JP2019164992A - Porous insulator, electrode, and non-aqueous storage element - Google Patents

Abstract

To provide a porous insulator, having high communication, a shape maintenance function, and a shutdown function and an electrode in which the porous insulator is formed on an electrode mixture.SOLUTION: A porous insulator 10 includes: a porous structure 11 formed of a polymer compound and having pores communicating with each other; and a solid 12 having a melting point or glass transition point lower than that of the polymer compound. Further, an electrode is configured so that an electrode mixture containing an active material is formed on an electrode substrate and the porous insulator is formed on the electrode mixture.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a porous insulator, an electrode, and a nonaqueous storage element.

  In a lithium ion secondary battery, when the positive electrode and the negative electrode are short-circuited due to damage or the like, a thermal runaway reaction may occur and abnormal heat may be generated. In order to prevent such a thermal runaway reaction, it is necessary to provide a separator having a shape maintaining function that prevents a short circuit between the positive electrode and the negative electrode by suppressing thermal contraction and a shutdown function that prevents a battery reaction by thermal deformation. It is effective.

  Conventionally, as the separator, a polyolefin microporous film having a melting point near 150 ° C. is mainly used.

  However, due to the strain at the time of forming the pores of the polyolefin microporous membrane, the polyolefin microporous membrane tends to shrink when thermally deformed, and the positive electrode and the negative electrode are easily short-circuited.

  Patent Document 1 discloses a separator for an electrochemical element comprising a porous film containing a porous substrate and a resin. Here, the porous substrate has a heat resistant temperature of 150 ° C. or higher and includes filler particles. The resin has a melting point in the range of 80 to 130 ° C.

  However, the separator of Patent Document 1 includes filler particles and a resin. In general, when filler particles that are likely to have a close-packed structure and a resin that closes the pores are used, the separator's communication tends to decrease. As a result, the ion permeability of the separator is lowered, so that the input / output characteristics of the lithium ion secondary battery are lowered or the durability is lowered due to factors such as overvoltage.

  An object of one embodiment of the present invention is to provide a porous insulator having high communication performance and a shape maintaining function and a shutdown function.

  One embodiment of the present invention is a porous insulator which is formed using a polymer compound and has a porous structure having pores that communicate with each other and a melting point or glass transition point lower than that of the polymer compound. Have a solid.

  According to one embodiment of the present invention, it is possible to provide a porous insulator having high communication performance and having a shape maintaining function and a shutdown function.

It is a cross-sectional schematic diagram which shows an example of the porous insulator of this embodiment. It is a cross-sectional schematic diagram which shows an example of the electrode of this embodiment. It is a schematic diagram explaining the shape maintenance function and shutdown function of the porous insulator of FIG. It is the schematic which shows an example of the non-aqueous electrical storage element of this embodiment. It is a cross-sectional schematic diagram which shows the device A of an Example. 2 is a SEM photograph of the porous insulator of Example 1. It is a cross-sectional schematic diagram which shows the device B of an Example.

  Hereinafter, modes for carrying out the present invention will be described. However, the following embodiments are preferred embodiments of the present invention, and the present invention is not limited to the embodiments.

<Porous insulator and electrode>
FIG. 1 shows an example of the porous insulator of the present embodiment.

  The porous insulator 10 is formed of a polymer compound, and includes a porous structure 11 having pores communicating with each other and a solid 12 having a melting point or a glass transition point lower than that of the polymer compound. Here, since the porous structure 11 is formed of a polymer compound without using filler particles, it is easy to form a structure with a high porosity. As a result, the porous insulator 10 has high communication properties. Become. Furthermore, when the porous insulator 10 is heated to the melting point (or glass transition point) of the solid 12, the solid 12 becomes a liquid (or rubber state) due to the difference between the melting point or glass transition point of the polymer compound and the solid 12. However, the polymer compound does not change to a liquid (or rubber state), and the porous structure 11 maintains its shape. For this reason, the porous insulator 10 has a shape maintaining function and a shutdown function. Here, since the void | hole which exists in the porous insulator 10 is connected, the solid 12 which changed into the liquid (or rubber state) can move in the void | hole, The shutdown function is improved.

  The porous insulator 10 can be applied to electrodes such as non-aqueous storage elements such as lithium ion secondary batteries and nickel hydride secondary batteries, and power generation elements such as fuel cells and solar cells.

  FIG. 2 shows an electrode having a porous insulator 10 as an example of the electrode of the present embodiment.

  In the electrode 20, an electrode mixture 23 including an active material 22 is formed on an electrode substrate 21, and the porous insulator 10 is formed on the electrode mixture 23. Here, since a part of the porous insulator 10 exists in a part of the electrode mixture 23, the bonding strength between the electrode mixture 23 and the porous insulator 10 is improved. Thereby, when an impact such as vibration is applied from the outside, the active material 22 becomes difficult to peel off, so that the durability of the non-aqueous storage element having the electrode 20 is improved. Further, when a conductor such as a nail penetrates the non-aqueous storage element having the electrode 20, it is difficult for a short circuit between the positive electrode and the negative electrode to occur, so that the safety of the non-aqueous storage element is improved.

  The region where the porous insulator 10 is present in the electrode mixture 23 (depth from the surface of the electrode mixture 23) is preferably 0.5% or more, and more preferably 1.0% or more. More preferred.

  Note that a part of the porous insulator 10 may not be present in a part of the electrode mixture 23.

  Next, the shape maintaining function and the shutdown function of the porous insulator 10 will be described with reference to FIG.

  In general, due to abnormal charging / discharging or the like, an excessive current may flow through the non-aqueous power storage element to cause abnormal heat generation. In such a case, when the electrode 20 is used, abnormal heat generation can be suppressed.

  Specifically, when the pore size of the porous structure 11 is smaller than the particle size of the solid 12 (see FIG. 3A), the pores 31 are blocked by the solid 12 being changed to the liquid 12 ′ by heating. (See FIG. 3B). As a result, ions existing in the non-aqueous electrolyte are prevented from moving through the communicating holes 31, and the progress of the electrochemical reaction in the non-aqueous storage element is suppressed. As a result, the current flow is interrupted, and the temperature rise is suppressed. Next, even after the solid 12 is changed to the liquid 12 ′, the temperature rises gradually for a certain period of time, so the liquid 12 ′ is connected to each other by moving in the holes 31 through which the liquid 12 ′ communicates. In addition, a more effective shutdown function can be exhibited. Furthermore, it is also conceivable that the liquid 12 ′ adheres around the active material 22 present in the porous insulator 10 (see FIG. 3C). As a result, the non-aqueous electrolyte is prevented from coming into contact with the active material 22, and the temperature rise is suppressed. On the other hand, when the internal temperature of the non-aqueous energy storage device reaches 160 ° C. or higher due to the surrounding environment such as a high temperature environment, the electrochemical reaction between the negative electrode and the non-aqueous electrolyte proceeds due to the decomposition of the SEI film. Thereafter, when the temperature reaches 180 ° C. or higher, the electrochemical reaction between the positive electrode and the non-aqueous electrolyte proceeds. When such a thermal runaway reaction proceeds, the temperature rises to 200 ° C. or more with a rapid temperature rise. However, the porous structure 11 does not change to a liquid even at a temperature at which the solid 12 changes to the liquid 12 ′, that is, does not thermally contract, and maintains its shape, thus preventing a short circuit between the positive electrode and the negative electrode. be able to.

