WO2013084767A1 - 重合体およびそれを用いた二次電池 - Google Patents
重合体およびそれを用いた二次電池 Download PDFInfo
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- WO2013084767A1 WO2013084767A1 PCT/JP2012/080741 JP2012080741W WO2013084767A1 WO 2013084767 A1 WO2013084767 A1 WO 2013084767A1 JP 2012080741 W JP2012080741 W JP 2012080741W WO 2013084767 A1 WO2013084767 A1 WO 2013084767A1
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- Prior art keywords
- group
- polymer
- salt
- secondary battery
- positive electrode
- Prior art date
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- 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
- 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
-
- 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
-
- 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
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a polymer useful even in the presence of an organic solvent, and a secondary battery using the polymer.
- Polymers containing a carboxyl group salt are generally widely used in fields such as water-absorbing materials and hydrogels because they have high ionic dissociation properties and strong hydrophilic properties in water.
- the salt of a carboxyl group has low ion dissociation properties in an organic solvent, metal ions are bound to the polymer. Therefore, a normal polymer containing a carboxyl group salt cannot sufficiently exhibit various functions based on its structure, for example, in an environment in which an organic solvent coexists.
- Patent Document 1 When a copolymer comprising a polymer unit based on vinylidene fluoride and a polymer unit having a side chain containing —CF 2 COOLi or —CF 2 SO 3 Li contains an organic solvent, its retention Attempts have been made to use it as a polymer electrolyte for lithium batteries because it has good ionic conductivity and high ion conductivity (Patent Document 1).
- the salt of the carboxyl group in the side chain of the copolymer described in Patent Document 1 is considered to have a high ion dissociation property in an organic solvent, and constitutes a highly ionic conductive polymer electrolyte based on such properties. Presumed to get.
- the copolymer described in Patent Document 1 has the above-mentioned characteristics, but is inferior in oxidation resistance (oxidative decomposition resistance), and there is a risk that the application field is limited.
- the current non-aqueous secondary battery lithium ion secondary battery
- the various materials to be used will be placed in an environment that is more susceptible to oxidation. Therefore, when the copolymer described in Patent Document 1 is applied to such a battery, there is a concern about loss of function due to oxidative decomposition and deterioration of battery characteristics due to decomposition products inhibiting the battery reaction.
- the present invention has been made in view of the above circumstances, a polymer excellent in oxidation resistance and capable of exhibiting a function based on a carboxyl group or a salt thereof well in the presence of an organic solvent, and the polymer It is providing the secondary battery using this.
- the polymer of the present invention is a polymer having a plurality of pendant groups, and the pendant group includes a carboxyl group or a salt thereof and a group interposed between the carboxyl group or a salt thereof and a main chain.
- a group interposed between the carboxyl group or a salt thereof and the main chain is a hydrocarbon group; a perfluorocarbon group; a hydrocarbon group, and at least one of an ester group and a carbonate group Or a perfluorocarbon group and at least one of an ester group and a carbonate group, and the carbonyl carbon of the carboxyl group or a salt thereof is the hydrocarbon group or the perfluorocarbon group.
- Fluorine is bonded to the carbon located at the ⁇ -position or ⁇ -position of the carbonyl carbon of the carboxyl group or a salt thereof.
- the secondary battery of the present invention is a secondary battery including a positive electrode containing a positive electrode active material, a negative electrode, a separator and an electrolyte, and is characterized by containing the polymer of the present invention.
- FIG. 1 is a graph showing the evaluation results of the charge / discharge cycle characteristics of the nonaqueous secondary batteries of Example 1 and Comparative Example 1.
- the polymer of the present invention has a structure in which a plurality of pendant groups are bonded to a main chain, and the pendant group is interposed between a carboxyl group or a salt thereof and the carboxyl group or a salt thereof and the main chain. It is made up of a group.
- Examples of the carboxyl group salt related to the pendant group include a metal salt of a carboxyl group and an ammonium salt of a carboxyl group.
- a metal salt of a carboxyl group an alkali metal salt (monovalent metal salt) such as lithium salt, sodium salt or potassium salt may be used, or an alkaline earth metal salt such as magnesium salt, calcium salt, strontium salt or barium salt. Or a metal salt having a valence of 2 or more.
