JPH10269847A - Fixed liquid film conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily provide a film having a large area, the holding property of an electrolytic solution in a wide temperature range, long-term stability, and improved mechanical strength by fixing an aprotic electrolytic solution to a polyolefin fine porous film containing organopolysiloxane having affinity to the aprotic electrolytic solution. SOLUTION: An organopolysiloxane solution solved in a solvent such as toluene not solving a polyolefin fine porous film is preferably applied by coating to the polyolefin fine porous film such as ultrahigh-molecular weight polyethylene containing an electronic conductive material. The film may be formed after organopolysiloxane is filled in the gelatinous molding of a polyolefin composition containing the electronic conductive material. The aprotic electrolytic solution is fixed by impregnating, and the film has the prescribed thickness and relative dielectric constant. This fixed liquid film conductor has the porous film base skeleton of polyolefin, the electronic conductivity is not reduced, and the safety at the time of an overcharge is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an immobilized liquid film conductor and a method for producing the same, and more particularly, to an immobilized liquid film conductor in which an ionic conductor is immobilized on a porous conductive film having high electron conductivity, and a method for manufacturing the same. It relates to a manufacturing method.

[0002]

2. Description of the Related Art A polymer material such as polyethylene, polypropylene, polyvinyl chloride, polysulfone, butadiene rubber, silicone rubber, ethylene-propylene-diene terpolymer, epoxy resin, etc. is mixed with an electronic conductive substance such as carbon black. Such conductors are widely known. And these conductors are antistatic materials,
It is used for electromagnetic wave shielding materials, conductive paints, adhesives, IC packaging materials, planar heating elements, planar switches, and the like.

Further, among such conductors, a thin film conductor (porous conductive film) which is porous but has high conductivity is extremely effective as an electrode or an electrode constituent material in a device using a solid polymer electrolyte or a liquid electrolyte. Can be used for That is, since it is porous, the contact interface between the electrode and the electrolyte can be increased in area, and thus, for example, using this, a lithium primary battery,
It is possible to manufacture a high-performance battery such as a lithium secondary battery.

As a development example of the above-mentioned thin film conductor, Ketjen black (Akzo black) is added to a plasticizer solution of polyethylene.
Chemic Co., Ltd.), and after forming and stretching a sheet, a porous thin film from which a plasticizer has been removed, and an electrolyte solution immobilized by utilizing the capillary condensation force, and a method for producing the same (Japanese Patent Laid-Open No. -87096). However, there is a problem in the electrolyte retention. On the other hand, recently, a copolymer of polyvinylidene fluoride and hexafluoropropylene has been
A technique has been proposed (US Pat. No. 5,296,318) in which a polymer gel impregnated with a carbonate-based solution in which n ₂ O ₄ and carbon black or petroleum coke and carbon black are mixed and a lithium salt is dissolved is used for a positive electrode or a negative electrode of a battery. However, there is a problem of electrolyte seepage due to gel shrinkage at a high temperature, and this is not a complete solution for electrolyte retention. Therefore, it is desired to develop a thin-film conductor which can be easily formed into a thin film and has a large area and has a stable ability to hold an electrolyte solution in a wide temperature range.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to easily form a thin film, to have a large area, and to have excellent aprotic electrolyte solution retention over a wide temperature range.
An object of the present invention is to provide an immobilized liquid film conductor having improved long-term stability and mechanical strength, and a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to overcome the problems of the prior art, and as a result, have found that the affinity of organopolysiloxane contained in a microporous polyolefin membrane containing an electronically conductive material is high. It has been found that the above object can be achieved by immobilizing an aprotic electrolyte on a membrane depending on the nature.

That is, the immobilized liquid film conductor of the present invention comprises:
An aprotic electrolyte solution is immobilized on a microporous polyolefin membrane containing an organopolysiloxane having an affinity for the aprotic electrolyte solution and an electron conductive material. Further, a first method for producing an immobilized liquid membrane conductor of the present invention comprises coating a polyolefin microporous membrane containing an electron conductive material with an organopolysiloxane having an affinity for an aprotic electrolyte solution. Is impregnated with an aprotic electrolyte solution to be immobilized.
Further, the second method for producing the immobilized liquid film conductor of the present invention comprises the step of adding an organopolysiloxane having an affinity to an aprotic electrolyte solution to a gel-like molded product comprising a polyolefin composition containing an electronic conductive material. The membrane is filled and formed into a film, which is impregnated with an aprotic electrolyte solution to be fixed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The immobilized liquid membrane conductor of the present invention is prepared by adding an aprotic electrolyte solution to a polyolefin microporous membrane containing an organopolysiloxane having an affinity for an aprotic electrolyte solution and an electronic conductive material. Is fixed. The details will be described below.