  Further, when the pore diameter of the porous structure 11 is larger than the particle diameter of the solid 12 (see FIG. 3D), the solid 12 is changed into the liquid 12 ′ by heating, and the inside of the communicating pores 31 is changed. By moving, it adheres to the periphery of the active material 22 present in the porous insulator 10 (see FIG. 3C). As a result, the non-aqueous electrolyte is prevented from coming into contact with the active material 22, and the temperature rise is suppressed.

  The melting point or glass transition point of the polymer compound is preferably 160 ° C. or higher, and more preferably 200 ° C. or higher, from the viewpoint of the shape maintaining function of the porous insulator 10.

  The presence distribution of the porous structure 11 and the solid 12 in the porous insulator 10 is not particularly limited and can be appropriately designed according to the required characteristics of the nonaqueous storage element. For example, as shown in FIG. 1, the solid 12 may be uniformly dispersed in the porous structure 11. Moreover, the solid 12 may exist locally in the porous structure 11 and the distribution of the solid 12 may be biased.

  Next, a difference in melting point or glass transition point between the polymer compound and the solid 12 will be described.

  When the non-aqueous power storage element generates heat due to an excessive current flow due to abnormal charging / discharging or the like, in the porous insulator 10, the solid 12 changes to the liquid 12 ′, so that the communicating holes 31 are formed. Blocked. As a result, the current flow is interrupted, thereby suppressing the temperature rise. However, after the solid 12 is changed to the liquid 12 ′, the temperature rise inside the nonaqueous storage element gradually proceeds for a certain period of time, and the shape of the porous structure 11 is maintained during this time, and the short circuit between the positive electrode and the negative electrode is performed. Need to prevent. Here, if the difference in melting point or glass transition point between the polymer compound and the solid 12 is too small, it is difficult to prevent a short circuit between the positive electrode and the negative electrode. From the above, the difference between the melting point or the glass transition point of the polymer compound and the solid 12 is preferably 20 ° C. or higher, and more preferably 50 ° C. or higher.

  The pore diameter of the porous insulator 10 is preferably 0.1 to 10 μm, and more preferably 0.1 to 1.0 μm. When the pore diameter of the porous insulator 10 is 0.1 μm or more, the permeability and ion permeability of the non-aqueous electrolyte of the porous insulator 10 are improved, and the reaction inside the non-aqueous power storage element proceeds efficiently. To do. On the other hand, when the pore diameter of the porous insulator 10 is 10 μm or less, it is possible to prevent a short circuit between the positive electrode and the negative electrode due to lithium dendride generated inside the nonaqueous storage element, and the safety of the nonaqueous storage element. Will improve.

  The porosity of the porous insulator 10 is preferably 30 to 90%, and more preferably 50 to 85%. When the porosity of the porous insulator 10 is 30% or more, the porosity of the porous insulator 10 is improved, so that the permeability and ion permeability of the non-aqueous electrolyte are improved, and the inside of the non-aqueous storage element is increased. The reaction proceeds efficiently. On the other hand, when the porosity of the porous insulator 10 is 85% or less, the strength of the porous insulator 10 is improved, so that the porous insulator 10 is broken when an impact such as vibration is applied from the outside. It becomes difficult to do.

  The polymer compound is not particularly limited as long as it has a melting point or glass transition point higher than that of the solid 12, and examples thereof include aramid, polyamideimide, polyimide, and cellulose.

  In addition, a high molecular compound may be used independently and may use 2 or more types together.

  The polymer compound is preferably cross-linked from the viewpoint of the shape maintaining function of the porous insulator 10. When the polymer compound is crosslinked, the chemical resistance and strength can be controlled by controlling the crosslinking density.

  The porous structure 11 when the polymer compound is crosslinked is not particularly limited, and is preferably a co-continuous structure having a three-dimensional branched network structure of the polymer compound as a skeleton from the viewpoint of a shutdown function.

  Examples of such a porous structure 11 include a monolith structure in which a carbon skeleton forms a three-dimensional network structure in a co-continuous structure.

  In the present specification and claims, when the polymer compound that is crosslinked does not have a melting point or glass transition point, the melting point or glass transition point is higher than that of the solid 12.

  The solid 12 is an electrochemically stable material that has electrical insulation, is stable with respect to a non-aqueous electrolyte, and is not easily oxidized or reduced within a voltage range applied when incorporated in a non-aqueous storage element. It is preferable to be configured.

  The solid 12 is not particularly limited as long as it has a melting point or glass transition point lower than that of the polymer compound, and may be any of a polymer compound and a low molecular compound (for example, ethylene carbonate).

  The melting point or glass transition point of the solid 12 is preferably 80 to 200 ° C, and more preferably 110 to 160 ° C. When the melting point or glass transition point of the solid 12 is 80 ° C. or higher, the shutdown function does not appear unless the inside of the non-aqueous power storage element reaches an abnormal temperature due to the external environment. On the other hand, when the melting point or glass transition point of the solid 12 is 200 ° C. or less, a shutdown function can be expressed in the initial stage when the non-aqueous storage element abnormally generates heat, The safety of the non-aqueous storage element is improved.

  The shape of the solid 12 is not particularly limited as long as it does not significantly hinder the communication of the pores 31 of the porous insulator 10.

  The solid 12 is preferably resin particles because the melting point or the glass transition point can be easily controlled by the molecular structure. Accordingly, the melting point or glass transition point of the solid 12 can be optimized in consideration of the safety of the nonaqueous storage element, and the shutdown function of the porous insulator 10 is improved.

  Examples of the resin constituting the resin particles include polyethylene (PE), modified polyethylene, polypropylene, paraffin, copolymerized polyolefin, polyolefin derivatives (for example, chlorinated polyethylene, polyvinylidene chloride, polyvinyl chloride, fluororesin), and polyolefin wax. Petroleum wax, carnauba wax and the like.