- the salt of the carboxyl group related to the pendant group is a metal salt having a valence of 2 or more
- a ring structure containing a plurality of pendant groups is formed in the molecule of the polymer, or a plurality of molecules are formed between the molecules of the polymer.
- a cross-linked structure with a pendant group may be formed.
- the carboxyl group related to the pendant group or a group interposed between the salt thereof and the main chain is composed of a hydrocarbon group (hydrocarbon chain) or a perfluorocarbon group (all hydrogen in the hydrocarbon group is fluorine).
- a substituted group or a hydrocarbon group (hydrocarbon chain) and at least one of an ester group (ester bond) and a carbonate group (carbonate bond), or a perfluorocarbon group. And at least one of an ester group and a carbonate group. Since these groups are less susceptible to oxidative decomposition than ether groups (ether bonds), the oxidation resistance of the polymer is improved.
- the carboxyl group related to the pendant group or a group interposed between the salt group and the main chain is at least one of a hydrocarbon group, an ester group and a carbonate group
- a structure in which a carboxyl group or a salt thereof is bonded to a hydrocarbon group, and the hydrocarbon group is bonded to the main chain via an ester group or a carbonate group is at least one of a hydrocarbon group, an ester group and a carbonate group.
- the carboxyl group related to the pendant group or the group interposed between the salt and the main chain is at least one of a perfluorocarbon group, an ester group and a carbonate group
- a structure in which a carboxyl group or a salt thereof is bonded to a perfluorocarbon group, and the perfluorocarbon group is bonded to the main chain via an ester group or a carbonate group can be mentioned.
- Examples of the hydrocarbon group interposed between the carboxyl group related to the pendant group or a salt thereof and the main chain include a linear or branched alkylene group (alkylene chain).
- alkylene chain alkylene chain
- the hydrocarbon group for example, a linear or branched alkylene group
- at least a part of the hydrogen needs to be substituted with fluorine.
- the number of carbon atoms in the hydrocarbon group is preferably 1-20, for example.
- the carbonyl carbon of the carboxyl group related to the pendant group or a salt thereof is directly bonded to the carbon of the hydrocarbon group or perfluorocarbon group in the pendant group.
- the group intervening between the carboxyl group or a salt thereof and the main chain is a hydrocarbon group or composed of at least one of a hydrocarbon group and an ester group and a carbonate group .
- Fluorine is bonded to at least the carbon at the ⁇ -position or ⁇ -position of the carbonyl carbon of the carboxyl group or a salt thereof among the carbons of the hydrocarbon group. That is, in the carbon located at the ⁇ -position or ⁇ -position of the carbonyl carbon, at least a part of the hydrogen that can be bonded to it is substituted with fluorine.
- the group intervening between the carboxyl group or a salt thereof and the main chain is a perfluorocarbon group, or is composed of a perfluorocarbon group and at least one of an ester group and a carbonate group.
- the carbonyl carbon of the carboxyl group or its salt is directly bonded to the carbon of the perfluorocarbon group, at least the carbon located at the ⁇ -position of the carbonyl carbon of the carboxyl group or its salt In this case, fluorine is bonded.
- fluorine having a strong electron-withdrawing property is bonded to the carbon at the ⁇ -position or ⁇ -position of the carbonyl carbon of the carboxyl group or a salt thereof, so that the electron density on the oxygen of the carboxyl group or the salt thereof is increased. Since it becomes low, hydrogen (in the case of a carboxyl group) and a counter ion (in the case of a salt of a carboxyl group) are easily dissociated. Therefore, the polymer of the present invention exhibits a good ion dissociation property even in an organic solvent.
- the pendant group preferably includes, for example, a structural portion represented by the following general formula (1).
- n is an integer of 1 to 20, and M is hydrogen, metal, or ammonium.
- M in the case of a metal, as described above, an alkali metal (monovalent metal) such as lithium, sodium or potassium; a divalent or higher valent metal such as alkaline earth metal such as magnesium, calcium, strontium or barium; Metal;
- the pendant group may be configured only by the structural portion represented by the general formula (1).
- the structural part represented by 1) and an ester group or a carbonate group, or the structural part represented by the general formula (1), and a hydrocarbon group or a perfluorocarbon group are an ester group or a carbonate. It may be constituted by bonding via a group.
