JP2009070606A - Lithium polymer battery - Google Patents
Lithium polymer battery Download PDFInfo
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- JP2009070606A JP2009070606A JP2007235355A JP2007235355A JP2009070606A JP 2009070606 A JP2009070606 A JP 2009070606A JP 2007235355 A JP2007235355 A JP 2007235355A JP 2007235355 A JP2007235355 A JP 2007235355A JP 2009070606 A JP2009070606 A JP 2009070606A
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- negative electrode
- positive electrode
- separator
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、リチウムポリマー電池に関する。 The present invention relates to a lithium polymer battery.
リチウムイオン２次電池は、小型軽量の充電可能な電池で、単位容積あるいは単位重量あたり蓄電容量が大きく、携帯電話、ノートパソコン、携帯情報端末（ＰＤＡ）、ビデオカメラ、デジタルカメラなどに広く利用され、小型軽量で比較的電力消費の大きな各携帯型機器には必要不可欠なものとなっている。また、近年では電動自転車や電動自動車に搭載する中型・もしくは大型のリチウムイオン２次電池の開発が進められており、環境負荷を低減させる手段としてもその開発に期待が寄せられている。 Lithium-ion secondary batteries are small, lightweight, rechargeable batteries with a large storage capacity per unit volume or unit weight, and are widely used in mobile phones, notebook computers, personal digital assistants (PDAs), video cameras, digital cameras, etc. It is indispensable for each portable device that is small, light and relatively large in power consumption. In recent years, the development of medium- or large-sized lithium ion secondary batteries to be mounted on electric bicycles and electric vehicles has been promoted, and the development is expected as a means for reducing environmental load.
現在、このリチウムイオン２次電池の電解液には、炭酸プロピレン、炭酸エチレンなどを主とした電解液溶媒にリチウム電解質塩を溶解した液状の電解液を使用しているものが殆どである。しかし液状の電解液を使用した電池では、電解液の漏洩の危険性に加えて、使用環境や誤使用・事故による温度上昇や内圧上昇、破裂、発火といった安全性が問題となる。 At present, most of the electrolyte solution of the lithium ion secondary battery uses a liquid electrolyte solution in which a lithium electrolyte salt is dissolved in an electrolyte solvent mainly composed of propylene carbonate, ethylene carbonate, or the like. However, in the case of a battery using a liquid electrolyte, in addition to the risk of leakage of the electrolyte, there are problems of safety such as temperature increase, internal pressure increase, rupture and ignition due to use environment, misuse and accident.
特に、自転車や自動車といった高容量・高出力用の用途で使用する場合には、非常に大きなエネルギー量を必要とするため、電池の安全性は重要な課題となる。この課題の解決に向けて電解質をゲル状または固体状の電解質で形成することが提案されている（特許文献１、２など）。 In particular, when used in high capacity / high output applications such as bicycles and automobiles, a very large amount of energy is required, and thus battery safety is an important issue. In order to solve this problem, it has been proposed to form an electrolyte with a gel or solid electrolyte (Patent Documents 1 and 2, etc.).
一方、電解液系電解質のリチウムイオン２次電池のセパレーターとして、電気絶縁性の無機皮膜を有する多孔性の基盤を用いることにより、電池にシャットダウンメカニズムを設け、電池の安全性を飛躍的に向上させることが可能なセパレーターの製造法が報告されている（特許文献３、４など）。 On the other hand, by using a porous substrate having an electrically insulating inorganic film as a separator for an electrolyte electrolyte lithium ion secondary battery, a shutdown mechanism is provided in the battery, and the safety of the battery is dramatically improved. It has been reported that a separator can be manufactured (Patent Documents 3, 4, etc.).
エチレン性不飽和基とエーテル結合を有するポリマー組成物を用いることにより、電解質のイオン伝導度と電池としてのサイクル特性やエネルギー密度を向上させることが提案されている（特許文献５）。
しかしながら、液状の電解質を利用したリチウムイオン２次電池と比較して安全性が高いとされるゲル状又は固体状電解質を有するリチウムポリマー電池であっても、中・大型用途にリチウム電池を使用する場合、従来技術では安全性が不十分であり、各メーカーがリチウム電池採用に踏み切れない原因となっている。 However, even if the lithium polymer battery has a gel or solid electrolyte, which is considered to be safer than a lithium ion secondary battery using a liquid electrolyte, the lithium battery is used for medium and large applications. In this case, the safety of the conventional technology is insufficient, which causes each manufacturer not to adopt lithium batteries.
また、電池製造の観点から見れば、粘度の高いポリマー溶液を如何に早く、均一に注液するかがポイントとなり、モノマー組成の検討、セパレーターへの含浸、電極微細構造を含めた解決すべき課題が多くある。これらの課題を解決するためには、含浸時間の延長や新設備の導入が必要となり、電池の製造効率を下げる原因にもなる。 Also, from the viewpoint of battery manufacturing, it is important to quickly and uniformly inject a polymer solution with a high viscosity. Problems to be solved, including examination of the monomer composition, impregnation into the separator, and electrode microstructure There are many. In order to solve these problems, it is necessary to extend the impregnation time and introduce new equipment, which causes a decrease in battery production efficiency.
本発明は、上記問題に鑑み、リチウムイオン２次電池に強く要求されている安全性の向上に向けて、電池構成材料の選択と吟味を行い、従来のリチウムポリマー電池よりも優れた電池性能と高い安全性を持ち合わせたリチウムポリマー電池を提供することを課題とする。 In view of the above problems, the present invention performs selection and examination of battery constituent materials to improve safety which is strongly demanded for lithium ion secondary batteries, and has battery performance superior to conventional lithium polymer batteries. It is an object to provide a lithium polymer battery with high safety.
本発明者らは、ラジカル重合性官能基を有する架橋性材料を用いたゲル電解質と、非導電性多孔質材料と電気絶縁性の粒子からなるセパレーターを組み合わせることにより、ポリマー電池の性能及び電池の安全性が飛躍的に向上することを見出した。また、電解液のセパレーターへの含浸性が向上することにより、従来の電池性能を保ったまま、電解液の漏洩や発煙、発火といった事故を防ぐことが可能になり、本発明を完成させるに至った。 By combining a gel electrolyte using a crosslinkable material having a radical polymerizable functional group and a separator made of a non-conductive porous material and electrically insulating particles, the inventors of the present invention have the following advantages. It was found that safety improved dramatically. In addition, by improving the impregnating property of the electrolyte into the separator, it is possible to prevent accidents such as leakage, smoke, and ignition of the electrolyte while maintaining the conventional battery performance, thereby completing the present invention. It was.
すなわち、請求項１に記載の発明は、ポリマー電解質、セパレーター及び電極材料からなるリチウムポリマー電池であって、前記ポリマー電解質が、溶媒、電解質塩及びラジカル重合性官能基を有する化合物を含む溶液を、活性放射線の照射及び／又は加熱により架橋して得られたポリマー電解質であり、前記セパレーターが非導電性多孔質材料と電気絶縁性の粒子からなるセパレーターであることを特徴とするリチウムポリマー電池である。 That is, the invention according to claim 1 is a lithium polymer battery comprising a polymer electrolyte, a separator, and an electrode material, wherein the polymer electrolyte includes a solution containing a solvent, an electrolyte salt, and a compound having a radical polymerizable functional group. A lithium polymer battery, characterized in that it is a polymer electrolyte obtained by crosslinking by irradiation with actinic radiation and / or heating, wherein the separator is a separator composed of a non-conductive porous material and electrically insulating particles. .
