JP2018141155A - Method for manufacturing base material having surface coating layer of network three-dimensional structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide method for manufacturing a base material having a surface coating layer of a network three-dimensional structure excellent in impregnation characteristics of a solvent, conductivity and conduction durability.SOLUTION: In a method for coating a composition (X) produced by graft-polymerizing a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and a polymerizable functional group with a fluorine-based polymer or a composition including Xand at least one kind of material selected from (X) and (X) as given below: X: a molten salt composed of an onium cation and a halogen atom-containing anion, or a molten salt monomer having a salt structure composed of the same and having a polymerizable functional group; and X: a polymer or a copolymer of a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group, the method comprises the steps as given below: (1) a step of coating a solvent solution of the composition on a base material; (2) a step of subjecting the coating layer to mist treatment; (3) a step of cleaning by spraying or a water bath; and (4) a step of drying.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a substrate having a surface coating layer having a network-like three-dimensional structure, and since the substrate having a surface coating layer having a network-like three-dimensional structure has excellent conductivity, It is useful as a separator for various applications requiring electrical conductivity, particularly for lithium ion secondary batteries. Furthermore, by applying a surface coating with a network-like three-dimensional structure to various resin materials and natural materials, it is widely used in applications requiring electrical conductivity used in industrial and household applications.

  Various polymer electrolyte compositions having excellent conductivity are known. For example, a monomer composition containing a molten salt monomer having a quaternary ammonium salt structure comprising a quaternary ammonium cation and a halogen atom-containing anion and a polymerizable functional group, and a charge transfer ion source, Composite polymer electrolyte compositions produced by graft polymerization in the presence of fluorine-based polymers such as vinylidene fluoride have been developed (Patent Documents 1 and 2). Non-Patent Document 1 describes a conductive polymer such as polyaniline. Patent Documents 1 and 2 describe that a separator for a lithium ion secondary battery is coated with a polymer electrolyte composition, but about forming a surface coating layer having a network three-dimensional structure by a treatment after coating. Not listed. Furthermore, when forming the surface coat layer of base materials, such as a resin film and a sheet | seat, it does not describe about providing electroconductivity, forming a network-like three-dimensional structure and utilizing the characteristic of a base material.

International Publication WO2004 / 088671 International Publication WO2010 / 113971

Literature

Issued on June 9, 2014 "High-functionality of conductive polymer materials and the forefront of application development" (NTN Publishing)

  The present invention relates to a substrate having a surface coating layer having a network-like three-dimensional structure excellent in conductivity and conductive durability, in particular, a porous separator for lithium ion secondary batteries, a resin film widely used, and various material sheets It is an object of the present invention to provide a method for producing a surface coat layer.

The above object is to provide a polymer conductive composition (X) obtained by graft polymerization of a molten salt monomer having a salt structure comprising an onium cation and a halogen atom-containing anion and having a polymerizable functional group onto a fluorine-based polymer. ¹ ) or X ¹ and at least one substance selected from the following (X ² ) to (X ⁴ ):
X ² : a molten salt comprising an onium cation and a halogen atom-containing anion, or a molten salt monomer having a salt structure thereof and having a polymerizable functional group,
X ³ : a polymer or copolymer of a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group,
A method for producing a surface coating layer having a network-like three-dimensional structure by coating a base material with a polymer conductive composition comprising a substrate having a network-like three-dimensional surface coating layer, comprising the following steps: Is achieved.
(1) A step of coating the one or both surfaces of the substrate with the solvent solution of the polymer conductive composition,
(2) a step of mist processing the coating layer;
(3) A step of washing the mist-treated coating layer with a spray and / or a water bath,
(4) A step of drying the washed coating layer.

  The above object is more preferably achieved in the above invention by including the step (5) of putting the waste liquid after washing into an ionic liquid and separating the polymer conductive composition and the solvent in the waste liquid.

Further, the above object is to provide a polymer conductive composition obtained by graft polymerization of a molten salt monomer having a salt structure comprising an onium cation and a halogen atom-containing anion and having a polymerizable functional group onto a fluorine-based polymer. (X ¹ ) or X ¹ and at least one substance selected from the following (X ² ) to (X ³ ) X ² : a molten salt comprising an onium cation and a halogen atom-containing anion, or a salt structure thereof And a molten salt monomer having a polymerizable functional group,
X ³ : A polymer conductive composition containing a polymer or copolymer of a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group is coated on a substrate. In the method for forming a surface coating layer having a network-like three-dimensional structure, the method includes a step of performing a plasma treatment before coating the base material with the polymer conductive composition, and includes the following steps, so that the network-like three-dimensional structure is more preferably included. A substrate having a surface coat layer can be obtained.
(1) A step of coating a substrate with a solvent solution of the polymer conductive composition on one or both sides,
(2) a step of mist processing the coating layer;
(4) A step of drying the washed coating layer.

According to the present invention, as will be apparent from the examples described later, a group having a surface coating layer having a network-like three-dimensional structure excellent in conductivity, particularly conductive durability, excellent in strength, and excellent in solvent impregnation properties. A material can be obtained. The obtained base material is useful as a conductive material. The conductivity by blending a solid electrolyte such as LIZ based material and _{Li 1.5 Al 0.5 Ge 1.5 P 3} O 12 , such as _Li 7 _La 3 _Zr 2 _{O 12} to the surface coat layer or substrate It can be improved, or a base material that exhibits not only ionic conduction but also electronic conduction can be obtained by blending various conductive materials.

These show the manufacturing process of this invention.

In the production method of the present invention, the effect of the present invention is manifested by combining the above-mentioned specific polymer conductive composition on the substrate and the above-mentioned treatment method for the specific substrate.
Accordingly, first, a polymer conductive composition (X) obtained by graft polymerization of a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group onto a fluorine-based polymer. ¹ ) is described.