  Examples of the copolymer polyolefin include an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, An ethylene-vinyl monomer copolymer such as an ethylene-vinyl alcohol copolymer may be mentioned.

  In addition, a resin particle may be used independently and may use 2 or more types together.

  The resin particles may be surface-modified. Thereby, the dispersibility of the resin particle in the coating liquid used for the porous insulator 10 can be improved. As a result, the distribution of the resin particles in the porous insulator 10 becomes uniform, and the shape maintaining function and the shutdown function of the porous insulator 10 are improved.

  As a method for modifying the surface of the resin particles, for example, using a reactive group such as an ethylenically unsaturated group or an epoxy group, a polar group such as an alkoxy group, an amide group, a carboxyl group or a sulfonic acid group is provided on the surface The method to introduce is mentioned.

  The particle size of the resin particles is preferably 0.01 to 100 μm, and more preferably 0.1 to 1 μm. When the particle size of the resin particles is 0.01 μm or more, the shutdown function of the porous insulator 10 is improved, and when it is 100 μm or less, the continuity of the pores 31 of the porous insulator 10 is improved.

<Method for producing porous insulator>
Examples of the method for producing the porous insulator 10 in the case where the polymer compound is not crosslinked include a method utilizing a phase separation phenomenon such as a heat-induced phase separation method and a poor solvent-induced phase separation method.

  In this case, the solvent used for the coating solution used for the production of the porous insulator 10 is not particularly limited, and is appropriately selected by paying attention to the solubility parameter so that a predetermined porous structure is formed. Can do.

  As a manufacturing method of the porous insulator 10 other than the above, for example, after applying a coating liquid containing a polymerization initiator, a polymerizable compound, and a solid 12 and dissolving the polymerizable compound, non-ionizing radiation, The method of irradiating with ionizing radiation or infrared rays is mentioned.

  When the polymer compound is crosslinked, the polymer compound is generally poorly soluble, and therefore, when the porous insulator 10 is manufactured, one or more polyfunctional polymerizable compounds (for example, a crosslinking monomer, A coating solution containing a crosslinkable oligomer) is used.

  The polyfunctional polymerizable compound means a compound having two or more polymerizable groups.

  In this case, the porous insulator 10 can be formed using a polymerization-induced phase separation method or the like.

  The polyfunctional polymerizable compound is not particularly limited as long as it can be crosslinked by irradiation with non-ionizing radiation, ionizing radiation, or infrared rays. For example, acrylate resin, methacrylate resin, urethane acrylate resin, vinyl Examples include ester resins, unsaturated polyesters, epoxy resins, oxetane resins, vinyl ethers, resins utilizing ene-thiol reaction, and the like. Among these, from the viewpoint of productivity, acrylate resins, methacrylate resins, urethane acrylate resins, and vinyl ester resins are preferable.

  Examples of the radical polymerizable monomer include unsaturated compounds such as myrcene, carene, osymene, pinene, limonene, camphene, terpinolene, tricyclene, terpinene, fenchen, ferrandrene, sylbestrene, sabinene, dipentene, bornene, isopulegol, and carvone. An ester compound in which a double bond of a terpene having a bond is epoxidized and acrylic acid or methacrylic acid is added; citronellol, pinocampheol, geraniol, fentil alcohol, nerol, borneol, linalool, menthol, terpineol, twill alcohol, Citronellal, Yonon, Iron, Cinerol, Citral, Pinol, Cyclocitral, Carbomenton, Ascaridol, Safranal, Piperitol, Mentenmono Alcohols derived from terpenes such as ru, dihydrocarvone, carbeol, sclareol, manol, hinokiol, ferruginol, totarol, sugiol, farnesol, patchouliol, nerolidol, carotol, casinomol, lanseol, eudesmol, phytol, and acrylic acid or methacrylic acid Ester compounds of acids; citronellolic acid, hinokic acid, santalic acid, menthone, carbotanaseton, ferrandral, pimelicenone, perillaldehyde, tsuyon, caron, daggerton, camphor, bisabolene, santalen, gingiveren, caryophyllene, curcumen, cedrene, Kazinen, Longifolene, Sesquibenien, Cedrol, Guayool, Kessoglycol, Ciperon, Eremofilon, Zel Bonn, camphorene, podocarprene, mylene, phyllocladene, totalene, ketomanoyl oxide, manoyl oxide, abietic acid, pimaric acid, neoabietic acid, levopimaric acid, iso-d-pimalic acid, agatendicarboxylic acid, rubenic acid, carotenoid, Examples thereof include acrylate or methacrylate compounds having a skeleton such as peralaldehyde, piperitone, ascaridol, pymene, fenken, sesquiterpenes, diterpenes, and triterpenes in the ester side chain.

  As the polymerization initiator, for example, a photopolymerization initiator or a thermal polymerization initiator can be used.

  As the photopolymerization initiator, a photo radical generator can be used.

Examples of the photo radical generator include α-hydroxyacetophenone, α-aminoacetophenone, 4-aroyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophene, p-dimethyl. Aminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophene, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2- Chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy Roxy-2-methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, benzoin isopropyl ether, benzoin methyl ether, benzoin Benzoin alkyl ethers and esters such as ethyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, (1-hydroxycyclohexyl) phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morphol Linophenyl) -butanone-1, (1-hydroxycyclohexylphenyl) ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (η ⁵ -2,4-cyclopentadien-1-yl) -Bis (2,6-di Fluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one monoacylphosphine oxide, bisacylphosphine oxide, titanocene, fluorescene, anthraquinone, thioxanthone or xanthone, lophine dimer, Trihalomethyl compound or dihalo Chill compounds, active ester compounds, organic boron compounds, and the like.

  A photocrosslinking radical generator such as a bisazide compound may be used in combination with the photoradical generator.

  Examples of the thermal polymerization initiator include azobisisobutyronitrile (AIBN).

  A photoacid generator may be used as the polymerization initiator. In this case, when the applied coating solution is irradiated with light, the photoacid generator generates an acid and the polyfunctional polymerizable compound is crosslinked.

  Examples of the polyfunctional polymerizable compound that crosslinks in the presence of an acid include a compound having a cyclic ether group such as an epoxy group, an oxetane group, and an oxolane group, an acrylic compound or a vinyl compound having the above-described substituent in the side chain, Cationic polymerization of carbonate compounds, low molecular weight melamine compounds, vinyl ethers and vinyl carbazoles, styrene derivatives, α-methylstyrene derivatives, vinyl alcohol esters such as ester compounds of vinyl alcohol with acrylic acid, methacrylic acid, etc. And monomers having a vinyl bond that can be used.