請求項２に記載の発明は、前記ラジカル重合性官能基を有する化合物が、アルキレンオキシド重合体のヒドロキシル基をラジカル重合基に変性した化合物であることを特徴とする請求項１に記載のリチウムポリマー電池である。 The invention according to claim 2 is the lithium polymer according to claim 1, wherein the compound having a radical polymerizable functional group is a compound obtained by modifying a hydroxyl group of an alkylene oxide polymer into a radical polymerizable group. It is a battery.
請求項３に記載の発明は、前記ラジカル重合性官能基を有する化合物が、下記一般式（１）、（３）、（４）、及び（５）で表される構造単位から選ばれる１種又は２種以上の構造単位を含有することを特徴とする請求項１又は２に記載のリチウムポリマー電池である。
本発明によれば、従来のポリマー電池よりも優れた性能を持ち、かつ安全性の高いリチウム電池の製造が可能になる。すなわち、電池のトラブルは内部温度の上昇から、内圧の上昇、さらには破裂、発火を引き起こし大事故になりかねないが、本願では内部温度の上昇に対して、ポリマー電解質に加えて、ポリマーや基材が万一溶融や収縮した場合にも、耐熱性があり、溶融しない材料粒子を用いることにより、大面積の内部短絡を引き起こさず、ポリマー電解質とセパレーターの二重の効果により従来の電解液系リチウム電池よりも高い安全性を付与することができる。 According to the present invention, it is possible to manufacture a lithium battery having performance superior to that of a conventional polymer battery and high safety. In other words, battery trouble may cause a major accident due to internal temperature increase, internal pressure increase, and further explosion and ignition, but in this application, in addition to polymer electrolyte, in addition to polymer electrolyte, In the unlikely event that the material melts or shrinks, the use of material particles that are heat resistant and do not melt does not cause a large internal short circuit, and the conventional electrolyte system due to the double effect of the polymer electrolyte and separator Safety higher than that of a lithium battery can be imparted.
また、このリチウム２次電池は、従来と同様の製造設備で製造することが可能で、新しい設備を必要としない。 Moreover, this lithium secondary battery can be manufactured with the same manufacturing equipment as before, and does not require new equipment.
さらに、本発明で挙げたセパレーターの使用により電池の安全性が向上するだけでなく、セパレーター表面の濡れ性が改善することで、電解液含浸時間の短縮が可能になり、ポリマー電解質を用いた場合にも電池の界面抵抗を低下させ、優れた電池性能が得られる。 Furthermore, the use of the separator mentioned in the present invention not only improves the safety of the battery but also improves the wettability of the separator surface. In addition, the interface resistance of the battery is reduced, and excellent battery performance can be obtained.
本発明において、前記ラジカル重合性官能基を有する化合物は、アルキレンオキサイド重合体のヒドロキシル基をラジカル重合基に変性した化合物であることが好ましい。 In the present invention, the compound having a radical polymerizable functional group is preferably a compound obtained by modifying a hydroxyl group of an alkylene oxide polymer into a radical polymerizable group.
前記ラジカル重合性官能基を有する化合物は、例えば、活性水素残基を１個以上有する化合物やアルコキサイドに１種類以上のアルキレンオキサイドの単量体を付加させて得られたアルキレンオキサイド重合体の主鎖または側鎖の末端に、重合性官能基や非重合性官能基を導入することにより得られる。各末端は、全て重合性官能基であっても、全て非重合性官能基であっても、両者が含まれていてもよい。 The compound having the radical polymerizable functional group is, for example, a main chain of an alkylene oxide polymer obtained by adding one or more alkylene oxide monomers to a compound having one or more active hydrogen residues or alkoxide. Alternatively, it can be obtained by introducing a polymerizable functional group or a non-polymerizable functional group at the end of the side chain. Each end may be a polymerizable functional group, or may be a non-polymerizable functional group, or may contain both.
全て非重合性官能基の場合には、他の重合性官能基を有する化合物と共に使用する。 重合性官能基を導入する場合の官能基の例としては、（メタ）アクリル酸、アリル基、ビニル基が挙げあられ、非重合性官能基の例としては、アルキル基又はホウ素原子を含む官能基が挙げられる。上記アルキル基としてはメチル基が特に好ましい。 In the case of all non-polymerizable functional groups, they are used together with compounds having other polymerizable functional groups. Examples of functional groups for introducing polymerizable functional groups include (meth) acrylic acid, allyl groups, and vinyl groups. Examples of non-polymerizable functional groups include functional groups containing alkyl groups or boron atoms. Is mentioned. The alkyl group is particularly preferably a methyl group.
重合性官能基の導入方法としては、アクリル酸、メタクリル酸などの不飽和有機酸のエステル化反応、あるいは、トリレンジイソシアネートなどのジイソシアネートとの反応後さらに、２−ヒドロキシエチルアクリレートや２−ヒドロキシプロピルアクリレートなどのヒドロキシル基を有するアクリレートによるウレタン反応、あるいは、アクリル酸クロリド、メタクリル酸クロリドなどの酸クロリド類を脱塩酸反応、またはハロゲン化アルキルなどの縮合反応によって得ることができる。 As a method for introducing a polymerizable functional group, an esterification reaction of an unsaturated organic acid such as acrylic acid or methacrylic acid, or a reaction with a diisocyanate such as tolylene diisocyanate, and further 2-hydroxyethyl acrylate or 2-hydroxypropyl It can be obtained by urethane reaction with acrylate having hydroxyl group such as acrylate, or acid chlorides such as acrylic acid chloride and methacrylic acid chloride by dehydrochlorination reaction or condensation reaction such as alkyl halide.
前記ラジカル重合性官能基を有する化合物は、下記一般式（１）、（３）、（４）、及び（５）で表される構造単位から選ばれる１種又は２種以上の構造単位を含有する。 The compound having a radical polymerizable functional group contains one or more structural units selected from structural units represented by the following general formulas (1), (3), (4), and (5). To do.
式中、Ｒ１は活性水素含有化合物残基を表し、Ｒ２は炭素数１〜６のアルキル基、Ｒ３は下記一般式（２）で表される置換基を示し、Ｒ４は（メタ）アクリル基またはアルキル基、ｍ及びｎはそれぞれ０又は１以上の数を示し、ｍ＝ｎ＝０の場合を含まず、ｘは１以上の整数を示し、構造単位−ＣＨ２ＣＨＲ２Ｏ−及び−ＣＨ２ＣＨＲ３Ｏ−は１種類又は２種類以上用いても良い。 In the formula, R 1 represents an active hydrogen-containing compound residue, R 2 represents an alkyl group having 1 to 6 carbon atoms, R 3 represents a substituent represented by the following general formula (2), and R 4 represents (meta ) Acrylic group or alkyl group, m and n each represent 0 or 1 or more, m = n = 0 is not included, x represents an integer of 1 or more, and the structural unit —CH 2 CHR 2 O— And —CH 2 CHR 3 O— may be used alone or in combination of two or more.
式中、ｙは０または１以上の数を示し、Ｒ５はアルキル基またはアルケニル基を示す。 In the formula, y represents 0 or a number of 1 or more, and R 5 represents an alkyl group or an alkenyl group.