Preferred examples of the fluorine-based polymer used for the graft polymerization include a polyvinylidene fluoride polymer or a copolymer. Also, as the polyvinylidene fluoride copolymer, vinylidene fluoride is represented by the formula:-(CR ¹ R ^2- CFX)-
In the formula, X is a halogen atom other than fluorine, R ¹ and R ² are a hydrogen atom or a fluorine atom, and both may be the same or different. , Chlorine atom is most suitable, but bromine atom and iodine atom are also mentioned,
A preferred example is a copolymer having a unit represented by:

In addition, as the fluorine-based polymer,
Formula _{^{:-( CR 3 R 4 -CR 5 F}} ) n - (CR 1 R 2 -CFX) m -
In the formula, X is a halogen atom other than fluorine,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom or a fluorine atom, and these may be the same or different,
n is 65 to 99 mol%,
m is 1-35 mol%,
And a copolymer represented by
Formula _{;-( CH 2 -CF 2) n -} (CF 2 -CFCl) m -
In the formula, n is 65 to 99 mol%,
m is 1-35 mol%,
The copolymer shown by these is suitable.

When the total of n and m is 100 mol%, n is preferably 65 to 99 mol%, m is preferably 1 to 35 mol%, more preferably n is 67 to 97 mol%, m is It is 3 to 33 mol%, optimally n is 70 to 90 mol%, and m is 10 to 30 mol%.
The fluoropolymer may be a block polymer or a random copolymer. In addition, other copolymerizable monomers can be used as long as the object of the present invention is not impaired.
The molecular weight of the fluoropolymer is preferably 30,000 to 2,000,000, more preferably 100,000 to 1,500,000 as a weight average molecular weight. Here, the weight average molecular weight is measured by an intrinsic viscosity method [η] as described later.

In order to graft polymerize the molten salt monomer to the fluoropolymer, an atom transfer radical polymerization method using a transition metal complex can be applied. The transition metal coordinated to this complex is a starting point by drawing out halogen atoms other than fluorine (for example, chlorine atoms) and further hydrogen atoms in the copolymer, and the molten salt monomer is incorporated into the polymer. Graft polymerize.
In the atom transfer radical polymerization used in the present invention, a copolymer of a vinylidene fluoride monomer and a vinyl monomer containing fluorine and a halogen atom other than fluorine (for example, a chlorine atom) is preferably used. Since the bond energy between carbon and halogen is lowered due to the presence of fluorine atoms and halogen atoms other than fluorine atoms (for example, chlorine atoms) in the trunk polymer, the extraction of halogen atoms other than fluorine (for example, chlorine atoms) by transition metals, Furthermore, drawing of hydrogen atoms occurs more easily than fluorine atoms, and graft polymerization of the molten salt monomer is started. In the present invention, a homopolymer of vinylidene fluoride monomer can also be used.

Transition metal halides are used as catalysts used in atom transfer radical polymerization, especially copper catalysts containing copper atoms such as copper (I) chloride, copper acetylacetonate (II), CuBr (I), CuI (I), etc. Are preferably used. The ligand forming the complex is 4,4′-dialkyl-2,2′-bipyridyl (bpy, etc.) (wherein alkyl is preferably C ₁ -C ₈ such as methyl, ethyl, propyl, butyl, etc.) Alkyl), tris (dimethylaminoethyl) amine (Me ₆ -TREN), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA), N, N, N ′, N′— Tetrakis (2-pyridylmethyl) ethylenediamine (TPEN), tris (2-pyridylmethyl) amine (TPMA) and the like are used. Among these, transition metal halide complexes formed of copper (I) chloride (CuCl) and 4,4′-dimethyl-2,2′-bipyridyl (bpy) can be preferably used.

As a reaction solvent, a solvent capable of dissolving a fluorine-based polymer can be used. Copolymerization of a vinylidene fluoride monomer and a vinyl monomer containing fluorine and a halogen atom other than fluorine (for example, a chlorine atom). N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile and the like that dissolve the coalesced can be used. The reaction temperature varies depending on the ligand of the complex used, but is usually in the range of 10 to 110 ° C.
In order to perform graft polymerization, radiation such as ultraviolet rays (using a photopolymerization initiator) or an electron beam can be irradiated. Electron beam polymerization is a preferred embodiment because it can be expected to undergo a crosslinking reaction of the polymer itself and a graft reaction of the monomer to the reinforcing material. The irradiation amount is preferably 0.1 to 50 Mrad, more preferably 1 to 20 Mrad.

  The monomer unit constituting the polymer is in a molar ratio range of 98 to 10 mol% and the molten salt monomer in a molar ratio of 2 to 90 mol%, that is, the grafting rate is 2 to 90 mol%. Graft polymerization is performed according to the target plastic properties and pH stability. When graft polymerizing a molten salt monomer to the polymer, the polymer may be either a solution or a solid. These graft polymers can be obtained by the method described in the above-mentioned prior patent WO 2010/113971 of the present applicant.

  In the present invention, the salt structure of a molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and containing a polymerizable functional group is an aliphatic, alicyclic, aromatic or heterocyclic ring. Includes a salt structure consisting of an onium cation and a halogen atom-containing anion. Here, the onium cation means an ammonium cation, a phosphonium cation, a sulfonium cation, an oxonium cation, and a guanidinium cation. Etc. A salt structure comprising at least one cation selected from the following ammonium cation group and at least one anion selected from the following anion group is preferable.

Ammonium cation group:
Pyrrolium cation, pyridinium cation, imidazolium cation, pyrazolium cation, benzimidazolium cation, indolium cation, carbazolium cation, quinolinium cation, pyrrolidinium cation, piperidinium cation, piperazinium cation, Alkyl ammonium cation {including those substituted with an alkyl group having 1 to 30 carbon atoms (for example, 1 to 10 carbon atoms), a hydroxyalkyl group, or an alkoxy group}. Any of them includes N and / or a ring having an alkyl group, hydroxyalkyl group, or alkoxy group having 1 to 30 carbon atoms (for example, 1 to 10 carbon atoms) bonded thereto.
Examples of the phosphonium cation include a tetraalkylphosphonium cation (an alkyl group having 1 to 30 carbon atoms), a trimethylethylphosphonium cation, a triethylmethylphosphonium cation, a tetraaminophosphonium cation, and a trialkylhexadecylphosphonium cation (having 1 to 30 carbon atoms). Alkyl group), triphenylbenzylphosphonium cation, phosphonium cation of a phosphine derivative having three alkyl groups having 1 to 30 carbon atoms, hexyltrimethylphosphonium cation, asymmetric phosphonium cation of trimethyloctylphosphonium cation, and the like.
Examples of the sulfonium cation include a trialkylsulfonium cation (alkyl group), diethylmethylsulfonium cation, dimethylpropylsulfonium, and dimethylhexylsulfonium asymmetric sulfonium cation.