  Examples of photoacid generators include onium salts, diazonium salts, quinonediazide compounds, organic halides, aromatic sulfonate compounds, bisulfone compounds, sulfonyl compounds, sulfonate compounds, sulfonium compounds, sulfamide compounds, iodonium compounds, sulfonyldiazomethane compounds, and the like. Is mentioned. Of these, onium salts are preferred.

  Examples of the onium salt include a diazonium salt and a phosphonium salt having a counter ion of a fluoroborate anion, a hexafluoroantimonate anion, a hexafluoroarsenate anion, a trifluoromethanesulfonate anion, a p-toluenesulfonate anion, and a p-toluenesulfonate anion. And sulfonium salts.

  As other photoacid generators, halogenated triazine compounds can also be used.

  In addition, a photo-acid generator may be used independently and may use 2 or more types together.

  When a photoacid generator is used, a sensitizing dye may be used in combination.

  Examples of the sensitizing dye include acridine compounds, benzoflavins, perylene, anthracene, and laser dyes.

  The coating solution used for manufacturing the porous insulator 10 preferably further contains a porogen. Here, the porogen is used to form the holes 31 in the porous insulator 10.

  The porogen is not particularly limited as long as the polymerizable compound and the polymerization initiator can be dissolved, and the polymerizable compound is a liquid substance that can be phase-separated as the polymerization proceeds. For example, ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, esters such as γ-butyrolactone and propylene carbonate, amides such as N, N-dimethylacetamide, etc. .

  Also, liquid substances having a relatively high molecular weight such as methyl tetradecanoate, methyl decanoate, methyl myristate, tetradecane, etc. tend to function as porogens.

  Among these, ethylene glycols are preferable because they have a high boiling point and improve the production stability of the porous insulator 10.

  In addition, a porogen may be used independently and may use 2 or more types together.

  The viscosity at 25 ° C. of the coating solution used for the production of the porous insulator 10 is preferably 1 to 150 mPa · s, and more preferably 5 to 20 mPa · s. Thereby, since the coating liquid penetrates into the gaps of the active material 22, a part of the porous insulator 10 can be present in a part of the electrode mixture 23.

  Moreover, it is preferable that it is 10-70 mass%, and, as for content of the polymeric compound in a coating liquid, it is more preferable that it is 10-50 mass%. When the content of the polymerizable compound in the coating solution is 10% by mass or more, the strength of the porous insulator 10 is improved, and when it is 70% by mass or less, the coating solution soaks into the gaps of the active material 22. Therefore, a part of the porous insulator 10 can be present in a part of the electrode mixture 23.

  The volume ratio of the polymerizable compound and the solid 12 contained in the coating solution is not particularly limited as long as it can be applied to the porous insulator 10, and can be appropriately selected according to the purpose. The ratio is preferably 1: 1 to 1:15, more preferably 1: 1 to 1:10. Thereby, the shutdown function of the porous insulator 10 is improved.

  The coating method for the coating solution is not particularly limited. For example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method. Various printing methods such as a method, a capillary coating method, a spray coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

  The electrode mixture 23 for a non-aqueous storage element can be formed, for example, by applying a coating liquid in which a powdery active material is dispersed in a dispersion medium, and then drying the coating liquid. .

  As a coating method of the coating liquid, for example, a printing method using spraying, a dispenser, a die coater, or a lift coating can be used.

  The positive electrode active material for the lithium ion secondary battery is not particularly limited as long as it can reversibly occlude and release alkali metal ions, and an alkali metal-containing transition metal compound can be used.

  In addition, a positive electrode active material may be used independently and may use 2 or more types together.

  Examples of the lithium-containing transition metal compound include a composite oxide containing lithium and one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium.

Specific examples of the positive electrode active material include lithium-containing transition metal oxides such as lithium cobaltate, lithium nickelate, and lithium manganate, olivine-type lithium salts such as LiFePO ₄ , chalcogen compounds such as titanium disulfide and molybdenum disulfide, Examples include manganese dioxide.

  The lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal, or a metal oxide in which a part of the transition metal in these metal oxides is substituted with a different element.

  Examples of the different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Among these, Mn, Al, Co, Ni, and Mg are preferable.

  In addition, a different element may be used independently and may use 2 or more types together.

  The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can reversibly occlude and release alkali metal ions, and a carbon material containing graphite having a graphite-type crystal structure is used. be able to.

  Examples of the carbon material include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), and the like.

  Examples of the negative electrode active material other than the carbon material include lithium titanate.

  Further, from the viewpoint of the energy density of the lithium ion secondary battery, a high capacity material such as silicon, tin, silicon alloy, tin alloy, silicon oxide, silicon nitride, and tin oxide can also be used as the negative electrode active material.

  Examples of the positive electrode active material for a nickel metal hydride secondary battery include nickel hydroxide.

Examples of the negative electrode active material for a nickel-hydrogen secondary battery include a Zr—Ti—Mn—Fe—Ag—V—Al—W alloy, a Ti ₁₅ Zr ₂₁ V ₁₅ Ni ₂₉ Cr ₅ Co ₅ Fe ₁ Mn ₈ alloy, and the like. AB ₂ type or A ₂ B type hydrogen storage alloy.

  The electrode mixture 23 may further contain a binder and a conductive agent.

  Examples of the binder include PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, and polyacrylic hexyl. Esters, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene butadiene rubber, carboxymethylcellulose, etc. Can be mentioned.

  As binders other than the above, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, And a copolymer of two or more monomers selected from the group consisting of hexadiene.

  In addition, a binder may be used independently and may use 2 or more types together.

  Examples of the conductive agent include natural graphite, artificial graphite graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and other carbon blacks, and conductive fibers such as carbon fibers and metal fibers. , Metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, conductive materials such as phenylene derivatives and graphene derivatives, etc. Can do.

  The electrode substrate 21 for the non-aqueous storage element is not particularly limited as long as it is a substrate having planarity and conductivity, and is used for secondary batteries and capacitors. Aluminum foil, copper foil, stainless steel foil, titanium foil, Alternatively, an etched foil in which fine holes are formed by etching these, a holed electrode base used in a lithium ion capacitor, or the like can be used.

  As an active material for a fuel cell, a material in which catalyst particles such as platinum particles, ruthenium particles and platinum alloy particles are supported on the surface of a catalyst carrier such as carbon is generally used.

  The electrode mixture 23 for a fuel cell is formed, for example, by applying a coating solution containing a catalyst carrier on which a catalyst particle precursor is supported on the electrode base 21 and then reducing the coating under a hydrogen atmosphere or the like. be able to.

