのEO5モル付加物14.7部、ジブチルスズラウリレート0.1部及びトルエン100部を加え80℃で6時間反応させた。次にトルエンを減圧下で除き、下記化学式(32)で示される化合物(A-16)17.0部を得た。化合物(A-16)を二次電池用添加剤(B-16)とした。
比較用化合物(A’-1)の合成
2-プロピン-1-オール3.4部をブタノール4.5部に変更したこと以外は実施例1と同様にして行い下記化学式(33)で示される化合物(A’-1)11.1部を得た。化合物(A’-1)を比較用添加剤(B’-1)とした。
1,9-デカジインを比較用化合物(A’-2)とし、比較用添加剤(B’-2)とした。
酢酸エチルを比較用化合物(A’-3)とし、比較用添加剤(B’-3)とした。
ジメチルスルホキシドを比較用化合物(A’-4)とし、比較用添加剤(B’-4)とした。
リン酸トリブチルを比較用化合物(A’-5)とし、比較用添加剤(B’-5)とした。
ヘキサメチレンジイソシアネートを比較用化合物(A’-6)とし、比較用添加剤(B’-6)とした。
リチウムイオン電池及び電極の評価
上記二次電池用添加剤(B)又は比較用添加剤(B’)を表2に示した配合部数で含有するリチウムイオン電池用電極を下記の方法で作製し、該電極を使用して下記の方法でリチウムイオン電池を作製した。
作製したリチウムイオン電池について、以下の方法で高電圧充放電サイクル特性、出力特性及びガス発生特性を評価した結果を表2に示した。
LiCoO2粉末90.0部、ケチェンブラック[シグマアルドリッチ(株)製]5部、ポリフッ化ビニリデン[シグマアルドリッチ(株)製]5部及び表2に示した部数の二次電池用添加剤(B)又は比較用添加剤(B’)を乳鉢で充分に混合した後、1-メチル-2-ピロリドン[東京化成工業(株)製]70.0部を添加し、更に乳鉢で充分に混合してスラリーを得た。得られたスラリーを、大気中でワイヤーバーを用いて厚さ20μmのアルミニウム電解箔上の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、15.95mmφに打ち抜き、実施例17~33及び比較例7~13のリチウムイオン電池用正極を作製した。
平均粒子径約8~12μmの黒鉛粉末92.5部、ポリフッ化ビニリデン7.5部、1-メチル-2-ピロリドン[東京化成工業(株)製]200部及び表2に示した部数の二次電池用添加剤(B)を乳鉢で充分に混合しスラリーを得た。得られたスラリーを、大気中でワイヤーバーを用いて厚さ20μmの銅箔の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、16.15mmφに打ち抜き、プレス機で厚さ3μmにして実施例17~33及び比較例7~13のリチウムイオン電池用負極を作製した。
2032型コインセル内の両端に、実施例17~33及び比較例7~13の正極及び負極をそれぞれの塗布面が向き合うように配置して、電極間にセパレータ(ポリプロピレン製不織布)を挿入し、リチウムイオン電池用セルを作製した。エチレンカーボネート(EC)とジエチルカーボネート(DEC)との混合溶媒(体積比率1:1)に、LiPF6を12重量%の割合で溶解させた電解液を作製したセルに注液密封した。以下の方法で高電圧充放電サイクル特性を評価した結果を表2に示した。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、得られたリチウムイオン電池を0.1Cの電流で電圧4.5Vまで充電し、10分間の休止後、0.1Cの電流で電池電圧を3.5Vまで放電し、この充放電を繰り返した。このときの初回充電時の電池容量と50サイクル目充電時の電池容量を測定し、下記式から充放電サイクル特性を算出した。数値が大きい程、充放電サイクル特性が良好であることを示す。
高電圧充放電サイクル特性(%)=(50サイクル目充電時の電池容量/初回充電時の電池容量)×100
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオン電池を0.1Cの電流で電圧4.5Vまで充電し、10分間の休止後、0.1Cの電流で電圧を3.5Vまで放電し、放電容量(以下0.1C放電容量と記載)を測定した。次に0.1Cの電流で電圧4.5Vまで充電し、10分間の休止後、1Cの電流で電圧を3.5Vまで放電し容量(以下1C放電容量と記載)を測定し、下記式から1C放電時の容量維持率を算出した。数値が大きい程、出力特性が良好であることを示す。