Fluorine atom-containing anions:
BF ₄ ⁻ , PF ₆ ⁻ , C _n F _{2n + 1} CO ₂ ⁻ (n is an integer of 1 to 4), C _n F _{2n + 1} SO ₃ ⁻ (n is an integer of 1 to 4), (FSO ₂ ) ₂ N ^{_{-, (CF 3 SO 2)}} 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) 3 N -, CF 3 SO 2 -N-COCF 3 -, R-SO 2 - Examples include anions containing halogen atoms such as N—SO ₂ CF ₃ ^— (R is an aliphatic group), ArSO ₂ —N—SO ₂ CF ₃ ^— (Ar is an aromatic group), CF ₃ COO ^{—, and the} like. .

  The species listed in the onium cations, particularly the ammonium cation group and the fluorine atom-containing anion group, are excellent in heat resistance, reduction resistance or oxidation resistance, have a wide electrochemical window, and have a voltage range of 0.7 to 5. Not only is it suitable for use in lithium-ion secondary batteries that are resistant to high and low voltages up to 5 V and lithium-ion capacitors that are excellent in low-temperature characteristics up to -45 ° C. As a kneading additive, it is possible to impart functional antistatic performance with excellent temperature characteristics to a non-conductive resin. Moreover, it is effective in the dispersion | distribution performance and smoothness performance of resin and an additive by mixing formulation with resin.

  Examples of the polymerizable functional group in the monomer include cyclic ethers having a carbon-carbon unsaturated group such as vinyl group, acrylic group, methacryl group, acrylamide group and allyl group, epoxy group and oxetane group, and tetrahydrothiophene. Examples thereof include cyclic sulfides and isocyanate groups.

(A) An onium cation having a polymerizable functional group, particularly an ammonium cation species, is particularly preferably a trialkylaminoethyl methacrylate ammonium cation, a trialkylaminoethyl acrylate ammonium cation, a trialkylaminopropylacrylamide ammonium cation, or a 1-alkyl. -3-vinylimidazolium cation, 4-vinyl-1-alkylpyridinium cation, 1- (4-vinylbenzyl) -3-alkylimidazolium cation, 2- (methacryloyloxy) dialkylammonium cation, 1- (vinyloxyethyl) ) -3-alkylimidazolium cation, 1-vinylimidazolium cation, 1-allylimidazolium cation, N-alkyl-N-allylammonium cation ON, 1-vinyl-3-alkylimidazolium cation, 1-glycidyl-3-alkyl-imidazolium cation, N-allyl-N-alkylpyrrolidinium cation, and quaternary diallyldialkylammonium cation. . However, alkyl is an alkyl group having 1 to 10 carbon atoms.
(B) As the fluorine atom-containing anion species, bis {(trifluoromethane) sulfonyl} imide anion, bis (fluorosulfonyl) imide anion, 2,2,2-trifluoro-N-{(trifluoromethane) is particularly preferable. Examples include anions such as sulfonyl)} acetimide anion, bis {(pentafluoroethane) sulfonyl} imide anion, tetrafluoroborate anion, hexafluorophosphate anion, trifluoromethanesulfonylimide anion.

Furthermore, as the molten salt monomer (salt with the cationic species and anionic species), particularly preferably, trialkyl aminoethyl methacrylate ammonium (where alkyl is C ₁ -C ₁₀ alkyl) bis (fluorosulfonyl) imide ( Provided that alkyl is C ₁ -C ₁₀ alkyl), 2- (methacryloyloxy) dialkylammonium bis (fluorosulfonyl) imide (wherein alkyl is C ₁ -C ₁₀ alkyl), N-alkyl-N-allylammonium bis { (Trifluoromethane) sulfonyl} imide (wherein alkyl is C ₁ -C ₁₀ alkyl), 1-vinyl-3-alkylimidazolium bis {(trifluoromethane) sulfonyl} imide (wherein alkyl is C ₁ -C ₁₀ alkyl) 1-vinyl-3-alkylimidazolium Tetrafluoroborate (where alkyl is _C 1 _{-C 10} alkyl), 4-vinyl-1-alkylpyridinium bis {(trifluoromethanesulfonyl) sulfonyl} imide (where alkyl is _C 1 _{-C 10} alkyl), 4-vinyl - 1-alkyl pyridinium tetrafluoroborate (where alkyl is _C 1 _{-C 10} alkyl), 1- (4-vinylbenzyl) -3-alkylimidazolium bis {(trifluoromethanesulfonyl) sulfonyl} imide (where alkyl is _{C 1} -C ₁₀ alkyl), 1- (4-vinylbenzyl) -3-alkylimidazolium tetrafluoroborate (where alkyl is _C 1 _{-C 10} alkyl), 1-glycidyl-3-alkyl - imidazolium bis {(trifluoperazine Lomethane) sulfonyl} imide (however, alkyl C ₁ -C ₁₀ alkyl), trialkyl aminoethyl methacrylate ammonium trifluoromethanesulfonyl imide (where alkyl is _C 1 _{-C 10} alkyl), 1-glycidyl-3-alkyl - tetrafluoroborate (where alkyl is C ₁ -C ₁₀ alkyl), N- vinyl carba tetrafluoroborate (where alkyl can be exemplified _C 1 _{-C 10} alkyl), and the like. These molten salt monomers can be used alone or in combination of two or more. These molten salt monomers are obtained by the method described in the above-mentioned prior patent WO 2010/113971 of the present applicant.