1. Raw materials a. Polyolefin Polyolefins include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1,
Poly-4-methylpentene-1 and the like. Of these, polyethylene is preferred. As the polyethylene, those made of ultra-high molecular weight polyethylene, high density polyethylene, medium-low density polyethylene can be used, but those containing ultra-high molecular weight polyethylene or components thereof from the viewpoint of strength, safety, film forming property, etc. It is preferable to use The polyolefin has a weight average molecular weight of 5 × 10 ⁵ or more, preferably 1 × 10 ⁶ to 1 × 10 5.
^It is preferred that the ultrahigh molecular weight component ⁷ is contained in an amount of 1% by weight or more and the molecular weight distribution (weight average molecular weight / number average molecular weight) is 10 to 300. When the content of the ultrahigh molecular weight polyolefin component is less than 1% by weight, the portion which contributes to the improvement of the stretchability of the film is insufficient. On the other hand, the upper limit is not particularly limited. On the other hand, if the molecular weight distribution exceeds 300, breakage due to low molecular weight components occurs, and the strength of the entire thin film decreases, which is not preferable.

B. Electronic conductive material Examples of the electronic conductive material include various metals and semiconductors, oxide and sulfide electronic conductive materials, and carbon or graphite. These may be in any shape such as a particle shape, a fiber shape, a fibril shape, a whisker shape and the like. Particularly preferred are TiS ₃ , TiS ₂ ,
TiO ₂ , V ₂ O ₅ , NbSe ₃ , MnO ₂ , LiCoO ₂ ,
Battery positive electrode active materials such as LiNiO ₂ , LiMn ₂ O ₄ , PbO ₂ , NiOOH, petroleum coke, natural graphite,
Battery negative electrode active materials such as carbon fiber, Pb and Cd, acetylene black, Ketjen black (Akz
oChemic), carbon whiskers, graphite whiskers, graphite fibrils and the like.

C. Organopolysiloxane The organopolysiloxane used in the present invention is a polymer having at least one silicon-carbon bond per silicon and having a silicon-oxygen bond (→ Si—O—Si ←) as a repeating unit. Compound. For example, commercially available silicone oils and silicone rubbers having a degree of polymerization of 10 or more, preferably 10 to 10,000 can be used. If the degree of polymerization is less than 10, volatilization and dissipation cannot be ignored, which is not preferable. On the other hand, if the degree of polymerization greatly exceeds 100, the viscosity becomes high and it becomes difficult to uniformly fill the gel-like molded product. Therefore, dilution with a volatile solvent is preferred.

Specific examples of the organopolysiloxane include polydimethylsiloxane in which the organic group is a methyl group, and hydrogen or hydrogen at the terminal or inside of the polysiloxane chain.
Modified polysiloxane to which vinyl group, hydroxyl group, amino group, carboxyl group, epoxy group, methacryloxy group, mercapto group, long-chain alkyl group, phenyl group, chlorine or fluorine are bonded, and non-polysiloxane part in main chain Examples thereof include an alkylene oxide-modified polysiloxane, a silicone-modified copolymer, and an alkoxysilane-modified polymer. Polymethylvinylsiloxane, polymethylphenylvinylsiloxane, polymethylfluorovinylsiloxane, or a modified polysiloxane in which a vinyl group or a hydroxyl group is bonded to the inside or end of a polysiloxane chain, such as a polydimethylsiloxane having a hydroxyl group blocked, may also be used. Yes, but-(CH
₂ CH ₂ O) _n modified polysiloxane or with an ether-based group in the side chain, such as -R - [(CH _{2) m} COO (CH
₂ ) A modified polysiloxane having an ester group such as _n ] -R is expected to have not only an affinity with an aprotic electrolyte solution but also a kind of complex with lithium ions to promote ion conduction.