前記一般式（１）で表される構造単位は、Ｒ１で表される活性水素含有化合物に−ＣＨ２ＣＨＲ２Ｏ−及び−ＣＨ２ＣＨＲ３Ｏ−で表されるアルキレンオキサイドの単量体を付加重合させることにより得られる。 The structural unit represented by the general formula (1) is an alkylene oxide monomer represented by —CH 2 CHR 2 O— and —CH 2 CHR 3 O— in the active hydrogen-containing compound represented by R 1. Can be obtained by addition polymerization.
前記アルキレンオキサイドの単量体は、エチレンオキサイド、プロピレンオキサイド、イソブチレンオキサイド、１−ブテンオキサイド、２−ブテンオキサイド、α−オレフィンオキサイド、トリメチルエチレンオキサイド、テトラメチルエチレンオキシド、ブタジエンモノオキシド、スチレンオキシド、α−メチルスチレンオキシド、１，１−ジフェニルエチレンオキシド、エピフルオロヒドリン、エピクロロヒドリン、エピブロモヒドリン、グリシドール、ブチルグリシジルエーテル、ヘキシルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、２−クロルエチルグリシジルエーテル、Ｏ−クロロフェニルグリシジルエーテル、エチレングリコールジグリシジルエーテル、ビスフェノールＡ、ジグリシジルエーテル、シクロヘキセンオキシド、ジヒドロナフタリンオキシド、ビニルシクロヘキセンモノオキシド、オキセタン、テトラヒドロフラン、テトラヒドロピラン、１，４−エポキシシクロヘキサン等が挙げられる。 The alkylene oxide monomers are ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, α-olefin oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monooxide, styrene oxide, α- Methylstyrene oxide, 1,1-diphenylethylene oxide, epifluorohydrin, epichlorohydrin, epibromohydrin, glycidol, butyl glycidyl ether, hexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether O-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenol A, diglycidyl ether And ether, cyclohexene oxide, dihydronaphthalene oxide, vinylcyclohexene monooxide, oxetane, tetrahydrofuran, tetrahydropyran, 1,4-epoxycyclohexane and the like.
前記活性水素化合物は特に限定されないが、エチレングリコールモノメチルエーテル、メタノール、エタノール、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、グリセリン、トリメチロールプロパン、ソルビトール、シュークローズ、ペンタエリスリトール、ジグリセリンなどの１価または多価アルコール、ブチルアミン、２−エチルヘキシルアミン、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、アニリン、ベンジルアミン、フェニレンジアミン等のアミン化合物、ビスフェノールＡ 、ハイドロキノン、ノボラック等のフェノール性活性水素化合物、モノエタノールアミン、ジエタノールアミンなどの１分子中に異種の活性水素残基を有する化合物等が挙げられる。特にアルキレンオキシドとの反応性がよい化合物が好ましく、エチレングリコールモノメチルエーテル、エチレングリコール、グリセリン、ジグリセリン、ペンタエリスリトール、ソルビトールが特に好ましい。 The active hydrogen compound is not particularly limited, but includes ethylene glycol monomethyl ether, methanol, ethanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, sorbitol, shoecloth, pentaerythritol, diglycerin, and the like. Monohydric or polyhydric alcohol, butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, amine compounds such as benzylamine, phenylenediamine, bisphenol A, Phenolic active hydrogen compounds such as hydroquinone and novolak, monoethanolamine, diethanolamine, etc. Compounds having an active hydrogen residue of a different like in the molecule. Particularly preferred are compounds having good reactivity with alkylene oxide, and ethylene glycol monomethyl ether, ethylene glycol, glycerin, diglycerin, pentaerythritol and sorbitol are particularly preferred.
前記一般式（１）におけるｘは１以上の整数であり、好ましくは１〜１２、さらに好ましくは１〜４である。ｘが１２を超える場合は、均一な重合反応が難しくなることがある。 X in the said General formula (1) is an integer greater than or equal to 1, Preferably it is 1-12, More preferably, it is 1-4. When x exceeds 12, a uniform polymerization reaction may be difficult.
前記一般式（１）におけるｍ＋ｎは１〜１５０００の数を示し、好ましくは４０〜１２０００である。 M + n in the general formula (1) represents a number of 1 to 15000, preferably 40 to 12000.
前記一般式（１）における−ＣＨ２ＣＨＲ２Ｏ−及び−ＣＨ２ＣＨＲ３Ｏ−の付加形態は、それぞれの単独重合、２種以上のランダム共重合又はブロック共重合であっても良い。 The addition form of —CH 2 CHR 2 O— and —CH 2 CHR 3 O— in the general formula (1) may be a homopolymerization, a random copolymerization of two or more kinds, or a block copolymerization.
前記一般式（２）におけるｙは０又は１〜２５の整数を示し、好ましくは１〜３である。 Y in the general formula (2) represents 0 or an integer of 1 to 25, preferably 1 to 3.
１分子中において、一般式（３）の構造単位は１〜２３０００個であり、好ましくは５〜１１４００個、より好ましくは１０〜５７００個である。 In one molecule, the number of structural units of the general formula (3) is 1 to 23000, preferably 5 to 11400, and more preferably 10 to 5700.
また、一般式（４）あるいは一般式（５）の構造単位数（但し、両者を含む時は合計数）は、１分子中において１〜１３６００個であり、好ましくは５〜６８００個、より好ましくは１０〜３４００個である。 In addition, the number of structural units of the general formula (4) or the general formula (5) (however, when both are included) is 1 to 13600 in a molecule, preferably 5 to 6800, and more preferably Is 10-3400.
本発明において、ラジカル重合開始剤は特に限定されるものではないが、熱重合開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス［Ｎ−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス［Ｎ−（２−プロペニル）−２−メチルプロピオンアミド］、２，２’−アゾビス（２，４，４−トリメチルペンタン）などアゾ化合物、メチルエチルケトンパーオキサイドなどのケトンパーオキサイド、１，１−ジ−ｔ−ブチルパーオキシシクロヘキサンなどのパーオキシケタール、ジイソプロピルベンゼンハイドロパーオキサイドなどのハイドロパーオキサイド、ジクミルパーオキサイドなどのジアルキルパーオキサイド、ジイソブチルパーオキサイドなどのジアシルパーオキサイド、ｔ−ブチルパーオキシイソプロピルカーボネートなどのパーオキシエステル、ジ−ｎ−プロピルパーオキシジカーボネートなどのパーオキシジカーボネートなどの有機過酸化物が挙げられる。 In the present invention, the radical polymerization initiator is not particularly limited. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile and 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis [N- (2-imidazolin-2-yl) propane], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2, Azo compounds such as 2'-azobis (2,4,4-trimethylpentane), ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di-t-butylperoxy Peroxyketals such as hexane, hydroperoxides such as diisopropylbenzene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, diacyl peroxides such as diisobutyl peroxide, peroxyesters such as t-butylperoxyisopropyl carbonate, And organic peroxides such as peroxydicarbonate such as di-n-propyl peroxydicarbonate.