  The graft ratio of the molten salt monomer to the fluoropolymer is preferably 2 to 90 mol%, more preferably 10 to 80 mol%, and most preferably 20 to 75 mol%. By satisfying the grafting ratio in this range, the object of the present invention can be achieved more suitably. In a region where the grafting rate is relatively low, for example, 2 to 40 mol%, preferably 10 to 35 mol%, more preferably 13 to 30 mol%, the sponge-like flexibility can be maintained, and the support Expected to be improved in adhesion and elasticity to the body, elasticity and adhesion. Further, in a region where the grafting rate is relatively high, such as 42 to 90 mol%, particularly 45 to 90 mol%, more preferably 45 to 75 mol%, the adhesion strength is improved because viscoelasticity increases. Furthermore, effects such as adhesion, impact resistance, dispersion smoothness of particle materials such as pigments, pH stability, temperature stability, and further improvement in conductive performance can be expected. The method for measuring the grafting rate will be described in Examples described later.

The graft polymerization of the molten salt monomer may be used alone or in combination with other monomers.
Here, in the polymer electrolyte composition (X ¹ ), SEI (solid electrolyte interface) film formation such as vinylene carbonates, vinylene acetate, 2-cyanofuran, 2-thiophenecarbonitrile, acrylonitrile and the like is formed. The monomer composition containing a raw material or a solvent is included.

In the present invention, the polymer conductive composition (X ¹ ) has a molten salt (ionic liquid) composed of an onium cation and a halogen atom-containing anion, and a polymerizable functional group having a salt structure composed of an onium cation and a halogen atom-containing anion. By adding a molten salt monomer salt (ionic liquid) (X ² ) having a group, or a polymer or copolymer (X ³ ) of the molten salt monomer, conductivity and conductivity durability are further improved. It can also be improved.
Here, as the molten salt composed of an onium cation and a halogen atom-containing anion, a molten salt composed of the ammonium cation group and the halogen atom-containing anion group, for example, a cyclic conjugated ionic liquid sharing a cation with two nitrogens, Examples include acyclic aliphatic ionic liquids containing alkylammonium and phosphonium, cyclic aliphatic ionic liquids containing quaternary ammonium, and various ionic liquids of pyrrolidinium cations. More specifically, 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide} (EMI • FSI), 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide} (EMI • TFSI) ), 1-butyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide} (BMI · FSI), and the like. The molten salt monomer having a salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group includes the molten salt monomer used in the graft polymerization described above.

Here, the halogen of the halogen atom-containing anion includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is optimal.
Moreover, as a polymer or copolymer of a molten salt monomer, the homopolymer of the said molten salt monomer is mentioned as a suitable example. Among these homopolymers, 1-alkyl-3-vinylimidazolium cation (AVI), 4-vinyl-1-alkylpyridinium cation, 1- (4-vinylbenzyl) -3-alkylimidazolium cation, 1- ( Vinyloxyethyl) -3-alkylimidazolium cation, 1-vinylimidazolium cation, quaternary diallyldialkylammonium cation (DAA), 2- (methacryloyloxy) ethyltrimethylammonium (MOETMA)} cation, dialkyl (aminoalkyl) acrylamide , Dialkyl (aminoalkyl) acrylates, homopolymers of hydroxyalkyl methacrylates, or copolymers of two or more of these monomers, with homopolymers being preferred. Moreover, the copolymer of the said molten salt monomer and another comonomer is mentioned. Further, in the polymer or copolymer (X ³ ) of these molten salt monomers, a monomer other than the molten salt monomer can be used as long as the object of the present invention is not hindered.

  Polymers or copolymers of these molten salt monomers include radical polymerizations using azo polymerization initiators (AIBN, etc.), peroxide polymerization initiators (BPO, etc.), or Bronsted acids and Lewis acids. It can obtain by the cationic polymerization reaction based on polymerization initiators. Of these polymerizations, radical polymerization is preferred.

The mixing ratio of the polymer conductive composition (X ^1), the polymeric conductive composition (X ¹⁾ and molten salt or molten salt monomer (X ^2), or polymer or copolymerization of the molten salt monomer 5 to 90% by weight, preferably 10 to 75% by weight, based on the total amount of the combined (X ³ ). In the present invention, by adding (X ² ) or (X ³ ) to (X ¹ ), the conductivity, adhesive adhesion, and durability thereof are further improved. One of these or two or more of X ² and X ³ can be used.

Furthermore, in this invention, electroconductivity and electroconductive durability improve by mix | blending a charge-transfer ion source. Here, the charge transfer ion source is typically a lithium salt, and preferably a lithium salt comprising the following lithium cation and fluorine atom-containing anion.
As the charge transfer ion source, LiBF ₄ , C _n F _{2n + 1} CO ₂ Li (n is an integer of 1 to 4), C _n F _{2n + 1} SO ₃ Li (n is an integer of 1 to 4), (FSO ₂ ) ₂ NLi , (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) ₂ NLi, (FSO ₂ ) ₂ CLi, (CF ₃ SO ₂ ) ₃ CLi, (CF ₃ SO ₂ —N—COCF ₃ ) Li,
Examples thereof include a lithium salt selected from the group consisting of (R—SO ₂ —N—SO ₂ CF ₃ ) Li (where R is an aliphatic group such as an alkyl group or an aromatic group). Further, other than lithium salts, generally, charge transfer ion sources such as indium tin oxide (ITO) and carbonates are also included. In general industrial applications, a conductive material imparted with electronic conductivity by blending carbon can be used.

Further, as the charge transfer ion source, a nitrogen-containing salt, preferably a salt composed of the following alkylammonium cation (for example, tetraethylammonium cation, triethylmethylammonium cation) and a fluorine atom-containing anion is also used.
Et ₄ −N ⁺ BF ₄ ⁻ , Et ₃ Me−N ⁺ BF ₄ ^{−
_{Et 4 -N + PF 6 -,}} Et 3 Me-N + PF 6 - and the like.
Two or more of the charge transfer ion sources can be blended.
The amount of the charge transfer ion source is 0.5 to 2 mol, preferably 0.7 to 1.5 mol, relative to the polymer electrolyte composition (X ¹ ).
As alkylene of tetraalkylene glycol dialkyl ether (TAGDAE) which is a counter ion of the charge transfer ion source, alkylene having 1 to 10 carbons such as methylene, ethylene and propylene, and alkyl having 1 carbon such as methyl, ethyl and propyl To 10 alkyls. Of these, tetraethylene glycol dimethyl ether (TEGDME) is most suitable. The blending ratio of TAGDAE to the charge transfer ion source is 0.2 to 2.0 mol, preferably 0.4 to 1.5 mol.