As the volatile solvent for diluting the organopolysiloxane having a high degree of polymerization, pentane, hexane,
Hydrocarbons such as heptane and toluene, chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride, fluorinated hydrocarbons such as ethane trichloride ethane, ethers such as diethyl ether and dioxane, and others such as methanol and ethanol Alcohols. The above-mentioned organopolysiloxane or its diluted solution may contain, if necessary, a crosslinking agent for the organopolysiloxane, for example, an organic peroxide, an organosilicon compound having three or more functional groups, an alkylorisilicate, a metal-based compound. A small amount of a reinforcing material such as a catalyst or synthetic silica and other additives may be blended.

D. Electrolyte solution As an electrolyte of the aprotic electrolyte solution, an alkali metal salt, an alkaline earth metal salt is used, for example, LiF,
NaI, LiI, LiClO ₄ , LiAsF ₆ , LiPF
₆ , LiBF ₄ , LiCF ₃ SO ₃ , NaSCN and the like. Further, as the aprotic solvent for dissolving the electrolyte of the aprotic electrolyte solution, a solvent stable to an alkali metal, specifically, propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethoxyethane, acetonitrile, form An aprotic high dielectric constant solvent such as amide, tetrahydrofuran, diethyl ether or the like is used alone or in combination of two or more.

2. Production Method The method for producing the immobilized liquid film conductor of the present invention is described in A.I. A method of coating an organopolysiloxane on a polyolefin microporous film containing an electronic conductive material and fixing an electrolyte solution,
B. There are two production methods: a method in which an organopolysiloxane is filled into a gel-like molded product made of a polyolefin composition containing an electronic conductive material to form a film, and an electrolyte solution is fixed.

A. Coating organopolysiloxane on polyolefin microporous film containing electronic conductive material,
Method for immobilizing electrolyte solution Aa. Manufacturing method of microporous membrane Polyolefin microporous membrane containing electronic conductive material,
It can be obtained by blending the above-mentioned electronic conductive material with polyolefin and forming a film. The compounding amount of the electronic conductive material is preferably 1 to 200% by weight, particularly preferably 5 to 100% by weight. If the amount is less than 1% by weight, it is difficult to obtain sufficient conductivity, and if it exceeds 200% by weight, it becomes difficult to obtain a film having practically sufficient strength. The film formation of the polyolefin composition containing the above electronic conductive material,
It may be performed by the method described in JP-A-60-242035 or JP-A-3-64334. For example, it can be performed as follows. First, a solution is prepared by heating and dissolving the polyolefin composition in a solvent. The solvent is not particularly limited as long as it can sufficiently dissolve the polyolefin composition, and may be the same as those described in JP-A-60-242035, but also readily volatile solvents such as decalin and xylene. Can be used. The heat dissolution is performed while stirring at a temperature at which the polyolefin composition is completely dissolved in the solvent. The temperature varies depending on the polymer and solvent used, but is preferably in the range of 140 to 250 ° C. The concentration of the polyolefin composition solution is 10 to 50% by weight, preferably 10 to 40% by weight.

Next, an electronic conductive material is uniformly blended with the polyolefin composition solution. Further, a heated solution of the polyolefin composition containing the electronic conductive material is extruded from a die and molded. As the die, a sheet die having a rectangular base shape is usually used, but a double cylindrical hollow fiber die, an inflation die, or the like can also be used. When a sheet die is used, the die gap is usually 0.1.
1-5mm, 140-250 ° C during extrusion
Heated. The extrusion speed at this time is usually 20 to 30.
cm / min to 5 to 10 m / min. The solution extruded from the die in this manner is formed into a gel by cooling. The cooling rate is preferably at least 50 ° C./min up to the gelation temperature or lower.

Next, this gel-like molded product is stretched. The stretching is performed at a predetermined magnification by heating the gel-like molded product and using a usual tenter method, a roll method, an inflation method, a rolling method or a combination of these methods. Biaxial stretching is preferred, and either longitudinal or transverse simultaneous stretching or sequential stretching may be used, but biaxial stretching is particularly preferred. The stretching temperature is equal to or lower than the melting point of polyethylene of the polyolefin composition + 10 ° C, preferably in the range from the crystal dispersion temperature to less than the crystal melting point. For example,
90-140 degreeC, More preferably, it is the range of 100-130 degreeC. Further, the solvent contained in the stretched film is extracted and removed with a volatile solvent such as methylene chloride, and then dried and heat-set. In addition, an antioxidant, an ultraviolet absorber, a lubricant,
Various additives such as an anti-blocking agent, a pigment, a dye, and an inorganic filler can be added as long as the object of the present invention is not impaired.