- one pendant group may contain a plurality of structural parts represented by the general formula (1).
- the pendant group has a hydrocarbon group (for example, an alkylene group) separately from the structural portion represented by the general formula (1), and the hydrocarbon group includes the general formula (1).
- the structure part represented by these may be comprised combining several.
- the polymer of the present invention may contain only a pendant group having a carboxyl group, may contain only a pendant group having a carboxyl group salt, a pendant group having a carboxyl group, and a salt of the carboxyl group And may contain a pendant group. Further, when one pendant group contains a plurality of carboxyl groups or salts thereof (for example, when a plurality of structural parts represented by the general formula (1) are contained), it contains only carboxyl groups. May contain only the salt of a carboxyl group, and may contain the salt of a carboxyl group and a carboxyl group.
- the main chain of the polymer is composed of only a hydrocarbon group, a perfluorocarbon group, a hydrocarbon group, an ester group, and a carbonate group. It is preferable that it is comprised by at least one of these, or is comprised by the perfluorocarbon group and at least one of the ester group and the carbonate group.
- a hydrocarbon group constituting the main chain for example, a linear or branched alkylene group (a part of hydrogen of the alkylene group may be substituted with fluorine) is preferable, and the main chain is constituted.
- the perfluorocarbon group examples include a linear or branched perfluoroalkylene group (a group in which all of the hydrogen atoms of the alkylene group are substituted with fluorine except the portion substituted with the pendant group).
- a hydrocarbon group not substituted with fluorine In particular, a linear or branched alkylene group is more preferable.
- the polymer may contain a group other than the pendant group in order to impart various properties.
- a group other than the pendant group for example, solubility in solvents, compatibility with other polymers, adsorption to other substances, decomposition resistance in electrolytes (for example, electrolytes used in secondary batteries), gas generation characteristics, etc. Groups that can be improved may be included.
- the secondary battery such as a non-aqueous electrolyte battery or an electric double layer capacitor is utilized by utilizing these characteristics.
- materials electrolyte additives
- solid electrolyte materials for solid electrolytes using solid electrolytes materials for dye-sensitized solar cells, and the like. it can.
- the polymer of the present invention since it has both a hydrophilic part and a hydrophobic part and can expect charge repulsion, it can be applied to a dispersant, a solubilizer, a surface conditioner, and the like. Alternatively, since it can function as a gel material by physical crosslinking, it can be applied to a hydrogel substitute material or an oil supply agent using an organic solvent (for example, an organic solvent having low volatility) instead of water. Since the polymer of the present invention is excellent in oxidation resistance, high durability can be expected even when applied to uses other than such electrochemical devices.
- the molecular weight of the polymer of the present invention is not particularly limited, and may be any molecular weight depending on the application to which the polymer is applied.
- the polymer of the present invention when the polymer of the present invention is applied to an electrolyte (non-aqueous electrolyte) of an electrochemical device, the polymer functions as an electrolyte salt that increases the ionic conductivity of the electrolyte by ionic dissociation in the electrolyte solvent (organic solvent).
- the molecular weight of the polymer is preferably not too high.
- the number average molecular weight of the polymer is preferably 500 or more, preferably 2 million or less, more preferably 1 million or less, and further preferably 500,000 or less. preferable.
- the polymer in the case where the polymer is disposed at a position in contact with the positive electrode active material and is not included in the electrolyte solvent, it is preferable that the polymer has a higher molecular weight.
- the number average molecular weight of the polymer is preferably 500 or more, preferably 5 million or less, more preferably 10,000 or more, and further preferably 30,000 or more. preferable.
- the number average molecular weight of the polymer is a number average molecular weight (polystyrene equivalent value) measured using gel permeation chromatography.
- the amount of the pendant group introduced into the polymer of the present invention is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 30 mol% with respect to the monomer constituting the main chain. % Or more is more preferable.
- the upper limit of the amount of pendant groups introduced into the polymer is not particularly limited, and may be selected according to solubility in the solvent used, restrictions due to ease of synthesis or steric hindrance, cost, and the like.
- the upper limit is 100 mol% of the pendant group with respect to the monomer constituting the main chain, but depending on the molecular structure of the monomer In some cases, a plurality of pendant groups can be introduced per monomer, and in this case, the upper limit of the amount of pendant groups introduced into the monomer constituting the main chain is 100 mol% or more.