  Further, as anion (ion conductive support salt) for supporting the charge transfer ion source, bis {(trifluoromethane) sulfonyl} imide, 2,2,2-trifluoro-N-{(trifluoromethane) sulfonyl)} acetimide, Bis {(pentafluoroethane) sulfonyl} imide, bis {(fluoro) sulfonyl} imide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonylimide and the like function effectively.

Various solvents are used in the polymer conductive composition. Examples of the solvent include dimethyl sulfoxide (DMSO), N-methylpyrrolidone, dimethylacetamide, acetone, acetonitrile, and a mixed solvent thereof. Water may be used as the solvent. Polymer conductive compositions include adhesives, UV absorbers, UV degradation inhibitors, fluorescent agents, brighteners, fragrances, compatibilizers, dispersants, antioxidants, slip agents, antiblocking agents, fillers. (Silica, calcium carbonate, magnesium hydroxide, talc, ceramics, etc.), dyes, pigments and the like can be appropriately blended depending on the purpose. Examples of the compatibilizer or dispersant include low molecular compounds (1,2-polybutadiene, polyamide / polyphenylene ether copolymer, natural rubber latex, liquid isoprene polymer emulsion), and phthalocyanine (hydroxyl-containing petroleum resin “Rio”). Noble "manufactured by Toyo Ink Manufacturing Co., Ltd.) is preferably used. The filler is preferably incorporated in an amount of 5 to 50% by weight relative to the resin (the total amount of the ^{X 1} or ^{X 1} and ^{X 2} and ^{X 3).} Dilution solvents used in the formulation include aromatic solvents, ether solvents, 2-propanol, N-methylpyrrolidone, ketone solvents, acetone, chloroalkylene solvents, ester solvents, halogen solvents, dimethyl sulfoxide ( DMSO), butyl acetate, cellosolve acetate, etc. can be used. In particular, by containing an ultraviolet absorber, it is possible to form an effective coating film that does not require heat curing as an ultraviolet curable coating material, and the strength of the coating layer is improved. Furthermore, after dissolving in the above solvent, it can be mixed with a ketone solvent and applied to paints and adhesives.

Next, the base material used in the present invention will be described.
Examples of the material for the base material include resins (synthetic resins and natural resins), inorganic substances, and wood. Here, as the resin, polyolefin resin, polyacrylic resin, polyhalogen resin, vinyl acetate resin, polyether resin, diene resin, polyester resin, polyamide resin, polysulfone resin, polyphenylene sulfide, polyimide And at least one resin selected from a base resin, a silicon resin, a polyurethane resin, an epoxy resin, a phenol resin, an amino resin, and a natural resin.

  Here, examples of the polyolefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, hexene polymer or copolymer, and copolystyrene. Examples of the polyacrylic resin include polymethyl methacrylate and polyacrylonitrile. , Polyacrylic acid salt, acrylonitrile-butadiene-styrene copolymer (ABS) and the like, and examples of the polyhalogen-based resin include polyvinyl chloride, polyvinylidene chloride, and resin tetrafluoride. Examples of the vinyl acetate resin include polyvinyl acetate and polyvinyl alcohol. Examples of the polyether resin include polyethylene oxide, polypropylene oxide, and polyether ketone. Examples of the diene resin include butadiene rubber, Examples include chloroprene rubber and isoprene rubber. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyoxybenzoate, unsaturated polyester, polycarbonate, and polycarbonate-polyester polymer alloy resin. Polyamide resins include polycaprolactam resin and polyhexamethylene. Examples include adipate-based resins and polyaromatic polyamide-based resins. Examples of polysulfone-based resins include polysulfone and polyethersulfone. Examples of silicon-based resins include silicone rubber, silicone resin, and polymerizable silicone resin. Examples of amino resins include urea resins and melamine resins, and examples of natural resins include cellulose resins, natural rubber resins, protein resins, guar gum, tamarind, Sutobingamu, xanthan gum, and the like Karagin.

Of these, polyacrylic resins, diene resins, silicon resins, polyolefin resins, polyether resins, and polyimide resins are suitable. In particular, a polyacrylic resin is most suitable, and as the polyacrylic resin, a polymer or copolymer of alkyl acrylate or alkyl (meth) acrylate is preferable, and as the copolymer, hydroxyethyl acrylamide, dialkyl acrylamide, Examples include dialkylaminoalkylacrylamide, acryloylmorpholine, butyl acrylate-benzyl acrylate-4-hydroxybutyl acrylate copolymer, and butyl acrylate-benzyl acrylate-phenoxyethyl acrylate-4-hydroxybutyl acrylate-acrylic acid copolymer.
As an inorganic substance, metal compounds, such as various metals, such as iron, steel, aluminum, and nickel, and a metal oxide, are mentioned.
Of these materials, resins are preferably used in the present invention.

  As the shape of the substrate, various three-dimensional structures such as films, sheets, plates, porous substrates, fibers (filaments, yarns, woven fabrics, knitted fabrics), paper, non-woven fabrics, particles, chips, spherical bodies (beads), deformed bodies Things. Among these shapes, in the present invention, a porous substrate (porous film, porous sheet), particularly a porous separator for a lithium ion secondary battery is preferably used. When various non-porous resin films or sheets are used, the surface coat layer having a network structure can be formed by mist treatment of the surface in the step of forming the surface coat layer.

Next, a method for coating the base material with the polymer conductive composition will be described.
First, (1) a solvent solution of the polymer conductive composition is coated on one side or both sides of a substrate. As a method for coating, a method in which a substrate is passed between rolls and coated with a roll is suitable. However, a comma coat, a die coat, a dip coat, a spray coat, a pressure-bond coat, a confetti thick coat method, and the like can also be applied. In particular, a method of applying a surface coating by blending a polyvinyl alcohol (PVA) composition with a fiber substrate can be applied. Either a continuous type or a batch type manufacturing method can be applied.