光重合開始剤としては、２，２−ジメトキシ−２−フェニルアセトフェノンなどのアセトフェノン系、トリメチルシリルベンゾフェノン、ベンゾイン、２−メチルベンゾイル、４−メトキシベンゾフェノン、ベンゾインメチルエーテルアントラキノン、ベンゾルジメチルケタールなどのベンゾフェノン系、ビス（２，６−ジメトキシベンゾイル）２，４，４−トリメチル−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイドなどのフォスヒンオキサイド系などが挙げられる。 Photopolymerization initiators include acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, benzophenones such as trimethylsilylbenzophenone, benzoin, 2-methylbenzoyl, 4-methoxybenzophenone, benzoin methyl ether anthraquinone, and benzoldimethyl ketal. And phosphine oxides such as bis (2,6-dimethoxybenzoyl) 2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
リチウム電解質塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＣＦ３ＳＯ４、ＬｉＣｌＯ４ 、リチウムビスオキサラトボラート（ＬｉＢＯＢ）及び／またはリチウム−ビス（トリフルオロメチルスルホニル）イミド（ＬｉＴＦＳＩ）、ビス（フルオロスルフォニル）イミドリチウム（ＬｉＦＳＩ）等が挙げられ、特にＬｉＰＦ６、ＬｉＢＦ４、ＬｉＴＦＳＩ及びＬｉＦＳＩが好ましい。電解質塩は１種類で用いても２種類以上を用いてもよい。 Lithium electrolyte salts include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 4 , LiClO 4 , lithium bisoxalatoborate (LiBOB) and / or lithium-bis (trifluoromethylsulfonyl) imide (LiTFSI). , Bis (fluorosulfonyl) imidolithium (LiFSI), and the like, and LiPF 6 , LiBF 4 , LiTFSI, and LiFSI are particularly preferable. The electrolyte salt may be used alone or in combination of two or more.
また、電解液のイオン導電率を高めるため、Ｌｉ以外の電解質塩を用いることが可能である。 Moreover, in order to increase the ionic conductivity of the electrolytic solution, it is possible to use an electrolyte salt other than Li.
例えば、ビス（フルオロスルホニル）イミド（ＦＳＩ）−、ＢＦ４ −、ＰＦ６ −、ＳｂＦ６ −、ＮＯ３ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、ＴＦＳＩ−、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＦ３ＣＯ２ −、Ｃ３Ｆ７ＣＯ２ −、ＣＨ３ＣＯ２ −、（ＣＮ）２Ｎ− 等のアニオンとカチオンの組合せから成る塩を用いてもよい。 For example, bis (fluorosulfonyl) imide (FSI) − , BF 4 − , PF 6 − , SbF 6 − , NO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , TFSI − , (C Anions such as 2 F 5 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 CO 2 − , C 3 F 7 CO 2 − , CH 3 CO 2 − , and (CN) 2 N − A salt composed of a combination of cations may be used.
前記カチオンとしては、Ｎ、Ｐ、Ｓ、Ｏ、Ｃ、Ｓｉのいずれかもしくは２種類以上の元素を構造中に含み、鎖状または５員環、６員環などの環状構造を骨格に有する化合物が挙げられ、鎖状化合物の例としてはアルキルアンモニウムなどが挙げられる。環状化合物の例としては、フラン、チオフェン、ピロール、ピリジン、オキサゾ−ル、イソオキサゾ−ル、チアゾ−ル、イソチアゾ−ル、フラザン、イミダゾール、ピラゾール、ピラジン、ピリミジン、ピリダジン、ピロリジン、ピペリジンなどの複素単環化合物、ベンゾフラン、イソベンゾフラン、インドール、イソインドール、イソドリジン、カルバゾールなどの縮合複素環化合物が挙げられる。 As the cation, a compound containing any of N, P, S, O, C, Si or two or more elements in the structure and having a chain structure or a cyclic structure such as a 5-membered ring or a 6-membered ring in the skeleton Examples of chain compounds include alkyl ammonium. Examples of cyclic compounds include furan, thiophene, pyrrole, pyridine, oxazole, isoxazole, thiazol, isothiazol, furazane, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, pyrrolidine, piperidine and the like. Examples thereof include condensed heterocyclic compounds such as a ring compound, benzofuran, isobenzofuran, indole, isoindole, isodolidine, and carbazole.
また、電解質塩が可溶な溶媒としては、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、プロピレンカーボネート（ＰＣ）、メチルプロピルカーボネート（ＰＭＣ）、ブチレンカーボネート（ＢＣ）、ジエチルカーボネート（ＤＥＣ）などのカーボネート類、γ−ブチラクトン（ＧＢＬ）、γ−バレロラクトンなどの環状カルボン酸エステル類、テトラヒドロフラン、メチルテトラヒドロフランなどの環状エーテル類、スルホランなどを使用することができる。このような電解液は、通常では、電解質塩として０．１〜５ｍｏｌ／Ｌ、特に有利に０．５〜２ｍｏｌ／Ｌとすることが好ましい。 Examples of the solvent in which the electrolyte salt is soluble include ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), methylpropyl carbonate (PMC), butylene carbonate (BC), and diethyl carbonate (DEC). Carbonates, cyclic carboxylic acid esters such as γ-butyrolactone (GBL) and γ-valerolactone, cyclic ethers such as tetrahydrofuran and methyltetrahydrofuran, sulfolane and the like can be used. Such an electrolytic solution is usually preferably 0.1 to 5 mol / L, particularly preferably 0.5 to 2 mol / L as an electrolyte salt.
上記電解液は、添加剤を含むものでもよい。添加剤としては、アザインドール、ベンゾイミダゾール、ベンゾヂチオール、ベンゾフラン、ベンゾチアゾール、１−ベンゾチオフェン、１Ｈ−ベンゾトリアゾール、ベンジルカプトン、１−ブロモ−３−フルオロベンゼンなどの含窒素・含硫黄系化合物、ビニレンカーボネート、ビニルアクリレート、ビニルブチレートなどのビニル系化合物の他にショ糖脂肪酸エステル類が挙げられ、その添加量は１０％以下、好ましくは３％以下である。また、添加剤はこれらを２種類以上組み合わせたものでも構わない。 The electrolytic solution may contain an additive. Additives include nitrogen- and sulfur-containing compounds such as azaindole, benzimidazole, benzodithiol, benzofuran, benzothiazole, 1-benzothiophene, 1H-benzotriazole, benzylcapton, 1-bromo-3-fluorobenzene In addition to vinyl compounds such as vinylene carbonate, vinyl acrylate and vinyl butyrate, sucrose fatty acid esters may be mentioned, and the amount added is 10% or less, preferably 3% or less. Further, the additive may be a combination of two or more of these.
前記ラジカル重合性官能基を有する化合物、熱重合開始剤、リチウム電解質及び溶媒からなる溶液を硬化する場合の温度は、特に限定されないが、２０〜１２０℃が好ましく、４０〜１００℃がより好ましい。 Although the temperature in the case of hardening | curing the solution which consists of the compound which has the said radical polymerizable functional group, a thermal polymerization initiator, a lithium electrolyte, and a solvent is not specifically limited, 20-120 degreeC is preferable and 40-100 degreeC is more preferable.
電極材料としてはリチウムイオンの挿入、脱離が可能であるものであれば、特に制限されるものではない。 The electrode material is not particularly limited as long as it can insert and desorb lithium ions.
