JP2000036219A5

JP2000036219A5 -

Info

Publication number: JP2000036219A5
Application number: JP1998219644A
Authority: JP
Filing date: 1998-07-17
Publication date: 2005-06-23
Anticipated expiration: 2018-07-17

Description

【０００６】
【課題を解決するための手段】
本発明者等は、前記従来技術を克服するために鋭意研究した結果、特定のポリオレフィン微多孔膜の製造工程において高分子固体電解質をその細孔部に充填した後、延伸操作を行い極性溶媒を含浸させると、高導電性の高分子固体電解質薄膜が得られることを見出し、本発明を完成した。
すなわち、本発明は、重量平均分子量５×１０ ^５以上の超高分子量ポリオレフィンを含有するポリオレフィン組成物１０〜５０重量％と、溶媒９０〜５０重量％からなる溶液を調製し、前記溶液をダイより押し出し、冷却ロールにより引き取りゲル状シートを成形後、シート中の残存溶媒を除去し、乾燥してポリオレフィン微多孔膜を製造後、高分子固体電解質を揮発性溶媒に溶解させた溶液を含浸させ、高分子固体電解質を多孔質膜の孔部分に５容量％以上充填させた後、加熱延伸し、次に極性溶媒を含浸させることを特徴とする厚さが２０μｍ以下で、１０ＫＨｚでの実部インピーダンスが８×１０ ^３ Ω・ｃｍ ^２以下である高分子固体電解質薄膜の製造方法、及び、重量平均分子量５×１０ ^５以上の超高分子量ポリオレフィンを含有するポリオレフィン組成物１０〜５０重量％と、溶媒９０〜５０重量％からなる溶液を調製し、前記溶液をダイより押し出し、冷却ロールにより引き取りゲル状シートを成形後、シート中の残存溶媒を除去し、乾燥してポリオレフィン微多孔膜を製造後、低分子量ポリマー電解質または電解質モノマーを揮発性溶媒に溶解させた溶液を含浸させ、低分子量ポリマー電解質または電解質モノマーを多孔質膜の孔部分に５容量％以上充填させた後、加熱延伸し、重合して低分子量ポリマーまたはモノマーを高分子量化した後、極性溶媒を含浸させることを特徴とする厚さが２０μｍ以下で、１０ＫＨｚでの実部インピーダンスが８×１０ ^３ Ω・ｃｍ ^２以下である高分子固体電解質薄膜の製造方法並びに、その製造方法により製造される高分子固体電解質薄膜並びにそれを用いた電池である。 0006
[Means for solving problems]
As a result of diligent research to overcome the above-mentioned prior art, the present inventors, after filling the pores of the polymer solid electrolyte in the manufacturing process of a specific polyolefin microporous film, perform a stretching operation to obtain a polar solvent. We have found that when impregnated, a highly conductive polymer solid electrolyte thin film can be obtained, and completed the present invention.
That is, the present invention provides a polyolefin composition from 10 to 50% by weight, containing a weight average molecular weight 5 × 10 ⁵ or more ultra-high molecular weight polyolefin, a solution comprising a solvent 90-50 wt% was prepared, from the die the solution After extruding and taking over with a cooling roll to form a gel-like sheet, the residual solvent in the sheet is removed, and the sheet is dried to produce a polyolefin microporous film, which is then impregnated with a solution of a polymer solid electrolyte dissolved in a volatile solvent. The pore portion of the porous film is filled with a polymer solid electrolyte in an amount of 5% by volume or more, then heat-stretched, and then impregnated with a polar solvent. the method of manufacturing a solid polymer electrolyte membrane but is 8 × 10 ³ Ω · cm ² or less, and a polyolefin composition from 10 to 50% by weight, containing a weight average molecular weight 5 × 10 ⁵ or more ultra-high molecular weight polyolefin and the solvent A solution consisting of 90 to 50% by weight is prepared, the solution is extruded from a die, taken up with a cooling roll to form a gel-like sheet, the residual solvent in the sheet is removed, and the solution is dried to produce a polyolefin microporous film. A solution in which a low molecular weight polymer electrolyte or an electrolyte monomer is dissolved in a volatile solvent is impregnated, the pores of the porous membrane are filled with 5% by volume or more of the low molecular weight polymer electrolyte or the electrolyte monomer, and then heat-stretched and polymerized. ^{A polymer having a thickness of 20 μm or less and a real part impedance of 8 × 10 3} Ω · cm ² or less at 10 KHz, which is characterized by impregnating a low molecular weight polymer or monomer with a high molecular weight and then impregnating with a polar solvent. A method for producing a solid electrolyte thin film, a polymer solid electrolyte thin film produced by the method, and a battery using the same.