Next, (2) the coating layer is subjected to mist treatment. As a method for mist treatment, when the solvent of the solvent solution of the polymer conductive composition is an organic solvent (DMSO, N-methylpyrrolidone, dimethylacetamide, acetone, acetonitrile, etc.), an aqueous mist, preferably water vapor, is preferably used as the mist. Is used. The substrate is moved from top to bottom in the vertical direction, and during that time, one or both sides of the coating layer surface are subjected to mist treatment. Such a vertical mist treatment is suitable, but a horizontal mist treatment in which the substrate is moved in the horizontal direction can also be applied. The temperature of the mist is preferably 30 to 60 ° C, and most preferably 40 to 50 ° C. The mist processing time is preferably 30 seconds to 5 minutes, and most preferably 1 to 3 minutes. The amount of mist used varies depending on the coat thickness and the like, but 1-30 mist g / base material m ² is preferable, and 5-10 mist g / base material m ² is optimal.
When the solvent of the solvent solution of the polymer conductive composition is water, an organic solvent (DMSO, N-methylpyrrolidone, dimethylacetamide, acetone, etc.) is used as the mist.
By performing such a mist treatment, the solvent in the polymer conductive composition is removed, and a surface coat layer having a network three-dimensional structure can be formed. Here, the net-like three-dimensional structure means a structure in which pores exist in a net-like shape to form a three-dimensional structure. The mesh may be a hole having a uniform size and shape, or a hole having a non-uniform size. Further, the mesh-like holes may penetrate through the surface coat layer or may not penetrate.

Next, (3) the coat layer subjected to the mist treatment is washed with a spray and / or a water bath. The spray is mainly water. 10-40 degreeC is suitable for the temperature of the water of a spray and the water of a tank, and 20-30 degreeC is optimal. The treatment time for spraying and water bath treatment needs to be as long as possible to remove the solvent on the surface of the coat layer as much as possible, preferably 30 seconds to 10 minutes, and most preferably 1 to 5 minutes.
Next, (4) the washed coat layer is dried. It is preferable to dry with hot air. The temperature of hot air drying is preferably 30 to 80 ° C, and most preferably 40 to 60 ° C. The hot air drying time is preferably 1 to 10 minutes, and most preferably 3 to 7 minutes.
Next, (5) the waste liquid after washing is put into an ionic liquid, and the polymer conductive composition and the solvent in the waste liquid are separated. Since the ionic liquid selectively absorbs the organic solvent and water, the polymer conductive composition and the organic solvent / water can be efficiently separated, and the polymer conductive composition and the organic solvent can be recovered and utilized.
Examples of the ionic liquid used here include a molten salt composed of an onium cation corresponding to X ² and a halogen atom-containing anion, and a molten salt monomer having these salt structures and having a polymerizable functional group. Is mentioned.

Next, another embodiment of the method of the present invention will be described.
In the method of coating a base material with a polymer conductive composition to form a surface coating layer having a three-dimensional network structure, the method includes a step of plasma treatment before coating the base material with the polymer conductive composition. According to this method, it is possible to obtain a base material having a surface-coated layer having a network three-dimensional structure by including the following steps.
(1) A step of coating a substrate with a solvent solution of the polymer conductive composition on one or both sides,
(2) a step of mist processing the coating layer;
(4) A step of drying the washed coating layer.
That is, according to this method, there is an advantage that the step (3) of cleaning the mist-treated coat layer by the spray and / or water bath in the above method can be omitted.
Here, as the plasma treatment, it is preferable to perform surface glow treatment with a direct current (DC) power of 30 to 200 W in a vacuum environment, and 40 to 100 W is optimal. The treatment time is preferably from 30 seconds to 3 minutes, and most preferably from 1 to 2 minutes. It is preferable to perform plasma treatment on the entire surface of the substrate.

In the present invention, both continuous type and batch type can be applied. Here, as a batch type method, a method of coating fine particles on a substrate by ultrasonic emulsification method, a method of depositing the surface of the polymer conductive composition by laser irradiation and surface coating, enzyme-immobilized carbon black and the polymer A method of surface-coating a composite with a conductive composition on a substrate, a method of coating a surface of a substrate by forming nanocomposite particles by treating inorganic particles with the above-described polymer conductive composition solution, a neuron-type polymer A method of forming a conductive composition and surface-coating the substrate, a method of coating the surface by forming a composite by light irradiation after mixing metal cation nanoparticles with the polymer composition containing the dopant anion, and a rust preventive material And a method of coating the surface of the base material by mixing a rust preventive pigment with the above polymer conductive tax, and the like.
Further, according to the method of the present invention, for example, after a porous polymer substrate for lithium ion battery (LIB) is coated with a conductive polymer composition (electrolytic polymer composition) and deeply impregnated to the inside, the LIB cell is manufactured. The cell can be further cured to form a polymer solid electrolyte, which is termed a two-shot solid electrolyte molding method. Moreover, rate characteristics and cycle characteristics can be improved by coating the positive and negative electrode plates with a polymer conductive composition. Furthermore, by combining these methods, it is possible to develop a safe, secure and reliable solid electrolyte system LIB. In addition, a composite material having the same multifunctional function is mixed with the above conductive polymer composition to form a composite material, and in the lithium ion battery manufacturing process, it is impregnated as an electrolytic solution and deployed, and charging / discharging starts. It is possible to develop a solid electrolyte system LIB by accelerating the effect in the battery cell by self-heating up to 50 ° C in the chemical conversion treatment stage as a curing, and this formulation is also a one-shot solid electrolyte molding method Named.
The following examples further illustrate the invention.