例えば、正極活物質としては、ＣｕＯ、Ｃｕ２Ｏ、ＭｎＯ２、Ｖ２Ｏ５、ＣｒＯ３、ＭｏＯ３、Ｆｅ２Ｏ３、Ｎｉ２Ｏ３、ＣｕＯ３等の金属酸化物、ＬｉｘＣＯ２、ＬｉｘＮｉＯ２、ＬｉｘＭｎ２Ｏ４、ＬｉＦｅＰＯ４等のリチウムと遷移金属との複合酸化物や、ＴｉＳ２、ＭｏＳ２、ＮｂＳｅ３等の金属カルコゲン化物、ポリアセン、ポリパラフェニレン、ポリピロール、ポリアニリン等の導電性化合物等が挙げられる。 For example, as the positive electrode active material, metal oxides such as CuO, Cu 2 O, MnO 2 , V 2 O 5 , CrO 3 , MoO 3 , Fe 2 O 3 , Ni 2 O 3 , CuO 3 , Li x CO 2 , Li x NiO 2 , Li x Mn 2 O 4 , LiFePO 4 and other complex oxides of lithium and transition metals, TiS 2 , MoS 2 , NbSe 3 and other metal chalcogenides, polyacene, polyparaphenylene, polypyrrole, Examples thereof include conductive compounds such as polyaniline.
特に本発明では、コバルト、ニッケル、マンガン、鉄等の遷移金属から選ばれる１種類以上とリチウムとの複合酸化物が好ましく、リチウムとの複合酸化物の具体例としては、ＬｉＣｏＯ２、ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉｘＣｏ（１−ｘ）Ｏ２、ＬｉＭｎａＮｉｂＣｏｃ（ａ＋ｂ＋ｃ＝１）、ＬｉＦｅＰＯ４などが挙げられる。 In particular, in the present invention, a composite oxide of lithium and at least one selected from transition metals such as cobalt, nickel, manganese, and iron is preferable. Specific examples of the composite oxide of lithium include LiCoO 2 , LiMnO 2 , Examples include LiMn 2 O 4 , LiNi x Co (1-x) O 2 , LiMn a Ni b Co c (a + b + c = 1), LiFePO 4, and the like.
また、これらのリチウム複合酸化物に、少量のフッ素、ホウ素、アルミニウム、クロム、ジルコニウム、モリブデン、鉄などの元素をドープしたものでもよい。 These lithium composite oxides may be doped with a small amount of elements such as fluorine, boron, aluminum, chromium, zirconium, molybdenum, and iron.
また、これらの活物質を混合したものを正極活物質として用いてもよい。 A mixture of these active materials may be used as the positive electrode active material.
負極活物質としては、リチウムを挿入、脱離可能な活物質やリチウムを可逆的に吸蔵、放出可能な活物質で、アルカリ金属、アルカリ金属合金、遷移金属カルコゲナイド、炭素材料などが挙げられる。 Examples of the negative electrode active material include an active material capable of inserting and extracting lithium and an active material capable of reversibly occluding and releasing lithium, and examples thereof include alkali metals, alkali metal alloys, transition metal chalcogenides, and carbon materials.
具体的には、金属リチウム、Ａｌ、Ｍｇ、Ｐｔ、Ｓｎ、Ｓｉ，Ｚｎ、Ｂｉなどのリチウム吸蔵金属、Ａｌ−Ｎｉ、Ａｌ−Ａｇ、Ａｌ−ＭｎなどのＡｌ系リチウム合金、ＳｂＳｎ、ＩｎＳｂ、ＣｏＳｂ３、Ｍｉ２ＭｎＳｂなどのアンチモン系リチウム合金、Ｓｎ２Ｍ（Ｍ＝Ｆｅ、Ｃｏ、Ｍｎ、Ｖ、Ｔｉ）、Ｓｎ５Ｃｕ６、Ｓｎ３Ｖ２、Ｓｎ１２Ａｇ１３、ＳｎＳｂ０．４などのＳｎ系リチウム合金、ＳｎＯ２、Ｓｎ２Ｐ２Ｏ７、ＳＮＰＢＯ６、ＳｎＰＯ４ＣｌなどのＳｎ酸化物、Ｓｉ−Ｃ複合系、Ｓｉ−Ｔｉ複合系、Ｓｉ−Ｍ薄膜などのＳｉ系リチウム合金、Ｓｎ、Ｓｉなどのナノ複合材料、Ｓｎ、Ｃｏ、炭素などのアモルファス合金材料、Ｓｎ−Ａｇ、Ｓｎ−ＣｕなどＳｎ系メッキ合金、Ｓｉ系アモルファス薄膜などが挙げられ、炭素材料としてはアモルファスカーボン、メソカーボンマイクロビーズ、グラファイト、天然黒鉛、難黒鉛化性炭素（ハードカーボン、以下ＨＣ）などがあり、これらの炭素材料の表面修飾物などが好適材料として挙げられ、特に炭素材料が好ましい。 Specifically, lithium storage metals such as metallic lithium, Al, Mg, Pt, Sn, Si, Zn, and Bi, Al-based lithium alloys such as Al—Ni, Al—Ag, and Al—Mn, SbSn, InSb, and CoSb 3 , antimony series lithium alloys such as Mi 2 MnSb, Sn 2 M (M = Fe, Co, Mn, V, Ti), Sn 5 Cu 6 , Sn 3 V 2 , Sn 12 Ag 13 , SnSb 0 . Sn-based lithium alloys such as 4 , Sn oxides such as SnO 2 , Sn 2 P 2 O 7 , SNPBO 6 , SnPO 4 Cl, Si-based such as Si—C composite, Si—Ti composite, and Si—M thin film Examples include lithium alloy, nanocomposite materials such as Sn and Si, amorphous alloy materials such as Sn, Co, and carbon, Sn-based plating alloys such as Sn-Ag and Sn-Cu, and Si-based amorphous thin films. There are carbon, mesocarbon microbeads, graphite, natural graphite, non-graphitizable carbon (hard carbon, hereinafter referred to as HC) and the like, and surface modified products of these carbon materials are listed as suitable materials, and carbon materials are particularly preferable.
上記正極及び負極には導電剤が用いられる。導電剤としては、電池性能に悪影響を及ぼさない電子伝導材料であれば使用することができる。通常、アセチレンブラックやケッチンブラック等のカーボンブラックが使用されるが、天然黒鉛、人造黒鉛、カーボンウイスカー、気相成長炭素などの炭素繊維、カーボンナノチューブ、フラーレン、導電性セラミック材料等を使用してもよく、これらは２種類以上の混合物として含ませることができる。 A conductive agent is used for the positive electrode and the negative electrode. Any conductive material that does not adversely affect battery performance can be used as the conductive agent. Usually, carbon black such as acetylene black and kettin black is used, but carbon fiber such as natural graphite, artificial graphite, carbon whisker, vapor grown carbon, carbon nanotube, fullerene, conductive ceramic material, etc. may be used. Often, these can be included as a mixture of two or more.
電極活物質の集電体としては、構成された電池において悪影響を及ぼさない電子伝導体であれば何でもよい。例えば、正極用集電体としては、アルミニウム、チタン、ステンレス銅、ニッケル、焼成炭素、導電性高分子、導電性硝子等の他に、接着性、導電性、耐酸化性向上の目的で、アルミニウムや銅等の表面をカーボン、ニッケル、チタンや銀等で処理したものを用いることができる。 The current collector for the electrode active material may be any electronic conductor as long as it does not adversely affect the constructed battery. For example, as a current collector for a positive electrode, in addition to aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, conductive glass, etc., aluminum is used for the purpose of improving adhesiveness, conductivity, and oxidation resistance. Or a surface treated with carbon, nickel, titanium, silver or the like can be used.
負極集電体としては、銅、ステンレス鋼、ニッケル、アルミニウム、チタン、焼成炭素、導電性高分子、導電性硝子、Ａｌ−Ｃｄ合金等の他に接着性、導電性、耐酸化性向上の目的で、銅等の表面をカーボン、ニッケル、チタンや銀等で処理したものを用いることができる。 As a negative electrode current collector, in addition to copper, stainless steel, nickel, aluminum, titanium, calcined carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., the purpose of improving adhesion, conductivity, and oxidation resistance And what processed the surface, such as copper, with carbon, nickel, titanium, silver, etc. can be used.