実施例１
重量平均分子量２．５×１０^６の超高分子量ポリエチレン４重量％、重量平均分子量３．３×１０^５の高密度ポリエチレン１６重量％及び流動パラフィン８０重量％を二軸押出機で溶融混練し、その先端に設置されたＴダイから押出し、冷却して７５μｍのゲル状シートを形成した。得られたシートを塩化メチレンで洗浄し、溶媒を除去した後、１２０℃で熱固定を行ってポリエチレン微多孔膜を得た。得られたポリエチレン微多孔膜に、平均分子量４０００のポリエチレングリコールの１モル塩化メチレン溶液及びＬｉＣｌＯ_４の０．２モル塩化メチレン溶液を含浸させた。次いで、アルゴン雰囲気下で１０分間自然乾燥し、塩化メチレンを除去し、さらに、アルゴン雰囲気の８０℃のオーブン中で１０分間乾燥させた。得られたシートはポリエチレングリコールを９．６容量％充填していた。得られた充填シートをバッチ式二軸延伸機で１１５℃にてＭＤ／ＴＤ＝３／３倍に延伸し、厚さ１１μｍの薄膜を得た。この薄膜に、プロピレンカーボネート：ジメトキシエタン（ＤＭＥ）＝１：１の１モルＬｉＣｌＯ_４溶液を含浸させ高分子固体電解質薄膜を得た。得られた高分子固体電解質薄膜のインピーダンスは、４．１×１０^３Ω・ｃｍ^２であり、膜のラフネスは５μｍ以下であった。また、１６φのＡｕ電極で高分子固体電解質薄膜を挟み込んで、デンドライトを測定したが、デンドライトによるショートは認められなかった。 Example 1
Melt-kneading ultrahigh molecular weight polyethylene 4 wt% of the weight-average molecular weight 2.5 × 10 ^6, high density polyethylene 16 wt% of the weight-average molecular weight 3.3 × 10 ⁵ and a liquid paraffin 80 wt% in a twin-screw extruder, It was extruded from a T-die installed at its tip and cooled to form a gel-like sheet of 75 μm. The obtained sheet was washed with methylene chloride to remove the solvent, and then heat-fixed at 120 ° C. to obtain a polyethylene microporous membrane. The obtained polyethylene microporous membrane was impregnated with a 1 mol methylene chloride solution of polyethylene glycol having an average molecular weight of 4000 and a 0.2 mol methylene _{chloride solution of LiClO 4.} Then, it was air-dried in an argon atmosphere for 10 minutes to remove methylene chloride, and further dried in an oven at 80 ° C. in an argon atmosphere for 10 minutes. The obtained sheet was filled with polyethylene glycol in an amount of 9.6% by volume. The obtained packed sheet was stretched at 115 ° C. at 115 ° C. with MD / TD = 3/3 times with a batch type biaxial stretching machine to obtain a thin film having a thickness of 11 μm. This thin, propylene carbonate: dimethoxyethane (DME) = 1: to obtain a polymer solid electrolyte film impregnated with 1 of 1 molar LiClO ₄ solution. The impedance of the obtained polymer solid electrolyte thin film was 4.1 × 10 ³ Ω · cm ² , and the roughness of the film was 5 μm or less. Further, the dendrite was measured by sandwiching the polymer solid electrolyte thin film with the 16φ Au electrode, but no short circuit due to the dendrite was observed.