[Graft polymer 1]
Vinylidene fluoride (PVdF) - as trifluorochloroethylene (CTFE) copolymer _{- (CH 2 -CF 2) n} - (CF 2 -CFCl) m - {n is 96 mol%, m is 4 mol%, Kureha Made by Chemical Industry Co., Ltd., trade name # 7500, intrinsic viscosity [η] = 2.55 (using Ostwald viscometer, solvent DMAC, measurement temperature 25 ° C.) [η] estimated molecular weight of 1,200,000} The salt monomer was graft polymerized under the following conditions.
A 1 L three-necked flask is equipped with a condenser, a stirrer, and a dropping device, 6 g of PVdF-CTFE copolymer # 7500 and 80 g of N-methylpyrrolidone (NMP) are added, and the mixture is heated to 80 ° C. in an oil bath and dissolved with stirring. did. Next, after sufficiently substituting the atmosphere with argon gas, molten salt monomer {compound name trimethylaminoethyl methacrylate bis (trifluoromethane) sulfonyl} imide (TMAEMA · TFSI)} and N, N, previously dissolved in 20 g of NMP 0.46 g of N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) and 0.08 g of CuCl were added. Further, the atmosphere was replaced with argon, and the temperature was raised to 90 ° C. and reacted for 23 hours. After the reaction, the reaction mixture was cooled to 40 ° C., diluted with acetone, poured into 50% aqueous methanol solution with stirring, and precipitated. The reaction product was further washed with a methanol solution and dried to obtain a crude polymer.
Next, the crude polymer was pulverized, and a mixed solvent of 40% acetone and 60% methanol was added and stirred. The ungrafted ionic liquid polymer and the unreacted molten salt monomer were dissolved, and the graft polymer swelled and settled, and thus was separated by a centrifuge. This extraction operation was repeated to obtain graft polymer 1. Furthermore, when it dried with a vacuum dryer at 30 degreeC, the yield was measured, the infrared spectrum was measured, and the grafting rate (mol%) was computed. It showed 71.7 mol%.
Note 1) Grafting rate (mol%)
A calibration curve was prepared by changing the blending ratio of the PVdF-CTFE copolymer and the graft polymer, measuring the infrared spectrum, and using this calibration curve, the grafting rate of the graft polymer of the sample (mol%) Asked.

Example 1
The graft polymer 1 {polymer conductive composition (X ¹ )} is mixed with a solvent (N-methylpyrrolidone and acetone in a weight ratio of 1: 1) to prepare a polymer conductive composition (CP) having a solid content of 30% by weight. A solvent solution was obtained.
The solvent solution of the polymer conductive composition is rolled on one side of a resin sheet (polyethylene porous sheet) by the process shown in FIG. 1 (coating process-mist treatment process-spraying and cleaning process-drying apparatus provided in one chamber). Coat and treat with steam mist (temperature 40 ° C., time 3 minutes) in vertical mist processing chamber, then spray with water, water bath treatment (temperature 20 ° C., time 2 minutes), then dry with hot air ( Temperature, 60 ° C., time 5 minutes), and wound up to obtain a substrate having a surface coat layer having pores having a mesh-like three-dimensional structure.
Also, using a waste liquid treatment apparatus provided outside the apparatus, the waste liquid is put into an ionic liquid {1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide} (EMI / TFSI), and the organic solvent in the waste liquid Water was absorbed into the ionic liquid, and the polymer conductive composition and the organic solvent / water in the waste liquid were separated.

Example 2
In Example 1, instead of the resin sheet (polyethylene perforated sheet), using a resin sheet (polyethylene sheet) whose surface has been plasma-treated (DC glow treatment under vacuum conditions: 60 W, 1 minute), a process of water bath treatment Except for omitting, a base material having a surface coating layer with a network-like three-dimensional structure was obtained in the same manner as in Example 1, and the waste liquid was treated to obtain a polymer conductive composition in the waste liquid and an organic solvent / water. separated.

Example 3
In Example 1, after preparing a solvent solution of the polymer conductive composition (CP), 10 wt% Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ solid electrolyte material was dispersed and mixed in a homogenizer In the same manner as in Example 1 except that the base material having a surface-coated layer having a network-like three-dimensional structure was obtained, and the waste liquid was treated to obtain a polymer conductive composition in the waste liquid and an organic solvent / water. Separated.

Example 4
In Example 1, after preparing a solvent solution of the polymer conductive composition (CP), a dispersion blend solution of 15 wt% Li ₇ La ₃ Zr ₂ O ₁₂ solid electrolyte material was obtained with a homogenizer. In the same manner as in Example 1, a substrate having a surface coating layer having a network-like three-dimensional structure was obtained, and the waste liquid was further treated to separate the polymer conductive composition and the organic solvent / water in the waste liquid.
When the electrical conductivity of the resin sheet which has the surface coat layer which has the hole which the network solid structure obtained in Examples 1-4 penetrated was measured, the following value was shown. These resin sheets were extremely excellent in solvent impregnation properties.
Example 1 Electrical conductivity (rate) 1.00 ^{−2 to} 1.00 ⁻³ S / cm
Volume resistivity 10 ⁻⁵ to 10 ⁻⁸ Ω · cm
Conductive durability No change (permanent)
Example 2 Electrical conductivity (rate) 1.00 ^{−2 to} 1.00 ⁻³ S / cm
Volume resistivity 10 ⁻⁶ to 10 ⁻⁹ Ω · cm
Conductive durability No change (permanent)
Example 3 Electrical conductivity (rate) 1.00 ^{−2 to} 1.00 ⁻³ S / cm
Volume resistivity 10 ⁻⁴ to 10 ⁻⁶ Ω · cm
Conductive durability No change (permanent)
Example 4 Electrical conductivity (rate) 1.00 ^{−2 to} 1.00 ⁻³ S / cm
Volume resistivity 10 ⁻³ to 10 ⁻⁵ Ω · cm
Conductive durability No change (permanent)
Note 1) Conductivity (rate): S / cm (Siemens per cm), a sample sandwiched between platinum electrodes with an electrode area of 0.95 cm ² , AC impedance method (0.1 V at 20 ° C. and 65% RH) The film resistance was measured at a frequency of 1 Hz to 10 MHz, and the film conductivity was calculated.
Note 2) Conductivity durability: Measures conductivity after standing for 6 months under the condition of 40 ° C-RH50%.
When the obtained resin sheet having a surface coating layer having a through-hole having a mesh-like three-dimensional structure is used for a separator for a lithium ion secondary battery, it has excellent characteristics for a secondary battery such as conductivity and conductive durability. Was.