これらの集電体材料は表面を酸化処理することも可能である。これらの形状については、フォイル状の他、フィルム状、シート状、ネット状、パンチ又はエキスパンドされた物、硝子体、多孔質体、発砲体等の成型体も用いられる。 The surface of these current collector materials can be oxidized. As for these shapes, in addition to a foil shape, a film shape, a sheet shape, a net shape, a punched or expanded material, a vitreous body, a porous body, a foamed body and the like are also used.
上記活物質を集電体に結着させるバインダーとしては、ポリフッ化ビニリデン（ＰＶＤＦとヘキサフルオロプロピレン（ＨＦＰ）やパーフルオロメチルビニルエーテル（ＰＦＭＶ）及び、テトラフルオロエチレン（ＴＦＥ）との共重合体などのＰＶＤＦ共重合体樹脂、ポリテトラフルオロエチレン（ＰＴＦＥ）、フッ素ゴムなどのフッ素系樹脂やスチレン−ブタジエンゴム（ＳＢＲ）、エチレン−プロピレンゴム（ＥＰＤＭ）、スチレン−アクリロニトリル共重合体などのポリマーが挙げられ、カルボキシメチルセルロース（ＣＭＣ）等の多糖類、ポリイミド樹脂等の熱可塑性樹脂などを併用することができるができるが、これに限定されるものではない。また、これらは２種類以上を混合して用いてもよい。その添加量としては、活物質量に対して０．２〜３０％が好ましく、さらに０．５〜１０％がより好ましい。 As a binder for binding the active material to the current collector, polyvinylidene fluoride (PVDF and hexafluoropropylene (HFP), perfluoromethyl vinyl ether (PFMV), a copolymer of tetrafluoroethylene (TFE), etc.) Polymers such as PVDF copolymer resins, polytetrafluoroethylene (PTFE), fluorine-based resins such as fluorine rubber, styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPDM), styrene-acrylonitrile copolymer, etc. , Polysaccharides such as carboxymethyl cellulose (CMC), thermoplastic resins such as polyimide resin, etc. can be used together, but are not limited to these. The amount added may be the amount of active material. 0.2 to 30% are preferred for further 0.5% to 10% is more preferable.
ＬｉＦｅＰＯ４のように表面を炭素被覆した正極活物質については、カルボン酸変性したＰＶＤＦまたはＳＢＲの水系バインダーも好ましい材料としてあげることができる。 As for the positive electrode active material whose surface is coated with carbon such as LiFePO 4 , a carboxylic acid-modified PVDF or SBR aqueous binder can also be mentioned as a preferable material.
セパレーターとしては、多孔性の膜が使用され、通常多孔性ポリマーフィルムや不織布が好適に使用される。 As the separator, a porous membrane is used, and usually a porous polymer film or a nonwoven fabric is preferably used.
本発明においては特に、非導電性多孔質材料と電気絶縁性の粒子からなるものが好適である。非導電性多孔質材料はポリアクリロニトリル、ポリエステル（ＰＥＴ）、ポリイミド、ポリアミド、ポリテトラフルオロエチレン、ポリオレフィン、ガラス、セラミック等から選択される。特に、平面状の柔軟な基材に、電気絶縁性の無機皮膜を有する不織布が好適であり、ポリエステル（ＰＥＴ）、ポリアミドが特に好ましい。 In the present invention, those composed of a non-conductive porous material and electrically insulating particles are particularly suitable. The non-conductive porous material is selected from polyacrylonitrile, polyester (PET), polyimide, polyamide, polytetrafluoroethylene, polyolefin, glass, ceramic and the like. In particular, a nonwoven fabric having an electrically insulating inorganic film on a flat flexible substrate is suitable, and polyester (PET) and polyamide are particularly preferred.
セパレーターに使用される絶縁性の粒子としては、無機材料としては少なくとも一種類のアルミナ、チタニア、珪素及び／又はジルコニアなどの無機酸化物、有機物材料としてはフッ素樹脂、ポリスチレン樹脂、アクリル樹脂などのポリマー粒子などが用いられる。 The insulating particles used for the separator include at least one inorganic oxide such as alumina, titania, silicon and / or zirconia as the inorganic material, and a polymer such as fluororesin, polystyrene resin, and acrylic resin as the organic material. Particles are used.
上記セパレーターは、さらにセパレーター又はセパレーター中に、所望の遮断温度で溶融する極めて薄いワックス粒子層、又はポリマー粒子層の遮断粒子が存在することでシャットダウンメカニズムを有することができる。この遮断粒子を形成するのに有利な材料としては、天然または人口のワックス、ポリオレフィンなどの低融点ポリマーがあり、この粒子が所望の遮断温度で溶融し、かつセパレーターの細孔を閉鎖することで、電池の異常作動時の更なる電流を抑制することができる。 The separator may further have a shutdown mechanism due to the presence of a very thin wax particle layer or polymer particle layer that melts at a desired barrier temperature in the separator or the separator. Advantageous materials for forming the blocking particles include natural or artificial waxes, low melting polymers such as polyolefins, which melt at the desired blocking temperature and close the pores of the separator. Further current during the abnormal operation of the battery can be suppressed.
本発明のリチウムポリマー電池は、円筒形、コイン型、角型、その他任意の形状に形成することができ、電池の基本構成は形状によらず同じであり、目的に応じて設計変更し実施することができる。 The lithium polymer battery of the present invention can be formed into a cylindrical shape, a coin shape, a rectangular shape, or any other shape, and the basic configuration of the battery is the same regardless of the shape, and the design is changed and implemented according to the purpose. be able to.
本発明のリチウムポリマー電池は、例えば、円筒形では、負極集電体に負極活物質を塗布してなる負極と、正極集電体に正極活物質を塗布してなる正極とを、セパレーターを介して捲回した捲回体を電池缶に収納し、硬化前のポリマー電解質を注入し上下に絶縁板を載置した状態で密封し、加熱することによりポリマーを硬化させることにより得られる。 In the lithium polymer battery of the present invention, for example, in a cylindrical shape, a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode formed by applying a positive electrode active material to a positive electrode current collector are interposed via a separator. It is obtained by storing the wound body in a battery can, injecting a polymer electrolyte before curing, sealing it with the insulating plates placed on the top and bottom, and curing the polymer by heating.
ポリマー電解質を紫外線硬化させる場合には、正極と負極とセパレーターを硬化前のポリマー電解質に含浸し、負極とセパレーターを積層し、紫外線を照射しゲル化した後、正極と負極の間にセパレーターを挟むように捲回した捲回体を電池缶に収納し上下に絶縁板を載置した状態で密封することにより得られる。 When the polymer electrolyte is cured with ultraviolet light, the positive electrode, the negative electrode, and the separator are impregnated with the polymer electrolyte before curing, the negative electrode and the separator are laminated, and after irradiation with ultraviolet light, the polymer is sandwiched between the positive electrode and the negative electrode. The wound body thus wound is housed in a battery can and sealed with the insulating plates placed on the top and bottom.