The microporous polyolefin membrane containing the above-mentioned electron conductive material has a thickness of 1 to 1000 μm, preferably 5 to 1000 μm.
It has a thickness of 500 μm. If the thickness is less than 1 μm, it is difficult to practically use from the viewpoint of mechanical strength and handling. On the other hand, if it exceeds 1000 μm, the effective resistance becomes large and the volume efficiency as a conductor is disadvantageous. The porosity of the film is not limited, but is in the range of 30 to 95%, more preferably 50 to 90%. If the porosity is less than 30%, the immobilization of the aprotic electrolyte solution may be insufficient. On the other hand, if the porosity exceeds 95%, the mechanical strength of the membrane becomes small and the practicability is poor. .

Ab. Coating method of organopolysiloxane As a coating method of organopolysiloxane,
Spraying or applying a solution of organopolysiloxane dissolved in an organic solvent that is a non-solvent to a microporous polyolefin membrane containing an electronic conductive material, coating or dipping the membrane into the liquid, and other coating operations Is mentioned. More preferably, the film obtained by evaporating and solidifying the organic solvent is further crosslinked. The coating thickness is
The thickness of the composite film is preferably 1 to 1000 μm.

Ac. Method of fixing electrolyte solution As a method of fixing an aprotic electrolyte solution to a polyolefin microporous membrane containing an electronic conductive material and an organopolysiloxane to form an aprotic electrolyte thin film, impregnation, coating or spraying alone or They can be used in combination. In addition, the electrolyte solution may be fixed before being incorporated into the battery, during the battery assembly process, or at the final battery assembly process. Among them, in view of the ease of handling during battery assembly, the prevention of wrinkles and the like, the adhesion to the positive and negative electrode surfaces, and the fact that the conventional battery assembly process can be applied as it is, the electrolyte may be used during the battery assembly process or the final battery assembly process. The method of immobilizing the solution is preferred.
The content of the electrolyte solution was 7% of that of the microporous polyolefin membrane containing the electronic conductive material and the organopolysiloxane.
It is 0 to 350% by weight, preferably 80 to 250% by weight. When the retention is less than 70% by weight, the specific conductivity is improved, but the interface with the electrolyte solution when used as an electrode material is reduced, and the application as a battery, a capacitor, and an electrochromic element is restricted from the viewpoint of practicality. . On the other hand, if it exceeds 350% by weight, the mechanical strength of the film becomes insufficient.

B. A method of filling an organopolysiloxane into a gel-like molded product made of a polyolefin composition containing an electronic conductive material to form a film, and fixing an electrolyte solution Ba-a. Preparation of gel-like molded article A gel-like sheet made of a polyolefin composition containing an electronic conductive material is prepared in the same manner as the gel-like sheet before the stretching step in the method for producing a microporous membrane described in A-a. That is, a gel-like sheet can be obtained by heating and dissolving an ultra-high molecular weight polyolefin in a solvent, uniformly mixing an electron conductive material, forming the solution into a sheet, and cooling the sheet.

Bb. Filling and film formation of organopolysiloxane In order to fill the organopolysiloxane, first, the solvent in the gel sheet is removed. Examples of the removal method include removal of the solvent by evaporation of the gel-like sheet by heating, removal by compression, extraction and removal of the solvent by a volatile solvent, and removal of the solvent while maintaining the network structure of the gel-like sheet by freeze-drying. However, in order to remove the solvent without significantly changing the structure of the gel-like sheet, extraction and removal with a volatile solvent is preferable. Further, it is preferable to remove the solvent in the gel-like sheet to 1% by weight or less.

The filling of the organopolysiloxane is carried out by immersing the gelled sheet subjected to the desolvation treatment in an organopolysiloxane liquid or a dilute solution thereof in the presence or absence of a volatile solvent used for the desolvation treatment. This is done by coating. Further, even in the case of an untreated gel-like sheet that has not been subjected to a solvent removal treatment, it can be filled by injecting an organopolysiloxane solution or a diluted solution thereof. However, it is more preferable to immerse the gel-like sheet in the presence of the volatile solvent after the desolvation treatment, because it can be easily filled.