- the amount of pendant groups introduced into the polymer referred to in this specification is based on the ratio of each element obtained from proton and fluorine 19 nuclear magnetic resonance spectroscopy (NMR) measurement, relative to the monomer constituting the main chain.
- NMR nuclear magnetic resonance spectroscopy
- the method for producing the polymer of the present invention is not particularly limited, and any method may be adopted.
- a typical production method is a method of reacting a hydroxyl group of polyvinyl alcohol with a fluorinated dicarboxylic acid anhydride; a method of transesterifying an acetyl group of polyvinyl acetate with a fluorinated dicarboxylic acid; A method of reacting a fluorinated dicarboxylic acid anhydride; and the like.
- the carboxyl group of the pendant group introduced into the main chain by such a method is reacted with a salt of a carboxyl group by reacting a metal or ammonium-containing hydroxide or a weak acid salt such as a carbonate with a counter ion.
- a polymer having a pendant group containing can be obtained.
- the polymer of this invention can also be manufactured by preparing the monomer which has the pendant group containing fluorinated carboxylic acid and its salt previously, and polymerizing this.
- the secondary battery of the present invention has a positive electrode (a positive electrode containing a positive electrode active material), a negative electrode, a separator, and an electrolyte, and contains the polymer of the present invention.
- the polymer of the present invention can be used, for example, as an additive for an electrolyte or an additive for protecting a positive electrode active material in a secondary battery. Therefore, in the secondary battery, it is preferable that the polymer is disposed at a position in contact with the electrolyte or the positive electrode active material, or is taken into the electrolyte.
- the polymer of the present invention has a high ion dissociation property. Therefore, the electrolyte of a secondary battery (an electrolyte solution such as an alkaline electrolyte or a non-aqueous electrolyte [a gel-like gel formed by the action of a gelling agent] The electrolyte is included.] The solid electrolyte containing the organic solvent is disposed at a position where it comes into contact with or taken into the electrolyte, thereby contributing to improvement of the ionic conductivity of the electrolyte.
- an electrolyte solution such as an alkaline electrolyte or a non-aqueous electrolyte [a gel-like gel formed by the action of a gelling agent]
- the electrolyte is included.
- the solid electrolyte containing the organic solvent is disposed at a position where it comes into contact with or taken into the electrolyte, thereby contributing to improvement of the ionic conductivity of the electrolyte.
- the polymer of the present invention can also be used as a protective agent for the positive electrode active material according to the secondary battery.
- a solid electrolyte interface SEI
- SEI solid electrolyte interface
- the polymer Since the polymer is also present on the surface of the positive electrode active material related to the secondary battery, the contact between the electrolyte of the secondary battery and the positive electrode active material is suppressed, and the decomposition of the electrolyte component is performed in the same manner as the SEI layer. The effect of suppressing the reaction can be expected. That is, since the polymer has a high ion dissociation property, even if it exists on the surface of the positive electrode active material, it does not inhibit the insertion and desorption of ions, but does not transmit electrons. It is speculated that it can be suppressed.
- the polymer of the present invention does not need to be formed by decomposing and polymerizing the additive in the battery. Therefore, in the secondary battery of the present invention, when the polymer is used as a protective agent for the positive electrode active material, it is preliminarily present on the surface of the positive electrode active material, or is taken into the electrolyte, What is necessary is just to make it contact with the positive electrode active material surface. When a secondary battery is formed using an electrolyte incorporating the polymer, the polymer is adsorbed on the surface of the positive electrode active material and functions as a protective agent.
- the secondary battery of the present invention includes an alkaline electrolyte secondary battery having an alkaline electrolyte, a nonaqueous secondary battery having a nonaqueous electrolyte (lithium ion secondary battery), and a solid secondary battery having a solid electrolyte (polymer secondary battery).
- an alkaline electrolyte secondary battery having an alkaline electrolyte a nonaqueous secondary battery having a nonaqueous electrolyte (lithium ion secondary battery), and a solid secondary battery having a solid electrolyte (polymer secondary battery).
- non-aqueous secondary battery examples include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
- the positive electrode of the non-aqueous secondary battery for example, one having a structure in which a positive electrode mixture layer containing a positive electrode active material, a conductive additive and a binder is provided on one side or both sides of a current collector is used.