本発明のリチウムポリマー電池を作製する場合、選択した電極活物質により、初回の充電時に多量のガスが発生し、セル性能に影響があるような場合には、硬化前のポリマー電解液混合溶液をプレ電池に注入後、前処理として充電、または充放電の処理を行った後、ポリマーの熱処理を行ってもよい。 When producing the lithium polymer battery of the present invention, the selected electrode active material generates a large amount of gas during the first charge, which may affect the cell performance. After injecting into the pre-battery, the polymer may be subjected to heat treatment after being charged or charged / discharged as a pretreatment.
［合成例］
（アルキレンオキサイドの合成）
架橋性材料となる一般式（１）で表される構造単位を含む化合物の出発物質、単量体（ｗｔ％）、単量体配列、分子量、末端基を表１に示す。
[Synthesis example]
(Synthesis of alkylene oxide)
Table 1 shows the starting material, monomer (wt%), monomer sequence, molecular weight, and terminal group of the compound containing the structural unit represented by the general formula (1), which is a crosslinkable material.
表１において、ＥＯ：エチレンオキサイド、ＰＯ：プロピレンオキサイド、ＢＯ：ブチレンオキサイド、ＡＧＥ：アリルグリシジルエーテル、ＭＥ１：−ＣＨ２Ｏ−ＣＨ２ＣＨ２Ｏ−ＣＨ３ 、ＭＥ２：−ＣＨ２Ｏ−（ＣＨ２ＣＨ２Ｏ）２−ＣＨ３、ＭＥ３：−ＣＨ２Ｏ−（ＣＨ２ＣＨ２Ｏ）３−Ｃ２Ｈ５を示し、配列はＨ：単独重合体、Ｒ：ランダム共重合体、Ｂ：ブロック共重合体を示す。 In Table 1, EO: ethylene oxide, PO: propylene oxide, BO: butylene oxide, AGE: allyl glycidyl ether, ME1: -CH 2 O-CH 2 CH 2 O-CH 3, ME2: -CH 2 O- (CH 2 CH 2 O) 2 -CH 3 , ME3: -CH 2 O- (CH 2 CH 2 O) shows the 3 -C 2 H 5, sequence H: homopolymer, R: random copolymer, B: A block copolymer is shown.
架橋性材料である一般式（３）、（４）及び（５）で表される構造単位を含む化合物の出発物質、単量体（ｗｔ％）、分子量、末端修飾基を表２に示す。 Table 2 shows the starting materials, monomers (wt%), molecular weights, and terminal modification groups of the compounds containing the structural units represented by the general formulas (3), (4) and (5) which are crosslinkable materials.
（熱重合でゲル電解質の場合）
〈実施例１〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ１２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮ−メチル−２−ピロリドン（ＮＭＰ）１６．３ｇで希釈し、固形分６５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
(In the case of gel electrolyte by thermal polymerization)
<Example 1>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 100g, acetylene black as a conductive agent (Denki Kagaku Kogyo Co., Denka Black) 6 g, PVDF as a binder (Ltd. Kureha KF Binder # 1120 NMP 12 wt% solution) 50 g (6 g as a solid content) and 16.3 g N-methyl-2-pyrrolidone (NMP) as a dispersion medium were diluted to prepare a positive electrode coating solution so that the solid content was 65 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるメソカーボンマイクロビーズ（ＭＣＭＢ）（大阪ガスケミカル（株）ＭＣＭＢ２５−２８）９５ｇ、ハードカーボン（（株）クレハ化学 カーボトロンＰ Ｓ（Ｆ））５ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ） 、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度 １．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of mesocarbon microbeads (MCMB) (Osaka Gas Chemical Co., Ltd. MCMB25-28) as a negative electrode active material, 5 g of hard carbon (Kureha Chemical Co., Ltd. Carbotron PS (F)), acetylene black (electrochemistry) as a conductive agent Industrial (Denka Black) 5g, PVDF (Kureha KF Binder # 1120 NMP 12wt% solution) 41.7g (5g as a solid content) as a binder, NMP 36.7g as a dispersion medium is mixed with a planetary mixer, A negative electrode coating solution having a solid content of 60 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and has an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１である出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％ランダム共重合体（分子量１００００）５ｇと、ＬｉＰＦ６ １．２ｍｏｌ／Ｌ、エチレンカーカーボネート（ＥＣ）：ジエチルカーボネート（ＤＥＣ）＝３：７（体積比）電解液９５ｇを溶解し、ポリマー５ｗｔ％を調整した。さらに、熱重合開始剤として上記溶液重量に対して、１ｗｔ％のアゾ化合物である２，２’−アゾビスイソブチロニトリルを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
4 functional terminal acryloyl modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 10000) 5 g, LiPF 6 1.2 mol / L, ethylene carbonate EC): Diethyl carbonate (DEC) = 3: 7 (volume ratio) An electrolyte solution of 95 g was dissolved to prepare 5 wt% polymer. Further, 1 wt% of 2,2′-azobisisobutyronitrile as an azo compound was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
得られた正極と負極の間にセパレーターとしてＰＥＴ素材の不織布にＳｉＯ２とＡｌ２Ｏ３を被覆した厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を挟んだ構造の積層体を作製し、端子を取り出すためのタブリードを溶接したのち、アルミラミネート包材に入れ、３方向を熱融着し、１方向に開口部を作った袋状のプレ電池を作製した。プレ電池にあらかじめ調整したポリマー／電解液混合溶液３ｇを注入した後、開放部のアルミラミネートを真空ヒートシーラーで封止し、６５℃、２０時間かけてポリマーを硬化し、試験用のセルを作製した。
[Production of lithium battery]
A laminated body having a structure in which Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm in which a non-woven fabric of PET material is coated with SiO 2 and Al 2 O 3 as a separator is sandwiched between the obtained positive electrode and the negative electrode is prepared, and a terminal After welding the tab lead for taking out the film, it was put into an aluminum laminate packaging material, and heat-sealed in three directions to produce a bag-shaped pre-battery having openings in one direction. After injecting 3 g of polymer / electrolyte mixed solution prepared in advance into the pre-battery, the aluminum laminate in the open part was sealed with a vacuum heat sealer, and the polymer was cured at 65 ° C. for 20 hours to produce a test cell. did.