1C放電時の容量維持率(%)=(1C放電容量/0.1C放電容量)×100
1C放電時の容量維持率(%)を、出力特性(%)として表2及び3に示した。
実施例17~33及び比較例7~13の正極及び負極をラミネートセル中にそれぞれの塗布面が向き合うように配置して、エチレンカーボネート(EC)とジエチルカーボネート(DEC)との混合溶媒(体積比率1:1)に、LiPF6を12重量%の割合で溶解させた電解液を注入・密封してリチウムイオン電池を作製し、そのセルの厚みを測定した(初期厚さ)。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオン電池を0.1Cの電流で電圧4.5Vまで充電し、10分間の休止後、0.1Cの電流で電圧3.5Vまで放電する、というサイクルを3回繰り返した。更に0.1Cの電流で電圧4.5Vまで充電し、電圧を維持したまま60℃で7日間保存した。その後、セルの厚みを測定した(測定後厚さ)。下記式から厚さ増加率(ガス発生特性)をもとめた。厚さ増加率が少ないほどガス発生抑制効果が大きいことを示す。
厚さ増加率(%)=(測定後厚さ/初期厚さ)×100
リチウムイオン電池及び電解液の評価
上記二次電池用添加剤(B)又は比較用添加剤(B’)を表3に示した配合部数で含有するリチウムイオン電池用電解液を使用したリチウムイオン電池を下記の方法で作製した。
電極の場合と同様に、作製したリチウムイオン電池について、上記の方法で高電圧充放電サイクル特性及び出力特性を、下記の方法でガス発生を評価し、結果を表3に示した。
エチレンカーボネートとジエチルカーボネートとの混合溶媒(体積比率1:1)87.5部に、表3に示した部数で二次電池用添加剤(B)又は比較用添加剤(B’)を配合し、そこに12重量%となるように電解質としてのLiPF6を溶解させ、実施例34~48及び比較例14~20の電解液を調製した。
LiCoO2粉末90.0部、ケチェンブラック[シグマアルドリッチ社製]5部及びポリフッ化ビニリデン[シグマアルドリッチ社製]5部を乳鉢で充分に混合した後、1-メチル-2-ピロリドン[東京化成工業(株)製]70.0部を添加し、更に乳鉢で充分に混合してスラリーを得た。得られたスラリーを、大気中でワイヤーバーを用いて厚さ20μmのアルミニウム電解箔上の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、15.95mmφに打ち抜き、リチウムイオン電池用正極を作製した。
平均粒子径約8~12μmの黒鉛粉末92.5部、ポリフッ化ビニリデン7.5部及び1-メチル-2-ピロリドン200部を乳鉢で充分に混合しスラリーを得た。得られたスラリーを、大気中でワイヤーバーを用いて厚さ20μmの銅箔の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、16.15mmφに打ち抜き、プレス機で厚さ3μmにしてリチウムイオン電池用黒鉛系負極を作製した。
2032型コインセル内の両端に、上記正極及び負極を、それぞれの塗布面が向き合うように配置して、電極間にセパレータ(ポリプロピレン製不織布)を挿入し、リチウムイオン電池用セルを作製した。
実施例34~48及び比較例14~20の電解液を、作製したリチウムイオン電池用セルに注液後密封し二次電池(リチウムイオン電池)を作製した。
上述正極及び負極をラミネートセル中にそれぞれの塗布面が向き合うように配置して、実施例34~48及び比較例14~20の電解液を注入・密封してリチウムイオン電池を作製し、そのセルの厚みを測定した(初期厚さ)。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオン電池を0.1Cの電流で電圧4.5Vまで充電し、10分間の休止後、0.1Cの電流で電圧3.0Vまで放電する、というサイクルを3回繰り返した。更に0.1Cの電流で電圧4.5Vまで充電し、電圧を維持したまま60℃で7日間保存した。その後、セルの厚みを測定した(測定後厚さ)。下記式から厚さ増加率をもとめた。厚さ増加率が少ないほどガス発生抑制効果が大きいことを示す。
厚さ増加率(%)=(測定後厚さ/初期厚さ)×100-100
リチウムイオンキャパシタ及び電極の評価
上記二次電池用添加剤(B)又は比較用添加剤(B’)を表4に示した配合部数で含有するリチウムイオンキャパシタ用電極を下記の方法で作製し、該電極を使用して下記の方法でリチウムイオンキャパシタを作製した。
以下の方法で高電圧充放電サイクル特性、出力特性及びガス発生特性を評価した結果を表4に示した。