- Examples of the positive electrode active material include lithium-containing transition metal oxides represented by Li 1 + x MO 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M: Co, Ni, Mn, etc.); lithium such as LiMn 2 O 4 Manganese oxide; LiMn (2-x) M x O 4 (0.01 ⁇ x ⁇ 0.5, M: Co, Ni, Fe, Mg, etc.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- SBR styrene butadiene rubber
- CMC carboxymethyl cellulose
- the conductive auxiliary agent related to the positive electrode mixture layer for example, graphite (graphite carbon material) such as natural graphite (flaky graphite), artificial graphite; acetylene black, ketjen black, channel black, furnace black, Examples thereof include carbon blacks such as carbon blacks such as lamp black and thermal black; carbon fibers.
- the positive electrode current collector may be the same as that used for the positive electrode of a conventionally known non-aqueous secondary battery, and for example, an aluminum foil having a thickness of 10 to 30 ⁇ m is preferable.
- the positive electrode for example, a paste-like or slurry-like positive electrode mixture-containing composition in which a positive electrode active material, a binder, a conductive auxiliary agent and the like are dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) is prepared (
- NMP N-methyl-2-pyrrolidone
- the binder may be dissolved in a solvent.
- the positive electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other methods.
- a positive electrode mixture-containing composition that also contains the polymer may be prepared by, for example, dissolving the polymer, and a positive electrode mixture layer may be formed by the above method using the composition.
- the amount of the polymer is from the viewpoint of ensuring better protection of the positive electrode active material by the polymer.
- the amount is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the positive electrode active material.
- the amount of the polymer in the non-aqueous secondary battery is too large, the cost is increased and the productivity of the battery is decreased, or the ionic conductivity is decreased and the internal resistance is increased. There is a risk of letting it go.
- the amount of the polymer is preferably 10 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. More preferably, it is 5 parts by mass or less.
- a lead body for electrical connection with other members in the nonaqueous secondary battery may be formed on the positive electrode according to a conventional method, if necessary.
- the thickness of the positive electrode mixture layer is preferably, for example, 10 to 100 ⁇ m per one side of the current collector.
- the amount of the positive electrode active material is preferably 60 to 95% by mass
- the amount of the binder is preferably 1 to 15% by mass
- the amount of the conductive auxiliary agent Is preferably 3 to 20% by mass.
- the negative electrode of the non-aqueous secondary battery has, for example, a negative electrode mixture layer made of a negative electrode mixture containing a negative electrode active material and a binder, and optionally a conductive additive, on one or both sides of the current collector.
- a negative electrode mixture layer made of a negative electrode mixture containing a negative electrode active material and a binder, and optionally a conductive additive, on one or both sides of the current collector.
- the thing of the structure, the thing comprised with the foil which consists of negative electrode active materials, etc. can be used.
- the negative electrode active material can occlude and release lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesophase carbon microbeads (MCMB), carbon fibers, etc.
- lithium such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesophase carbon microbeads (MCMB), carbon fibers, etc.
- MCMB mesophase carbon microbeads
- One kind or a mixture of two or more kinds of carbon-based materials is used.
- a simple substance containing an element such as Si, Sn, Ge, Bi, Sb, In, a compound and an alloy thereof, a compound that can be charged and discharged at a low voltage close to a lithium metal such as a lithium-containing nitride or a lithium-containing oxide, or lithium Metals, lithium / aluminum alloys, and Ti oxides represented by Li 4 Ti 5 O 12 can also be used as the negative electrode active
- the same negative electrode binder and conductive additive as those exemplified above as those that can be used for the positive electrode can be used.
- a current collector When a current collector is used for the negative electrode, a copper or nickel foil, a punching metal, a net, an expanded metal or the like can be used as the current collector, but a copper foil is usually used.
- the upper limit of the thickness is preferably 30 ⁇ m, and the lower limit is 5 ⁇ m in order to ensure mechanical strength. Is desirable.
- a negative electrode active material, a binder, and a conductive auxiliary agent used as necessary are prepared in a paste-like or slurry-like negative electrode mixture-containing composition in which a solvent such as NMP or water is dispersed. (However, the binder may be dissolved in a solvent.) After this is applied to one or both sides of the current collector and dried, it is manufactured through a step of applying a calender treatment if necessary.