  As a method of supporting the catalyst particle precursor on the surface of the catalyst carrier, for example, the catalyst particle precursor is added to and dissolved in a suspension in which the catalyst carrier is suspended in water. In addition, there is a method in which a metal hydroxide is generated and supported on the surface of a catalyst carrier.

  Catalyst particle precursors include chloroplatinic acid, dinitrodiaminoplatinum, diplatinum chloride, diplatinum chloride, bisacetylacetonatoplatinum, dichlorodiammineplatinum, dichlorotetramineplatinum, diplatinum sulfate ruthenium acid, iridium chloride Examples thereof include acid, rhodium chloride, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, iron sulfate, and copper chloride.

  Examples of the electrode base 21 for the fuel cell include a non-woven or woven flat electrode made of carbon paper used in a fuel cell, and one having fine holes among the perforated electrode base. Can be used.

Examples of active materials for solar cells include WO ₃ powder, TiO ₂ powder, SnO ₂ powder, ZnO powder, ZrO ₂ powder, Nb ₂ O ₅ powder, CeO ₂ powder, SiO ₂ powder, Al ₂ O ₃ powder, and the like. The oxide semiconductor powder is mentioned.

  The electrode mixture 23 for a solar cell can be formed, for example, by applying a coating solution containing an oxide semiconductor powder carrying a dye on the electrode substrate 21.

  Examples of the dye include a ruthenium-tris transition metal complex, a ruthenium-bis transition metal complex, an osmium-tris transition metal complex, an osmium-bis transition metal complex, and a ruthenium-cis-diaqua-bipyridyl complex. Phthalocyanine and porphyrin, organic-inorganic perovskite crystals, and the like.

  As the electrode substrate 21 for a solar cell, a transparent substrate such as an indium / titanium oxide or zinc oxide formed on a flat substrate such as glass or plastic used in a solar cell, conductive A material on which an electrode film is deposited can be used.

<Non-aqueous storage element>
The non-aqueous storage element of this embodiment has the electrode of this embodiment. At this time, the electrode of this embodiment is a positive electrode and / or a negative electrode.

  Although the positive electrode and the negative electrode are arrange | positioned through the separator as for the non-aqueous electrical storage element of this embodiment, it is preferable that the positive electrode and the negative electrode are laminated | stacked alternately via the separator. At this time, the number of stacked positive electrodes and negative electrodes can be arbitrarily determined.

  In addition, since the electrode of this embodiment has the porous insulator of this embodiment, a separator can be omitted as necessary.

  The non-aqueous storage element of this embodiment is preferably filled with a non-aqueous electrolyte and sealed with an exterior. At this time, in order to insulate from the exterior, it is preferable that a separator is provided between the electrodes on both sides and the exterior.

  There is no restriction | limiting in particular as a non-aqueous electrical storage element, Although it can select suitably according to the objective, For example, a non-aqueous secondary battery, a non-aqueous capacitor, etc. are mentioned.

  The shape of the non-aqueous storage element is not particularly limited and can be appropriately selected from known shapes according to its use. For example, a laminate type, a cylinder type in which a sheet electrode and a separator are spiraled And a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, a coin type in which a pellet electrode and a separator are stacked, and the like.

  FIG. 4 shows an example of the non-aqueous storage element of this embodiment.

  The non-aqueous storage element 40 includes a positive electrode 41, a negative electrode 42, a separator 43 that holds a non-aqueous electrolyte, an outer can 44, a lead wire 45 of the positive electrode 41, and a lead wire 46 of the negative electrode 42. .

<Separator>
The separator is provided between the negative electrode and the positive electrode in order to prevent a short circuit between the negative electrode and the positive electrode.

  The separator has ion permeability and does not have electronic conductivity.

  The separator is not particularly limited and can be appropriately selected depending on the purpose.For example, paper such as kraft paper, vinylon mixed paper, synthetic pulp mixed paper, cellophane, polyethylene graft membrane, polypropylene melt flow nonwoven fabric, etc. Examples thereof include a polyolefin nonwoven fabric, a polyamide nonwoven fabric, a glass fiber nonwoven fabric, a polyethylene microporous membrane, and a polypropylene microporous membrane.

  The separator preferably has a porosity of 50% or more from the viewpoint of holding the non-aqueous electrolyte.

  The average thickness of the separator is preferably 3 to 50 μm, and more preferably 5 to 30 μm. When the average thickness of the separator is 3 μm or more, it becomes easy to prevent a short circuit between the negative electrode and the positive electrode, and when it is 50 μm or less, the electrical resistance between the negative electrode and the positive electrode is difficult to increase.

  The shape of the separator is not particularly limited as long as it can be applied to a non-aqueous energy storage device, and can be appropriately selected according to the purpose. Examples thereof include a sheet shape.

  The size of the separator is not particularly limited as long as it can be applied to a non-aqueous storage element, and can be appropriately selected according to the purpose.

  The separator may have a single layer structure or a laminated structure.

<Non-aqueous electrolyte>
The nonaqueous electrolytic solution is an electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent.

<Nonaqueous solvent>
There is no restriction | limiting in particular as a non-aqueous solvent, Although it can select suitably according to the objective, An aprotic organic solvent is preferable.

  As the aprotic organic solvent, carbonate-based organic solvents such as chain carbonates and cyclic carbonates can be used.

  Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), and methyl propionate (MP).

  Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and the like.

  Among these, it is preferable to use ethylene carbonate (EC) and dimethyl carbonate (DMC) in combination. At this time, the ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is not particularly limited and can be appropriately selected according to the purpose.

  In this embodiment, you may use nonaqueous solvents other than a carbonate type organic solvent as needed.

  As the non-aqueous solvent other than the carbonate organic solvent, an ester organic solvent such as a cyclic ester or a chain ester, an ether organic solvent such as a cyclic ether or a chain ether, or the like can be used.

  Examples of the cyclic ester include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.

  Examples of the chain ester include propionic acid alkyl ester, malonic acid dialkyl ester, acetic acid alkyl ester (methyl acetate (MA), ethyl acetate, etc.), formic acid alkyl ester (methyl formate (MF), ethyl formate, etc.) and the like. It is done.

  Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane and the like.

  Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, and the like.

<Electrolyte salt>
The electrolyte salt is not particularly limited as long as it has high ionic conductivity and can be dissolved in a non-aqueous solvent, but a lithium salt is preferable.