活性炭粉末90.0部、ケチェンブラック[シグマアルドリッチ社製]5.0部、ポリフッ化ビニリデン[シグマアルドリッチ社製]5.0部及び表4に示した部数の二次電池用添加剤(B)又は比較用添加剤(B’)を乳鉢で充分に混合した後、1-メチル-2-ピロリドン[東京化成工業(株)製]70.0部を添加し、更に乳鉢で充分に混合してスラリーを得た。得られたスラリーを、大気中でワイヤーバーを用いて厚さ20μmのアルミニウム電解箔上の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、15.95mmφに打ち抜き、リチウムイオンキャパシタ用正極を作製した。
平均粒子径約8~12μmの黒鉛粉末92.5部、ポリフッ化ビニリデン7.5部、1-メチル-2-ピロリドン[東京化成工業(株)製]200部及び表4に示した部数の二次電池用添加剤(B)を乳鉢で充分に混合しスラリーを得た。得られたスラリーを、厚さ20μmの銅箔の片面に塗布し、80℃で1時間乾燥させた後、更に減圧下(1.3kPa)、80℃で2時間乾燥して、16.15mmφに打ち抜き、プレス機で厚さ30μmにした。得られた電極と、リチウム金属箔を、セパレータ(ポリプロピレン製不織布)で挟んでビーカーセルにセットし、負極理論容量の約75%のリチウムイオンを約10時間かけて負極に吸蔵させ、リチウムイオンキャパシタ用負極を作製した。
ポリプロピレンのアルミラミネートフィルムからなる収納ケースに、実施例49~65及び比較例21~27の正極及び負極を、それぞれの塗布面が向き合うように配置して、電極間にセパレータ(ポリプロピレン製不織布)を挿入し、キャパシタ用セルを作製した。プロピレンカーボネート(PC)に、LiPF6を12重量%の割合で溶解させた電解液を作製したセルに注液密封してリチウムイオンキャパシタを作製した。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオンキャパシタを1Cの電流で電圧3.8Vまで充電し、10分間の休止後、1Cの電流で電圧2.0Vまで放電し、この充放電を繰り返した。このときの初回充電時の電池容量と50サイクル目充電時の電池容量を測定し、下記式から充放電サイクル特性を算出した。数値が大きい程、充放電サイクル特性が良好であることを示す。
高電圧充放電サイクル特性(%)=(50サイクル目充電時の電池容量/初回充電時の電池容量)×100
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオンキャパシタを1Cの電流で電圧3.8Vまで充電し、10分間の休止後、1Cの電流で電圧を1.0Vまで放電し、放電容量(以下1C放電容量と記載)を測定した。次に1Cの電流で電圧3.8Vまで充電し、10分間の休止後、10Cの電流で電圧を2.0Vまで放電し容量(以下10C放電容量と記載)を測定し、下記式から10C放電時の容量維持率を算出した。数値が大きい程、出力特性が良好であることを示す。
10C放電時の容量維持率(%)=(10C放電容量/1C放電容量)×100
10C放電時の容量維持率(%)を、出力特性(%)として表4及び5に示した。
上記方法で作製したラミネートセル(リチウムイオンキャパシタ)の厚みを測定した(初期厚さ)。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオンキャパシタを1Cの電流で電圧3.8Vまで充電し、10分間の休止後、1Cの電流で電圧2.0Vまで放電し容量を測定した(初回電池容量)。更に1Cの電流で電圧3.8Vまで充電し、電圧を維持したまま60℃で7日間保存した。その後、セルの厚みを測定した(測定後厚さ)。下記式から厚さ増加率をもとめた。厚さ増加率が少ないほどガス発生抑制効果が大きいことを示す。
厚さ増加率(%)=(測定後厚さ/初期厚さ)×100-100
リチウムイオンキャパシタ及び電解液の評価
上記二次電池用添加剤(B)又は比較用添加剤(B’)を表5に示した配合部数で含有するリチウムイオンキャパシタ用電解液を使用したリチウムイオンキャパシタを下記の方法で作製した。電極の場合と同様に、上記の方法で高電圧充放電サイクル特性、出力特性及びガス発生特性を評価し、結果を表5に示した。
プロピレンカーボネート87.5部からなる非水溶媒に、表5に示した部数で二次電池用添加剤(B)又は比較用添加剤(B’)を配合し、そこに12重量%となるように電解質としてのLiPF6を溶解させ、実施例66~80及び比較例28~34の電解液を調製した。