- the negative electrode active material is the above-mentioned various alloys or lithium metal
- the foil can be used alone or laminated on the current collector as a negative electrode agent layer to form a negative electrode.
- the negative electrode is not limited to those manufactured by these manufacturing methods, and may be manufactured by other methods.
- a lead body for electrical connection with other members in the lithium secondary battery may be formed on the negative electrode according to a conventional method, if necessary.
- the thickness of the negative electrode mixture layer is preferably, for example, 10 to 100 ⁇ m per side of the current collector.
- the composition of the negative electrode mixture layer is preferably 80.0 to 99.8 mass% for the negative electrode active material and 0.1 to 10 mass% for the binder, for example.
- the amount of the conductive auxiliary in the negative electrode mixture layer is preferably 0.1 to 10% by mass.
- the separator of the nonaqueous secondary battery is preferably a porous film composed of polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer; polyester such as polyethylene terephthalate or copolymer polyester;
- the separator preferably has a property (that is, a shutdown function) that closes the pores at 100 to 140 ° C. Therefore, the separator is composed of a thermoplastic resin having a melting point, that is, a melting temperature of 100 to 140 ° C. measured using a differential scanning calorimeter (DSC) in accordance with the provisions of Japanese Industrial Standard (JIS) K 7121.
- DSC differential scanning calorimeter
- polyethylene and a resin having a melting point higher than that of polyethylene such as polypropylene are used by mixing or laminating, it is desirable that the polyethylene constituting the porous membrane is 30% by mass or more, and 50% by mass or more. It is more desirable.
- a resin porous membrane for example, a porous membrane composed of the above-mentioned exemplified thermoplastic resin used in a conventionally known non-aqueous secondary battery or the like, that is, a solvent extraction method, a dry type Alternatively, an ion-permeable porous film manufactured by a wet stretching method or the like can be used.
- the positive electrode and the negative electrode are non-aqueous as a laminated body (laminated electrode body) formed by overlapping the separators, or a wound electrode body obtained by winding the laminated body in a spiral shape. Used for the next battery.
- a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent can be used.
- the organic solvent include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ⁇ -butyrolactone, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxymethane, dioxolane derivatives , Sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, die
- a salt of a fluorine-containing compound such as lithium perchlorate, lithium organic boron, trifluoromethanesulfonate, imide salt, or the like is preferably used.
- electrolyte salts for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C n F 2n (SO 3) 2 ( 1 ⁇ n ⁇ 8), LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (2 ⁇ n ⁇ 8), LiN (Rf 3 OSO 2 ) 2 , Rf represents a fluoroalkyl group.
- LiPF 6 and LiBF 4 are more preferable because of good charge / discharge characteristics. This is because these fluorine-containing organic lithium salts have a large anionic property and are easily ion-separated, and thus are easily dissolved in the solvent.
- the concentration of the electrolyte salt in the nonaqueous electrolytic solution is not particularly limited, but is usually 0.5 to 1.7 mol / L.
- vinylene carbonates 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, fluorobenzene, and t-butylbenzene are used to improve battery safety, charge / discharge cycle characteristics, and high-temperature storage characteristics.
- Additives such as can also be appropriately added to the non-aqueous electrolyte.
- a gelled gel (gel electrolyte) can be used by adding a known gelling agent.
- the polymer of the present invention in order to incorporate the polymer of the present invention into a non-aqueous electrolyte that is an electrolyte, the polymer may be dissolved in the non-aqueous electrolyte.
- the concentration of the polymer is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.
- the concentration of the polymer in the nonaqueous electrolytic solution is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
- the heavy battery is placed on a portion that can come into contact with the electrolyte inside the secondary battery (for example, the inner wall of the exterior body).
- a method of forming a film of the polymer by applying a coating solution prepared by dissolving the coalescence in a solvent and drying it may be employed.
- the film is eluted in the electrolyte (non-aqueous electrolyte) and acts as an ion conductivity improving component of the electrolyte, or further adsorbed on the surface of the positive electrode active material and acts as a protective agent.
- the secondary battery of the present invention can be applied to the same uses as various uses in which conventionally known secondary batteries are used.