The lithium salt is not particularly limited and can be appropriately selected depending on the purpose. For example, lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate (LiClO ₄ ), lithium chloride (LiCl), borofluoride Lithium (LiBF ₄ ), lithium hexafluoroarsenide (LiAsF ₆ ), lithium trifluorometasulfonate (LiCF ₃ SO ₃ ), lithium bis (trifluoromethylsulfonyl) imide (LiN (CF ₃ SO ₂ ) ₂ ), lithium bis (Perfluoroethylsulfonyl) imide (LiN (C ₂ F ₅ SO ₂ ) ₂ ) and the like. Among these, LiPF ₆ is particularly preferable from the viewpoint of the amount of anion stored in the carbon electrode.

  In addition, electrolyte salt may be used independently and may use 2 or more types together.

  The content of the electrolyte salt in the nonaqueous electrolytic solution is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.7 to 4 mol / L, and preferably 1.0 to 3 mol / L. It is more preferable that it is 1.0-2.5 mol / L.

<Applications of non-aqueous energy storage devices>
The application of the non-aqueous storage element of the present embodiment is not particularly limited and can be used for various applications. For example, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, walkie-talkie, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, motor, lighting equipment, toy, game Equipment, watches, strobes, cameras, etc.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

  By using the devices A and B (see FIGS. 5 and 7) produced by the method described later, the following methods are used for insulation, porosity of the porous insulator, and porosity of the porous insulator during heating. Rate change was evaluated.

<Insulation during heating>
Using devices A and B, the insulating properties during heating were evaluated. Specifically, the DC resistance value between the negative electrode substrates when the devices A and B were heated to 200 ° C. was measured. Insulating properties during heating were determined according to the following criteria.

◯: When the DC resistance value between the negative electrode substrates is 1 MΩ or more Δ: When the DC resistance value between the negative electrode substrates is 1 KΩ or more and less than 1 MΩ ×: When the DC resistance value between the negative electrode substrates is less than 1 KΩ <Porous Porosity of insulator>
Using device A, the porosity of the porous insulator at room temperature (25 ° C.) was evaluated. Specifically, first, the device A was filled with unsaturated fatty acid (commercially available butter) and then subjected to osmium staining. Next, after cutting out the cross-sectional structure of the porous insulator inside the device A using a focused ion beam (FIB), the porosity of the porous insulator is measured using a scanning electron microscope (SEM). did. The porosity of the porous insulator was determined according to the following criteria.

A: When the porosity is 50% or more O: When the porosity is 30% or more and less than 50% X: When the porosity is less than 30% <Change in porosity of the porous insulator during heating>
Using device A, the change in the porosity of the porous insulator during heating was evaluated. Specifically, first, device A was heated at 200 ° C. for 15 minutes using a hot plate. Next, after filling device A with unsaturated fatty acid (commercially available butter), osmium staining was performed. Next, after cutting out the cross-sectional structure of the porous insulator inside the device A using a focused ion beam (FIB), the porosity of the porous insulator during heating is measured using SEM, The difference from the porosity of the porous insulator was determined. The change in the porosity of the porous insulator during heating was determined according to the following criteria.

◎: When the porosity reduction is 30% or more ◯: When the porosity reduction is 5% or more and less than 30% △: When the porosity reduction is 1% or more and less than 5% ×: Porosity When the decrease is less than 1% <Example 1>
Device A shown in FIG. 5 was manufactured by the steps shown in [1] to [3].

[1] Preparation of ink for porous insulator 14 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex) as a crosslinkable monomer, dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen ) 32 parts by mass, 0.7 part by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, and 54 parts by mass of polypropylene (PP) wax particles having a melting point of 140 ° C. (manufactured by Mitsui Chemicals) as resin particles Then, an ink for a porous insulator was prepared.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1: 4.

[2] Formation of porous insulator After applying ink for porous insulator on a copper foil having a thickness of 8 μm as a negative electrode substrate using a dispenser, UV irradiation is performed in an N ₂ atmosphere. The crosslinkable monomer was crosslinked. Next, the solvent was removed by heating at 100 ° C. for 1 minute using a hot plate to form a porous insulator.

  As a result of observing the surface of the porous insulator using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed (see FIG. 6).

[3] Fabrication of Device A Device A was fabricated by superposing an 8 μm-thick copper foil as a negative electrode substrate on the negative electrode substrate on which a porous insulator was formed.

  Next, device A was used to evaluate changes in insulation during heating, porosity of the porous insulator, and porosity of the porous insulator during heating (see Table 2).

  In addition, when the direct current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation of 20 Mohm or more was shown.

  Next, the device B shown in FIG. 7 was manufactured by the steps shown in [4] to [6].

[4] Formation of negative electrode mixture 97 parts by mass of graphite particles having an average particle diameter of 10 μm as a negative electrode active material, 1 part by mass of cellulose as a thickener, and 2 parts by mass of acrylic resin as a binder The negative electrode mixture ink was obtained by uniformly dispersing in water.

  The negative electrode mixture ink was applied on a copper foil having a thickness of 8 μm as a negative electrode substrate using a dispenser, dried at 120 ° C. for 10 minutes, and pressed to form a negative electrode mixture having a thickness of 60 μm. .

  Finally, the electrode base on which the negative electrode mixture was formed was cut out to 50 mm × 33 mm.

[5] Formation of porous insulator After applying the ink for porous insulator on the electrode substrate on which the negative electrode mixture is formed, using a dispenser, UV irradiation is performed in an N ₂ atmosphere. The crosslinkable monomer was crosslinked. Next, the solvent was removed by heating at 100 ° C. for 1 minute using a hot plate to form a porous insulator.

  As a result of observing the surface of the porous insulator using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

[6] Production of Device B Device B was produced by superposing an 8 μm-thick copper foil as a negative electrode substrate on an electrode substrate on which a porous insulator was formed.

  Next, using device B, the insulation during heating was evaluated (see Table 2).

<Example 2>
[1] Preparation of ink for porous insulator 14 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex) as a crosslinkable monomer, dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen ) 32 parts by mass, 0.7 part by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, and 54 parts by mass of polyethylene (PE) wax particles (manufactured by Mitsui Chemicals) having a melting point of 110 ° C. as resin particles Then, an ink for a porous insulator was prepared.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1: 4.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 3>
[1] Preparation of ink for porous insulator 9 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex) as a crosslinkable monomer, dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen ) 20 parts by mass, 0.4 part by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, 70 parts by mass of polyvinylidene fluoride (PVDF) particles Trepearl (manufactured by Toray Industries, Inc.) having a melting point of 151 ° C. as resin particles By mixing, an ink for porous insulator was prepared.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1: 4.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 4>
[1] Preparation of ink for porous insulator 23 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex) as a crosslinkable monomer, dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen ) 53 parts by mass, 1.1 parts by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, 23 parts by mass of polypropylene wax particles having a melting point of 140 ° C. (manufactured by Mitsui Chemicals) as resin particles are mixed and porous An insulating insulator ink was prepared.