正極活物質として、アルカリ賦活法によって得られた比表面積が約2200m2/gである活性炭を用いた。活性炭粉末、アセチレンブラック及びポリフッ化ビニリデンを、それぞれ重量比80:10:10の割合となるように混合し、この混合物を、溶媒である1-メチル-2-ピロリドン中に添加し、撹拌混合してスラリーを得た。このスラリーを、厚さ30μmのアルミニウム箔の上にドクターブレード法で塗布し、仮乾燥した後、電極サイズが20mm×30mmとなるように切り取った。電極の厚みは約50μmであった。セルの組み立て前には、電極を真空中で120℃、10時間乾燥しリチウムイオンキャパシタ用の正極を作製した。
平均粒子径約8~12μmの黒鉛粉末80部、アセチレンブラック10部、及びポリフッ化ビニリデン10部を混合し、この混合物を溶媒である1-メチル-2-ピロリドンに添加して撹拌混合し、スラリーを得た。このスラリーを、厚さ18μmの銅箔の上にドクターブレード法で塗布し、仮乾燥した後、電極サイズが20mm×30mmとなるように切り取った。電極の厚みは、約50μmであった。更に真空中で120℃、5時間乾燥した。得られた電極と、リチウム金属箔を、セパレータ(ポリプロピレン製不織布)で挟んでビーカーセルにセットし、負極理論容量の約75%のリチウムイオンを約10時間かけて負極に吸蔵させ、リチウムイオンキャパシタ用負極を作製した。
上記正極と負極の間に、セパレータ(ポリプロピレン製不織布)を挿入し、これに実施例66~80及び比較例28~34の電解液を含浸させ、ポリプロピレンのアルミラミネートフィルムからなる収納ケースに入れて密封しリチウムイオンキャパシタセルを作製した。
リチウムイオン電池の安全性評価
[リチウムイオン電池の作製]
上記二次電池用添加剤(B)又は比較用添加剤(B’)の配合部数を表6に示した配合部数としたこと以外は、実施例17~33及び比較例7~13と同様の方法でリチウムイオン電池用電極作製し、該電極を使用してリチウムイオン電池を作製した。
作製したリチウムイオン電池について、以下の方法で発熱量及び発熱ピーク温度を評価し結果を表6に示した。発熱量が低く、発熱ピーク温度が高いほど安全性が向上している。
充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ(株)製]を用いて、リチウムイオン電池を0.1Cの電流で電圧4.3Vまで充電し、10分間の休止後、0.1Cの電流で電池電圧を3.0Vまで放電し、この充放電を3回繰り返した後、0.1Cの電流で電圧4.3Vまで充電した。この電池をアルゴン雰囲気下で分解して正極を取り出し、ジエチルカーボネートで洗浄し、減圧下(1.3kPa)で2時間乾燥した。続いて、アルゴン雰囲気下でLVCパン(耐圧パン)に上記正極を約3mgと、エチレンカーボネート(EC)とジエチルカーボネート(DEC)との混合溶媒(体積比率1:1)に、LiPF6を12重量%の割合で溶解させた電解液を約2mg入れ、測定用サンプルを作製した。
示差走査熱量計(DSC)[パーキンエルマー社製]を用いて、25℃から320℃まで5℃/分の速度で昇温し、発熱量及び発熱ピーク温度を測定した。
Claims (13)
- 3~5個の原子で構成され、電気陰性度が3以上である原子を2~4個有し、少なくとも1個の二重結合を有する原子団(X)及び三重結合(b)を有する化合物(A)を含有する二次電池用添加剤。
- 一般式(6)で表される基がウレタン基、ウレア基、アロファネート基及びビウレット基からなる群より選ばれる少なくとも1つの基に含まれる基である請求項3に記載の二次電池添加剤。
- 三重結合(b)が炭素-炭素三重結合及び/又は炭素-窒素三重結合である請求項1~4のいずれか1項に記載の二次電池用添加剤。
- 化合物(A)が更にアルキレンオキシ基(d)を有する請求項1~5のいずれか1項に記載の二次電池用添加剤。
- 化合物(A)が三重結合(b)及び前記アルキレンオキシ基(d)を下記一般式(7)又は(8)で表される構造単位として有する請求項6に記載の二次電池用添加剤。
- 請求項1~9のいずれか1項に記載の二次電池用添加剤を含有する電極。
- 請求項1~9のいずれか1項に記載の二次電池用添加剤を含有する電解液。
- 請求項10に記載の電極及び/又は請求項11に記載の電解液を有するリチウムイオン電池。
- 請求項10に記載の電極及び/又は請求項11に記載の電解液を有するリチウムイオンキャパシタ。
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