- Example 1 In a 100 mL three-necked reaction flask equipped with a magnetic stirrer, heating oil bath, dropping device, cooling pipe and nitrogen inlet, 0.39 g of polyvinyl alcohol (“PVA203” manufactured by Kuraray Co., Ltd.) and dimethylacetamide (Wako Pure Chemical Industries, Ltd.) (Made by Kogyo Co., Ltd.) 20 mL was added, and the oil bath was heated to 100 ° C. with stirring to dissolve polyvinyl alcohol.
- PVA203 polyvinyl alcohol
- dimethylacetamide Wide by Kogyo Co., Ltd.
- the obtained polymer has a main chain derived from the main chain of polyvinyl alcohol, a structural part where n is 3 and M is Li represented by the general formula (1), and the structural part It has a pendant group containing an ester group between the main chain. Furthermore, the amount of pendant groups introduced into the polymer was about 55 mol% with respect to the vinyl alcohol units constituting the main chain. The number average molecular weight of the polymer was about 50,000.
- Nickel / cobalt / lithium manganate as a positive electrode active material (atomic ratio of nickel, cobalt, and manganese is 5: 2: 3): 47 parts by mass, carbon as a conductive additive: 1 part by mass, PVDF as a binder: 2 parts by mass and the polymer: 0.1 part by mass were mixed using NMP as a solvent to prepare a positive electrode mixture-containing composition.
- This positive electrode mixture-containing composition is applied to one side of an aluminum foil having a thickness of 15 ⁇ m so that the exposed portion of the aluminum foil remains in a part, dried and calendered, and a positive electrode mixture having a thickness of about 75 ⁇ m. A positive electrode having a layer was obtained. This positive electrode was punched into a circle having a diameter of 13 mm including the exposed portion of the current collector.
- the above-mentioned positive electrode and a negative electrode (lithium thickness 0.5 mm, size 20 ⁇ 17 mm) in which metallic lithium was bonded to one side of a rectangular stainless steel plate were laminated with a separator (a porous film made of PE having a thickness of 18 ⁇ m and a nonwoven fabric).
- a nonaqueous electrolyte solution (a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 3: 7). was injected into the exterior body, and then the exterior body was sealed to produce a non-aqueous secondary battery (lithium ion secondary battery).
- Example 1 A positive electrode mixture-containing composition prepared in the same manner as in Example 1 was used except that the polymer was not added, and a positive electrode was produced in the same manner as in Example 1. And the non-aqueous secondary battery was produced like Example 1 except having used this positive electrode.
- the charge / discharge cycle characteristics of the nonaqueous secondary batteries of Example 1 and Comparative Example 1 were evaluated by the following method. Each battery is charged to 4.7 V with a current value of 8 mA, and further, constant current-constant voltage charging (total charging time 5 hours) is performed with a constant voltage of 4.7 V, and then 2.5 V with a current value of 8 mA. A series of operations for discharging until 1 cycle was repeated 50 times, and the discharge capacity for each cycle number was measured. These results are shown in FIG.
- the secondary battery has a higher capacity when evaluating charge / discharge cycle characteristics than the battery of Comparative Example 1 that does not use the polymer. This is because the polymer having excellent ionic dissociation property and non-oxidation resistance in a non-aqueous electrolyte solvent (organic solvent) protects the positive electrode active material without inhibiting the insertion and desorption of ions.