The concentration of the diluted organopolysiloxane solution varies depending on the amount of the organopolysiloxane to be filled in the gel sheet, but is preferably at least 0.05% by weight or more, particularly preferably 0.5% by weight or more. If the concentration is less than 0.05% by weight, the amount of the organopolysiloxane filled in the gel-like sheet is insufficient, and pinholes are easily generated during stretching. The solution viscosity is 5 at 25 ° C. in order to uniformly fill the entire gel sheet.
It is preferably less than 00 cSt, particularly preferably less than 100 cSt. The filling amount of the organopolysiloxane in the gel sheet is preferably from 5 to 90% by weight, particularly preferably from 10 to 80% by weight. Next, the obtained organopolysiloxane-containing gel-like sheet is stretched. The stretching method can be performed in the same manner as the stretching step of the gel-like molded product described in A-a.

B-c. Method for Immobilizing Electrolyte Solution The method for immobilizing the electrolyte solution can be performed in the same manner as the method described in Ac.

3. The film thickness and specific conductivity of the immobilized liquid film conductor The immobilized liquid film conductor of the present invention constituted by the above,
It has a thickness of 1 to 1000 μm. The specific conductivity is
It is at least 10 ^-5 Scm ^-1 , preferably at least 10 ^-3 Scm ^-1 . If the specific conductivity is less than 10 ^-5 Scm ^-1 , the effective resistance becomes large and is not practical. For example, when the film thickness is 1 μm, the effective resistance is 1 μm / 10 ⁻⁵ Scm ⁻¹ , that is, 10 Ωcm ² .

[0028]

The present invention will be described in more detail with reference to the following specific examples. In the test method of the film thickness in the examples, the cross section was measured by a scanning electron microscope.

Example 1 Polyethylene (polyethylene 2 having a weight average molecular weight of 400,000)
5 parts by weight, 30 parts by weight of petroleum coke powder and 30 parts by weight of Ketjen black powder (trademark of Akzo Chemical Co.)
Mixture 10 containing 3 parts by weight and 70 parts by weight of liquid paraffin
0.37 parts by weight of an antioxidant was added to 0 parts by weight, and the mixture was heated and kneaded with a twin screw extruder. This was extruded from a die having a rectangular die and taken up with a chill roll to form a 1 mm thick sheet. This sheet is subjected to batch stretching using a batch type biaxial stretching machine.
Polyethylene containing an electron conductive material is stretched simultaneously at 20 ° C. by 5 × 5 times, washed with n-hexane for remaining liquid paraffin, dried at 120 ° C. while fixed to a metal frame, and heat-set. A microporous membrane was obtained.

A two-part room temperature curing silicone rubber compound (trade name: KE103RTV, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 15% by weight with xylene in a polyethylene microporous membrane (thickness: 30 μm) containing the obtained electronically conductive material. Was applied and left to stand at room temperature for 24 hours to cure, thereby obtaining a composite film having an organopolysiloxane loading of 53% by weight. A 10 × 10 mm square polyethylene microporous film containing an electron conductive material filled with this organopolysiloxane was added to a propylene carbonate solution containing 1 mol of LiPF ₆ at 25 ° C.
This was immersed for a period of time to obtain an immobilized liquid film conductor having a swelling ratio (weight increase ratio) of 125%. The obtained immobilized liquid membrane conductor was set to a diameter of 10
mm, and this is sandwiched between platinum black electrodes.
The specific electrical conductivity calculated from the measured electrical resistance value with an alternating current of Hz and the thickness and the area of the immobilized liquid film conductor was 7 × 10
^-2 Scm ^-1 .