Claims

重量平均分子量５×１０^５以上の超高分子量ポリオレフィンを含有するポリオレフィン組成物１０〜５０重量％と、溶媒９０〜５０重量％からなる溶液を調製し、前記溶液をダイより押し出し、冷却ロールにより引き取りゲル状シートを成形後、シート中の残存溶媒を除去し、乾燥してポリオレフィン微多孔膜を製造後、高分子固体電解質を揮発性溶媒に溶解させた溶液を含浸させ、高分子固体電解質を多孔質膜の孔部分に５容量％以上充填させた後、加熱延伸し、次に極性溶媒を含浸させることを特徴とする厚さが２０μｍ以下で、１０ＫＨｚでの実部インピーダンスが８×１０ ^３ Ω・ｃｍ ^２以下である高分子固体電解質薄膜の製造方法。A solution comprising 10 to 50% by weight of a polyolefin composition containing an ultra-high molecular weight polyolefin having a weight average molecular weight of 5 × 10 ⁵ or more and a solvent of 90 to 50% by weight is prepared. The solution is extruded from a die and taken up by a cooling roll. After forming the gel sheet, the residual solvent in the sheet is removed, dried to produce a polyolefin microporous membrane, and then impregnated with a solution in which the polymer solid electrolyte is dissolved in a volatile solvent, so that the polymer solid electrolyte is porous. The pore portion of the membrane is filled with 5% by volume or more, then stretched by heating, and then impregnated with a polar solvent. The thickness is 20 μm or less, and the real part impedance at 10 KHz is 8 × 10 ³ Ω. -The manufacturing method of the polymer solid electrolyte membrane which is cm < ² > or less .

重量平均分子量５×１０^５以上の超高分子量ポリオレフィンを含有するポリオレフィン組成物１０〜５０重量％と、溶媒９０〜５０重量％からなる溶液を調製し、前記溶液をダイより押し出し、冷却ロールにより引き取りゲル状シートを成形後、シート中の残存溶媒を除去し、乾燥してポリオレフィン微多孔膜を製造後、低分子量ポリマー電解質または電解質モノマーを揮発性溶媒に溶解させた溶液を含浸させ、低分子量ポリマー電解質または電解質モノマーを多孔質膜の孔部分に５容量％以上充填させた後、加熱延伸し、重合して低分子量ポリマーまたはモノマーを高分子量化した後、極性溶媒を含浸させることを特徴とする厚さが２０μｍ以下で、１０ＫＨｚでの実部インピーダンスが８×１０ ^３ Ω・ｃｍ ^２以下である高分子固体電解質薄膜の製造方法。A solution comprising 10 to 50% by weight of a polyolefin composition containing an ultra-high molecular weight polyolefin having a weight average molecular weight of 5 × 10 ⁵ or more and a solvent of 90 to 50% by weight is prepared. The solution is extruded from a die and taken up by a cooling roll. After forming the gel sheet, the residual solvent in the sheet is removed and dried to produce a polyolefin microporous membrane, which is then impregnated with a solution in which a low molecular weight polymer electrolyte or electrolyte monomer is dissolved in a volatile solvent, and then a low molecular weight polymer. It is characterized by filling the pore portion of the porous membrane with 5% by volume or more of an electrolyte or electrolyte monomer, then heating and stretching, polymerizing to polymerize a low molecular weight polymer or monomer, and then impregnating with a polar solvent. thickness at 20μm or less, a polymer solid electrolyte real part impedance is 8 × 10 ³ Ω · cm ² or less at 10KHz Method of manufacturing the film.

請求項１又は２に記載の高分子固体電解質薄膜の製造方法により製造されたことを特徴とする高分子固体電解質薄膜。A polymer solid electrolyte thin film produced by the method for producing a polymer solid electrolyte thin film according to claim 1.

請求項３記載の高分子固体電解質薄膜を用いた電池。A battery using the solid polymer electrolyte thin film according to claim 3 .