- a non-aqueous electrolyte solvent organic solvent
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Abstract
Description
本発明の重合体は、複数のペンダント基が主鎖に結合した構造を有しており、前記ペンダント基は、カルボキシル基またはその塩と、前記カルボキシル基またはその塩と主鎖との間に介在する基とで構成されている。
本発明の二次電池は、正極(正極活物質を含有する正極)、負極、セパレータおよび電解質を有しており、かつ本発明の重合体を含有している。
磁性攪拌器、加熱油浴、滴下装置、冷却管および窒素導入口を備えた100mLの三つ口反応フラスコに、ポリビニルアルコール(クラレ社製「PVA203」)0.39g、およびジメチルアセトアミド(和光純薬工業社製)20mLを入れ、攪拌しながら油浴を100℃に加熱してポリビニルアルコールを溶解した。油浴を外して室温まで放冷した三つ口反応フラスコ内に、ピリジン4mLにヘキサフルオログルタル酸無水物3.1gを混合した溶液を滴下し、滴下終了後1時間撹拌を継続した。その後、三つ口反応フラスコ内に水70μLを加えて20分攪拌し、更に水酸化リチウム1水和物0.76gを加えて溶解した後、1N水酸化リチウム水溶液を当量まで加えた。
前記重合体を添加しなかった以外は実施例1と同様にして調製した正極合剤含有組成物を使用し、実施例1と同様にして正極を作製した。そして、この正極を用いた以外は、実施例1と同様にして非水二次電池を作製した。
Claims (8)
- 複数のペンダント基を有する重合体であって、
前記ペンダント基は、カルボキシル基またはその塩と、前記カルボキシル基またはその塩と主鎖との間に介在する基とで構成されており、
前記カルボキシル基またはその塩と主鎖との間に介在する基が、炭化水素基であるか;パーフルオロカーボン基であるか;炭化水素基と、エステル基およびカーボネート基のうちの少なくとも一方とで構成されているか;またはパーフルオロカーボン基と、エステル基およびカーボネート基のうちの少なくとも一方とで構成されており、
前記カルボキシル基またはその塩の有するカルボニル炭素は、前記炭化水素基または前記パーフルオロカーボン基の有する炭素と直接結合しており、
前記カルボキシル基またはその塩と主鎖との間に介在する基が、炭化水素基であるか;または炭化水素基と、エステル基およびカーボネート基のうちの少なくとも一方とで構成されている場合には、前記炭化水素基の有する炭素のうち、少なくとも、前記カルボキシル基またはその塩の有するカルボニル炭素のα位またはβ位に位置する炭素には、フッ素が結合していることを特徴とする重合体。 - 前記主鎖が、炭化水素基で構成されているか;パーフルオロカーボン基で構成されているか;炭化水素基と、エステル基およびカーボネート基のうちの少なくとも一方とで構成されているか;またはパーフルオロカーボン基と、エステル基およびカーボネート基のうちの少なくとも一方とで構成されている請求項1に記載の重合体。
- 二次電池内で使用される請求項1に記載の重合体。
- 正極活物質を含有する正極、負極、セパレータおよび電解質を含む二次電池であって、請求項1に記載の重合体を含有することを特徴とする二次電池。
- 前記重合体が、電解質または正極活物質と接触する箇所に配置されているか、電解質中に取り込まれている請求項5に記載の二次電池。
- 前記重合体が、前記正極活物質の表面に存在している請求項5に記載の二次電池。
- 前記電解質が非水電解液である請求項5に記載の二次電池。
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JP2013548192A JP5843885B2 (ja) | 2011-12-05 | 2012-11-28 | 重合体およびそれを用いた二次電池 |
US14/342,047 US20140227589A1 (en) | 2011-12-05 | 2012-11-28 | Polymer and secondary battery using same |
CN201280042032.7A CN103764692A (zh) | 2011-12-05 | 2012-11-28 | 聚合物以及使用其的二次电池 |
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KR101746927B1 (ko) | 2014-06-13 | 2017-06-14 | 주식회사 엘지화학 | 리튬 전극 및 이를 포함하는 리튬 전지 |
WO2024080827A1 (ko) * | 2022-10-13 | 2024-04-18 | 한국화학연구원 | 겔 고분자 전해질 형성용 조성물, 그로부터 제조된 겔 고분자 전해질 및 그 제조방법 |
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US10559826B2 (en) * | 2017-03-20 | 2020-02-11 | Global Graphene Group, Inc. | Multivalent metal ion battery having a cathode of recompressed graphite worms and manufacturing method |
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- 2012-11-28 US US14/342,047 patent/US20140227589A1/en not_active Abandoned
- 2012-11-28 CN CN201280042032.7A patent/CN103764692A/zh active Pending
- 2012-11-28 WO PCT/JP2012/080741 patent/WO2013084767A1/ja active Application Filing
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WO2024080827A1 (ko) * | 2022-10-13 | 2024-04-18 | 한국화학연구원 | 겔 고분자 전해질 형성용 조성물, 그로부터 제조된 겔 고분자 전해질 및 그 제조방법 |
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US20140227589A1 (en) | 2014-08-14 |
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CN103764692A (zh) | 2014-04-30 |
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