Example 5
In Example 1, in place of X ^1, except for using X 1 ⁽⁹⁰ wt%) and X ^{2 (10} wt%), the surface having through-holes of the reticulated three-dimensional structure in the same manner as in Example 1 A substrate having a coating layer was obtained. Here, as the ^{X 2} using molten salt monomer {2- (methacryloyloxy) ethyl trimethyl ammonium bis (fluorosulfonyl) imide)} (MOETMA-FSI).

Example 6
In Example 1, in place of X ^1, except for using X 1 ⁽⁵⁰ wt%) and X ^{3 (50} wt%), the surface having through-holes of the reticulated three-dimensional structure in the same manner as in Example 1 A substrate having a coating layer was obtained. Here, as X ³ , a homopolymer of molten salt monomer {2- (methacryloyloxy) ethyltrimethylammonium bis (fluorosulfonyl) imide)} (MOETMA-FSI) was used.

  The substrate having a surface coat layer having holes having a mesh-like three-dimensional structure obtained in Example 5 and Example 6 is also extremely excellent in conductivity, conductivity durability, and solvent impregnation property as in Example 1. It was. In addition, when the obtained resin sheet having a surface coating layer having a through-hole having a mesh-like three-dimensional structure was used for a separator for a lithium ion secondary battery, it exhibited excellent characteristics for a secondary battery such as conductivity and conductive durability. Had.

  The base material having a surface coating layer with a network-like three-dimensional structure obtained by the present invention exhibits excellent properties in solvent impregnation characteristics such as an electrolytic solution, and has excellent conductivity and excellent conductivity durability. It is particularly useful as a conductive separator (filter) for lithium ion secondary batteries, capacitors, fuel cells, etc., and is used in fields that require electrical conductivity, such as resins, inorganic substances (metals, metal oxides, etc.), and wood. It is also useful for various conductive applications composed of films, sheets, plates, fibers (filaments, threads, fabrics, etc.), paper, nonwoven fabrics, particles, and other various three-dimensional structures. It is also useful for optical use such as polarizing plates and magnetic tape.

(1) ・ ・ Coating (coating) process (2) ・ ・ Mist treatment process for forming a three-dimensional network structure (3) ・ ・ Spraying process using nozzle, washing process using submerged tank (4) ・ ・ Using hot air drying tank Drying process (5) ... Waste liquid treatment process with ionic liquid

Claims (10)

Polymer conductive composition (X ¹ ) or X obtained by graft polymerization of a molten salt monomer having a salt structure comprising an onium cation and a halogen atom-containing anion and having a polymerizable functional group onto a fluorine-based polymer ¹ and at least one substance selected from the following (X ² ) to (X ³ ):
X ² : a molten salt comprising an onium cation and a halogen atom-containing anion, or a molten salt monomer having a salt structure thereof and having a polymerizable functional group,
X ³ : a polymer or copolymer of a molten salt monomer having a molten salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group,
A method for producing a substrate having a network-like three-dimensional surface coat layer, comprising the steps of: coating a base material with a polymer conductive composition comprising:
(1) A step of coating the one or both surfaces of the substrate with the solvent solution of the polymer conductive composition,
(2) a step of mist processing the coating layer;
(3) A step of washing the mist-treated coating layer with a spray and / or a water bath,
(4) A step of drying the washed coating layer. → New insertion The method for producing a substrate having a surface coating layer having a network-like three-dimensional structure according to claim 1, wherein the halogen atom-containing anion is a fluorine atom-containing anion.   3. A substrate having a surface coating layer having a mesh-like three-dimensional structure according to claim 1, comprising a step (5) of putting the waste liquid after washing into an ionic liquid and separating the polymer conductive composition and the solvent in the waste liquid. Manufacturing method. A polymer conductive composition obtained by graft polymerization of a molten salt comprising an onium cation and a halogen atom-containing anion, or a molten salt monomer having such a salt structure and having a polymerizable functional group onto a fluoropolymer ( X ¹ ) or X ¹ and at least one substance selected from the following (X ² ) to (X ³ ) X ² : a molten salt structure comprising an onium cation and a halogen atom-containing anion, or a salt structure thereof And a molten salt monomer having a polymerizable functional group,
X ³ : a polymer or copolymer of a molten salt monomer having a molten salt structure composed of an onium cation and a halogen atom-containing anion and having a polymerizable functional group,
In the method of coating the base material with a polymer conductive composition containing a surface of the network structure, the method includes the step of plasma treatment before coating the base material with the polymer conductive composition, and The manufacturing method of the base material which has a surface coating layer of a network-like three-dimensional structure including a process.
Manufacturing method.
(1) A step of coating a substrate with a solvent solution of the polymer conductive composition on one or both sides,
(2) a step of mist processing the coating layer;
(4) A step of drying the washed coating layer. → New Insertion The method for producing a substrate having a surface coating layer having a network structure according to claim 4, wherein the halogen atom-containing anion is a fluorine atom-containing anion.   6. A substrate having a surface coating layer having a network-like three-dimensional structure according to claim 4 or 5, which comprises a step (5) of putting the waste liquid after washing into an ionic liquid and separating the polymer conductive composition and the solvent in the waste liquid. Manufacturing method.   The manufacturing method of the base material which has a surface coating layer of the network-like three-dimensional structure in any one of Claims 1-6 whose manufacturing method is a continuous or batch type.   The base material is resin, inorganic material, wood, and the shape is various three-dimensional structures such as film, sheet, plate, porous base material, fiber, paper, nonwoven fabric, particle, chip, spherical body, deformed body, The manufacturing method of the base material which has a surface coating layer of the network-like three-dimensional structure in any one of Claims 1-7.   The base material is polyolefin resin, polyimide resin, polyamide resin, polycarbonate resin, polyurethane resin, polyester resin, acrylic resin, halogen resin, diene resin, vinyl acetate resin, polyether resin The mesh shape according to any one of claims 1 to 8, which is at least one resin selected from a resin, a silicone resin, and a thermosetting resin (urea-based, phenol-based, melamine-based, unsaturated polyester-based, epoxy-based). A method for producing a substrate having a three-dimensional surface coat layer.   The manufacturing method of the base material which has a surface coating layer of the network-like three-dimensional structure in any one of Claims 1-9 whose base material is a porous separator for lithium ion secondary batteries.