Example 2 Polyethylene (polyethylene 2 having a weight average molecular weight of 400,000)
5 parts by weight, 30 parts by weight of petroleum coke powder and 30 parts by weight of Ketjen black powder (trademark of Akzo Chemical Co.)
Mixture 10 containing 3 parts by weight and 70 parts by weight of liquid paraffin
0.37 parts by weight of an antioxidant was added to 0 parts by weight, and the mixture was heated and kneaded with a twin screw extruder. This was extruded from a die having a rectangular die and taken up with a chill roll to form a 1 mm thick sheet. The sheet was immersed in a large amount of methylene chloride for 60 minutes, and immediately without drying the sheet, methyl vinyl silicone oil (manufactured by Nippon Unicar, trade name: NUC silicone gum stock W-961) was used.
3) After being transferred into a 20% by weight methylene chloride solution and immersed for 60 minutes, methylene chloride was dried and removed in a state where all sides were fixed to obtain a sheet having a methyl vinyl silicone oil filling amount of 45% by weight.

This methyl vinyl silicone oil-filled sheet was simultaneously biaxially stretched 5 × 5 times at 125 ° C. using a batch type biaxial stretching machine. When the infrared absorption spectrum of the obtained film was measured, no vinyl group was recognized, and no elution of methylvinylsilicone oil by methylene chloride extraction was observed. A polyethylene film containing an electron conductive material filled with this organopolysiloxane is
It was immersed in a propylene carbonate solution containing 1 mol of LiPF ₆ at 5 ° C. for 1 hour to obtain an immobilized liquid film conductor having a film thickness of 24 μm and a swelling ratio (weight increase ratio) of 117%. The obtained immobilized liquid film conductor was punched out to a diameter of 10 mm, this was sandwiched between platinum black electrodes, and the electrical resistance was measured with an alternating current of 1 kHz, and calculated from this value and the thickness and area of the immobilized liquid film conductor. The measured specific conductivity was 9 × 10 ⁻² Scm ⁻¹ .

COMPARATIVE EXAMPLE 1 In Example 1, a 10 cm × 10 cm square of a microporous polyethylene film (thickness: 30 μm) containing an electronic conductive material before filling with an organopolysiloxane was treated at 25 ° C.
Was immersed in a propylene carbonate solution containing 1 mol of LiPF ₆ for 1 hour to obtain an immobilized liquid membrane conductor having a swelling ratio (weight increase ratio) of 81.5%. The obtained immobilized liquid film conductor was punched out to a diameter of 10 mm, this was sandwiched between platinum black electrodes, the electric resistance was measured with an alternating current of 1 kHz, and calculated from this value and the thickness and area of the immobilized liquid film conductor. The measured specific conductivity was 4 × 10 ⁻² Scm ⁻¹ .

[0034]

The immobilized liquid membrane conductor of the present invention immobilizes the electrolyte solution by the affinity of the filled organopolysiloxane, and suppresses the excessive swelling by the porous membrane base skeleton made of polyolefin. Since the electrolyte solution can be stably held in a wide temperature range and the evaporation rate of the electrolyte solution can be kept extremely low, good conductivity can be maintained over a wide temperature range. That is, safety in overcharging can be improved without significantly lowering the electronic conductivity. Further, the immobilized liquid film conductor has excellent mechanical strength due to a skeleton made of polyolefin, and can be applied with almost no change in a conventional battery manufacturing process. In addition, since this immobilized liquid film conductor has both ion and electron conductivity,
It is useful for an electrode of an electrolyte, particularly a battery using a liquid electrolyte, an electrochromic device, an electric double layer capacitor, a liquid crystal device and the like. Since the ionic conductor in the immobilized liquid membrane conductor is continuous with the electrolyte between the electrodes and is in close contact with the porous conductive film over a wide area, it is effective as an electrode material for various cells and elements using the electrolyte. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // H05K 9/00 H05K 9/00 W

Claims (3)

[Claims] An immobilized liquid membrane conductor comprising an aprotic electrolyte solution immobilized on a microporous polyolefin membrane containing an organopolysiloxane having an affinity for an aprotic electrolyte solution and an electron conductive material. 2. An immobilization method in which a microporous polyolefin membrane containing an electroconductive material is coated with an organopolysiloxane having an affinity for an aprotic electrolyte solution, and impregnated with the aprotic electrolyte solution for immobilization. A method for producing a liquid film conductor. 3. A gel-like molded product comprising a polyolefin composition containing an electronic conductive material is filled with an organopolysiloxane having an affinity for an aprotic electrolyte solution to form a film. A method for producing an immobilized liquid film conductor, wherein the conductor is impregnated and immobilized.