  Here, the volume ratio of the crosslinkable monomer and the resin particles contained in the porous insulator ink is 1: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 5>
As a crosslinkable monomer, 23 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 53 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Irgacure 184 (manufactured by BASF) 1.1 parts by mass and 23 parts by mass of polyethylene wax particles having a melting point of 110 ° C. (manufactured by Mitsui Chemicals) as resin particles were mixed to prepare an ink for porous insulator.

  Here, the volume ratio of the crosslinkable monomer and the resin particles contained in the porous insulator ink is 1: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 6>
19 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex) as a crosslinkable monomer, 43 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Irgacure 184 (manufactured by BASF) 0.9 parts by mass and 37 parts by mass of polyvinylidene fluoride particle trepal (manufactured by Toray Industries, Inc.) having a melting point of 151 ° C. as resin particles were mixed to prepare a porous insulator ink.

  Here, the volume ratio of the crosslinkable monomer and the resin particles contained in the porous insulator ink is 1: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 7>
When preparing an ink for porous insulator, AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator is used instead of a photopolymerization initiator, and when forming a porous insulator, UV is used. The devices A and B were prepared in the same manner as in Example 1 except that the material was heated to 70 ° C. instead of irradiating the film, and the insulation during heating, the porosity of the porous insulator, the porous insulation during heating Changes in body porosity were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 8>
When preparing an ink for porous insulator, AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator is used instead of a photopolymerization initiator, and when forming a porous insulator, UV is used. The devices A and B were prepared in the same manner as in Example 2 except that the material was heated to 70 ° C. instead of irradiating, and the insulation during heating, the porosity of the porous insulator, the porous insulation during heating Changes in body porosity were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 9>
When preparing an ink for porous insulator, AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator is used instead of a photopolymerization initiator, and when forming a porous insulator, UV is used. The devices A and B were prepared in the same manner as in Example 3 except that the material was heated to 70 ° C. instead of irradiating, and the insulation during heating, the porosity of the porous insulator, the porous insulation during heating Changes in body porosity were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 10>
As a crosslinkable monomer, 26 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 60 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Ink for porous insulator was prepared by mixing 1.0 part by mass of Irgacure 184 (manufactured by BASF) and 13 parts by mass of polypropylene wax particles having a melting point of 140 ° C. (manufactured by Mitsui Chemicals) as resin particles.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 2: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 11>
As a crosslinkable monomer, 26 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 60 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Ink for porous insulator was prepared by mixing 1.0 part by mass of Irgacure 184 (manufactured by BASF) and 13 parts by mass of polyethylene wax particles having a melting point of 110 ° C. (manufactured by Mitsui Chemicals) as resin particles.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 2: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 12>
As a crosslinkable monomer, 23 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 53 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Then, 1.0 part by mass of Irgacure 184 (manufactured by BASF) and 23 parts by mass of polyvinylidene fluoride particle trepar (manufactured by Toray Industries, Inc.) having a melting point of 151 ° C. as resin particles were mixed to prepare a porous insulator ink.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 2: 1.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 13>
As a crosslinkable monomer, 6 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 13 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Irgacure 184 (manufactured by BASF) 0.3 parts by mass and 81 parts by mass of polypropylene wax particles having a melting point of 140 ° C. (manufactured by Mitsui Chemicals) as resin particles were mixed to prepare a porous insulator ink.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1:14.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 14>
As a crosslinkable monomer, 6 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 13 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Irgacure 184 (manufactured by BASF) 0.3 parts by mass and 81 parts by mass of polyethylene wax particles having a melting point of 110 ° C. (manufactured by Mitsui Chemicals) as resin particles were mixed to prepare a porous insulator ink.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1:14.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Example 15>
As a crosslinkable monomer, 3 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Daicel Ornex), 7 parts by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) as a porogen, as a photopolymerization initiator Irgacure 184 (manufactured by BASF), 0.2 parts by mass, and 89 parts by mass of polyvinylidene fluoride particle trepar (manufactured by Toray Industries, Inc.) having a melting point of 151 ° C. as resin particles were mixed to prepare a porous insulator ink.

  Here, the volume ratio of the crosslinkable monomer to the resin particles contained in the porous insulator ink is 1:14.

  Except for using the above porous insulator ink, the steps [2] to [7] were carried out in the same manner as in Example 1 to produce devices A and B. Changes in the porosity of the porous insulator and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Comparative Example 1>
[1] Preparation of ink for porous insulator 20 parts by mass of polypropylene wax particles having a melting point of 140 ° C. (made by Mitsui Chemicals) as resin particles, 1 mass of polyvinylidene fluoride W # 9100 (made by Kureha) as a binder Part and 79 parts by mass of cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent were mixed to prepare a porous insulator ink.

When forming the porous insulator, devices A and B were used in the same manner as in Example 1 except that the obtained porous insulator ink was used and UV irradiation was omitted in an N ₂ atmosphere. And the change in the insulating property during heating, the porosity of the porous insulator, and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Comparative example 2>
Devices A and B were prepared in the same manner as in Comparative Example 1 except that polyethylene wax particles (manufactured by Mitsui Chemicals, Inc.) having a melting point of 110 ° C. were used instead of polypropylene wax particles when preparing the porous insulator ink. And the change in the insulating property during heating, the porosity of the porous insulator, and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

<Comparative Example 3>
In preparing the porous insulator ink, instead of polypropylene wax particles, the same procedure as in Comparative Example 1, except that polyvinylidene fluoride particle trepal (manufactured by Toray Industries, Inc.) having a melting point of 151 ° C. was used. B was prepared, and the insulation during heating, the porosity of the porous insulator, and the change in the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

<Comparative example 4>
Devices A and B were prepared in the same manner as in Comparative Example 1 except that silica particles having high heat resistance (manufactured by JGC Catalysts and Chemicals Co., Ltd.) were used instead of polypropylene wax particles when preparing the porous insulator ink. And the change in the insulating property during heating, the porosity of the porous insulator, and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

<Comparative Example 5>
Devices A and B were prepared in the same manner as in Example 1 except that polypropylene wax particles were not added when preparing the porous insulator ink, and the insulation during heating and the voids in the porous insulator were performed. The change in porosity and the porosity of the porous insulator during heating was evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Comparative Example 6>
Devices A and B were prepared in the same manner as in Example 1 except that silica particles having high heat resistance (manufactured by JGC Catalysts and Chemicals Co., Ltd.) were used instead of polypropylene wax particles when preparing the porous insulator ink. And the change in the insulating property during heating, the porosity of the porous insulator, and the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Comparative Example 7>
Devices A and B were prepared in the same manner as in Example 1 except that cyclohexanone having high solubility in the polymer of the crosslinkable monomer was used instead of porogen when preparing the porous insulator ink. In addition, the insulating property during heating, the porosity of the porous insulator, and the change in the porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were not formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

<Comparative Example 8>
Devices A and B were prepared in the same manner as in Comparative Example 5 except that cyclohexanone having high solubility in a crosslinkable monomer was used instead of porogen when preparing the porous insulator ink. Insulation properties, porosity of the porous insulator, and changes in porosity of the porous insulator during heating were evaluated (see Table 2).

  As a result of observing the surfaces of the porous insulators of devices A and B using SEM, it was found that macropores having a pore diameter of about 0.1 to 10 μm were not formed.

  Moreover, when the direct-current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation property of 20 Mohm or more was shown.

  Table 1 shows the configuration of the porous insulator ink.

Here, the volume ratio is a volume ratio of the crosslinkable monomer and the resin particles contained in the porous insulator ink.

<Comparative Example 9>
The device A shown in FIG. 5 was produced by the process shown in [1].

[1] Fabrication of device A A polyolefin porous film, UPORE (manufactured by Ube Industries Co., Ltd.) having macropores with a pore diameter of 0.1 to 10 μm on a copper foil having a thickness of 8 μm as a negative electrode substrate, copper having a thickness of 8 μm The device A was produced by superimposing the foils, and the insulation during heating was evaluated (see Table 2).

  In addition, when the direct current resistance value between the negative electrode base | substrates of the device A was measured at room temperature, the high insulation of 20 Mohm or more was shown.

  Next, the device B shown in FIG. 7 was manufactured by the process shown in [2].

[2] Fabrication of device B Polyolefin porous film Upore (manufactured by Ube Industries Co., Ltd.) having macropores with a pore diameter of about 0.1 to 10 μm on the electrode substrate on which the negative electrode composite is formed, and a copper foil having a thickness of 8 μm A device B was produced in the same manner as in Example 1 except that the two layers were superposed, and the insulation during heating was evaluated (see Table 2).

  Using devices A and B, the insulating properties during heating, the porosity of the porous insulator, and changes in the porosity of the porous insulator during heating were evaluated (see Table 2).

  Table 2 shows the evaluation results of the insulating property during heating, the porosity of the porous insulator, and the change in the porosity of the porous insulator during heating.

From Table 2, it can be seen that the porous insulators of Examples 1 to 15 have a high porosity. Moreover, since the porous insulator of Examples 1-15 has the big change of the insulation at the time of a heating, and the porosity at the time of a heating, it turns out that a shape maintenance function and a shutdown function are high. This is because a porous structure is formed by a cross-linked polymer compound having high heat resistance by using an ink for porous insulator containing an appropriate cross-linking monomer, porogen, and resin particles. This is considered to be because the insulation of the body was maintained. In addition, since the porous insulator has resin particles having a melting point lower than that of the polymer compound, the resin particles melt before the shape of the polymer compound changes during heating, and the porous structure has an empty space. Since the hole is closed, the shutdown function is considered to be high.

  Since the porous insulator of Example 1 has a higher resin particle content than the porous insulator of Example 4, the porosity of the porous insulator during heating is large, and the shutdown function is high. it is conceivable that.

  The porous insulators of Examples 2, 3, 5, and 6 include resin particles having a melting point different from that of Example 1, but the resin particles have a lower melting point than the polymer compound. The same effect as the porous insulator of Example 1 is obtained.

  The porous insulators of Examples 7 to 9 are obtained by crosslinking the crosslinkable monomer using a thermal polymerization initiator, but the same effects as those of the porous insulators of Examples 1 to 6 are obtained and appropriate. It shows that a porous insulator having a high shape maintaining function, a shutdown function, and a high porosity can be formed by using an ink for a porous insulator containing a crosslinkable monomer, a porogen, and resin particles.

  Since the porous insulators of Examples 10 to 12 have a small resin particle content, the change in porosity during heating is smaller than that of the porous insulators of Examples 1 to 9.

  Since the porous insulators of Examples 13 to 15 have a high content of resin particles, the porosity is lower than that of the porous insulators of Examples 1 to 9.

  Since the porous insulators of Comparative Examples 1 to 3 are composed of resin particles and a binder, they have a shutdown function, but have a low porosity. This is considered to be because the resin particles have a structure close to the closest packing. Moreover, since the resin particle which comprises a porous structure will change to a liquid and the shape will change rapidly when the porous insulator of Comparative Examples 1-3 reaches predetermined | prescribed temperature, a shape maintenance function is low.

  Since the porous insulator of Comparative Example 4 has silica particles with high heat resistance, the shape maintaining function is high, but it has the same structure as the porous insulators of Comparative Examples 1 to 3, so the porosity is low. . Further, since the silica particles do not melt even when the temperature reaches 200 ° C., the porous insulator of Comparative Example 4 has a small change in porosity during heating and a low shutdown function.

  The porous insulators of Comparative Examples 5 and 6 have a porosity, but do not contain resin particles, so the change in the porosity during heating is small and the shutdown function is low.

  The porous insulators of Comparative Examples 7 and 8 have a high porosity but a low porosity. This is considered to be due to the fact that the phase separation hardly proceeds even when the polymerization of the crosslinkable monomer proceeds because the solubility of the crosslinkable monomer in the solvent is high.

  The porous insulator of Comparative Example 9 has a high porosity and a shutdown function, but has a low insulating property during heating. This is considered to be caused by heat shrinkage due to distortion during the production of the porous insulator.

DESCRIPTION OF SYMBOLS 10 Porous insulator 11 Porous structure 12 Solid 12 'Liquid 20 Electrode 21 Electrode base 22 Active material 23 Electrode compound 31 Hole 40 Nonaqueous storage element

International Publication No. 2006/062153

Claims (6)

A porous structure formed of a polymer compound and having pores communicating with each other;
A porous insulator having a solid having a melting point or a glass transition point lower than that of the polymer compound.   The porous insulator according to claim 1, wherein the solid is resin particles.   The porous insulator according to claim 1, wherein the polymer compound is crosslinked. An electrode mixture containing an active material is formed on the electrode substrate,
An electrode, wherein the porous insulator according to any one of claims 1 to 3 is formed on the electrode mixture.   The electrode according to claim 4, wherein a part of the porous insulator is present in a part of the electrode mixture.   A non-aqueous storage element comprising the electrode according to claim 4.