〈実施例２〉
［正極の作製］
正極活物質であるＬｉＭｎ２Ｏ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５８．３ｇ（固形分として７ｇ）、分散媒としてＮＭＰ１．４ｇで希釈し固形分６８ｗｔ％になるように正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 2>
[Production of positive electrode]
LigMn 2 O 4 100 g as a positive electrode active material, acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) 5 g as a conductive agent, PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) 58.3 g as a binder A positive electrode coating solution was prepared so that the solid content was 7 g) and the dispersion medium was diluted with 1.4 g of NMP to a solid content of 68 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるＭＣＭＢ（大阪ガスケミカル（株）ＭＣＭＢ１０−２８）９５ｇ、難黒鉛化炭素（（株）クレハ カーボトロン Ｐ（Ｓ））５ｇ、導電剤としてアセチレンブラック５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し固形分５３．６％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of MCMB (Osaka Gas Chemical Co., Ltd. MCMB10-28), 5 g of non-graphitizable carbon (Kureha Carbotron P (S)), 5 g of acetylene black as a conductive agent, and PVDF as a binder Kureha KF Binder # 1120 NMP 12 wt% solution) 41.7 g (5 g as a solid content) and 36.7 g NMP as a dispersion medium were mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 53.6%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物２である出発物質にグリセリンを用いた３官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％ランダム共重合体（分子量８０００）５ｇと、ＬｉＰＦ６１ｍｏｌ／Ｌ、ＥＣ：ジメチルカーボネート（ＤＭＣ）＝３：７（体積比）電解液９５ｇを溶解し、ポリマー５ｗｔ％を調整した。さらに、熱重合開始剤として上記溶液重量に対して、０．２ｗｔ％のパーオキシカーボネート系有機化酸化物であるビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Trifunctional terminal acryloyl-modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 8000) 5 g, LiPF 6 1 mol / L, EC: dimethyl carbonate (DMC) = 3: 7 (volume ratio) 95 g of an electrolytic solution was dissolved to prepare 5 wt% polymer. Further, bis (4-t-butylcyclohexyl) peroxydicarbonate, which is 0.2 wt% peroxycarbonate-based organic oxide, is dissolved as a thermal polymerization initiator with respect to the weight of the above solution, and the pre-curing solution is dissolved. It was adjusted.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例３〉
［正極の作製］
正極活物質であるＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ３．６ｇで希釈し固形分７０ｗｔ％になるように正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 3>
[Production of positive electrode]
The positive electrode active material LiNi 0 . 8 Co 0 . 15 Al 0 . 05 O 2 100 g, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, 50 g of PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder, 6 g as a solid content, dispersion medium Was diluted with 3.6 g of NMP to prepare a positive electrode coating solution so as to have a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質である平均粒径１２μｍ、比表面積４．３ｍ２／ｇ の天然黒鉛１００ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
100 g of natural graphite having an average particle diameter of 12 μm and a specific surface area of 4.3 m 2 / g as a negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and PVDF (Kureha KF Binder, Inc.) as a binder # 1120 NMP 12 wt% solution) 41.7 g (5 g as solid content) and NMP 36.7 g as a dispersion medium were mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 60 wt%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物３の出発物質にグリセリンを用いた３官能性末端アクリロイル変性プロピレンオキサイド単独重合体（分子量５０００）２ｇと化合物１１のメチル基変性エチレンオキサイド７５ｗｔ％、プロピレンオキサイド１５ｗｔ％、アリルグリシジルエーテルランダム共重合体（分子量２５００００）１ｇ、ＬｉＰＦ６ １．２ｍｏｌ／Ｌ、ＥＣ：プロピレンカーボネート（ＰＣ）：ＤＥＣ＝６：１：１３（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、１ｗｔ％の有機過酸化物であるｔ−ブチルパーオキシネオデカネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
2 g of trifunctional terminal acryloyl-modified propylene oxide homopolymer (molecular weight 5000) using glycerin as the starting material of compound 3, methyl group-modified ethylene oxide 75 wt%, propylene oxide 15 wt%, allyl glycidyl ether random copolymer of compound 11 (Molecular weight 250,000) 1 g, LiPF 6 1.2 mol / L, EC: propylene carbonate (PC): DEC = 6: 1: 13 (volume ratio) 97 g of an electrolytic solution was dissolved to prepare 3 wt% polymer. Further, t-butylperoxyneodecanate, which is 1 wt% organic peroxide, was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてポリアミドにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み２５μｍのセパレーターを使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
A separator was prepared in the same manner as in Example 1 except that a separator having a thickness of 25 μm obtained by coating polyamide with SiO 2 and Al 2 O 3 was used.
〈実施例４〉
［正極の作製］
正極活物質であるＬｉＣｏＯ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ２１．８ｇで希釈し固形分６３ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 4>
[Production of positive electrode]
LiCoO 2 100 g which is a positive electrode active material, acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) 5 g as a conductive agent, PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) 50 g (solid content 6 g) ), A positive electrode coating solution was prepared so as to be diluted with 21.8 g of NMP as a dispersion medium to a solid content of 63 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質である平均粒径２０μｍ、比表面積１．７ｍ２／ｇ の天然黒鉛１００ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
100 g of natural graphite having an average particle diameter of 20 μm and a specific surface area of 1.7 m 2 / g as a negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and PVDF (Kureha KF Binder, Inc.) as a binder # 1120 NMP 12 wt% solution) 41.7 g (5 g as solid content) and NMP 36.7 g as a dispersion medium were mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 60 wt%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物４である出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド５ｗｔ％、ブチレンオキサイド１５ｗｔ％のランダム共重合体（分子量１００００）２ｇと化合物６のアクリロイル基変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％のランダム共重合体（分子量２８００）１ｇ、ＬｉＰＦ６１．５ｍｏｌ／Ｌ、ＥＣ：ＧＢＬ：ＤＥＣ＝５：１：１２（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、１ｗｔ％の有機過酸化物であるα−クミルパーオキシネオデカネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
2 g of a random copolymer (molecular weight 10,000) of 80% by weight of tetrafunctional terminal acryloyl-modified ethylene oxide, 5% by weight of propylene oxide, and 15% by weight of butylene oxide using diglycerin as a starting material as compound 4 and acryloyl group-modified ethylene of compound 6 1 g of a random copolymer (molecular weight 2800) of 80 wt% of oxide and 20 wt% of propylene oxide, 1.5 mol / L of LiPF 6 , and 97 g of an electrolyte solution of EC: GBL: DEC = 5: 1: 12 (volume ratio) were dissolved into a polymer. 3 wt% was adjusted. Further, α-cumylperoxyneodecanate, which is 1 wt% organic peroxide, was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３５μｍのセパリオンＳ４５０Ｐ３５（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S450P35 (Degussa Japan Co., Ltd.) having a thickness of 35 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例５〉
［正極の作製］
正極活物質である被覆炭素量２ｗｔ％のＬｉＦｅＰＯ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてカルボン酸変性タイプのＰＶＤＦ（（株）クレハ ＫＦバインダー＃９１３０ ＮＭＰ １３ｗｔ％溶液）６１．５ｇ（固形分として８ｇ）、分散媒としてＮＭＰ８４．６ｇで希釈し固形分４５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度１．８ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 5>
[Production of positive electrode]
100 g of LiFePO 4 having a coating carbon amount of 2 wt% as a positive electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and a carboxylic acid-modified PVDF (Kureha KF Binder # 9130) as a binder NMP 13 wt% solution) 61.5 g (8 g as solid content) and NMP 84.6 g as a dispersion medium were diluted with NMP 84.6 g to prepare a positive electrode coating solution so that the solid content was 45 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed to obtain an active material density of 1.8 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (single side Per) was obtained.
［負極の作製］
負極活物質として平均粒径２８μｍ、比表面積２．１ｍ２／ｇ の人造黒鉛１００ｇを用いた以外は実施例１と同様に作製した。
[Production of negative electrode]
It was produced in the same manner as in Example 1 except that 100 g of artificial graphite having an average particle size of 28 μm and a specific surface area of 2.1 m 2 / g was used as the negative electrode active material.
［硬化前溶液の調整］
化合物１である出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％のランダム共重合体（分子量１００００）２ｇと化合物５の出発物質にエチレングリコールを用いた２官能性末端アクリロイル基変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％のランダム共重合体（分子量３０００）１ｇ、ＬｉＢＦ４１．５ｍｏｌ／Ｌ、ＥＣ：ＰＣ：ＤＥＣ＝５：２：１３（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して０．２ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
2 g of a random copolymer (molecular weight 10,000) of tetrafunctional terminal acryloyl-modified ethylene oxide 80 wt% and propylene oxide 20 wt% using diglycerin as the starting material which is compound 1 and 2 using ethylene glycol as the starting material of compound 5 Functional terminal acryloyl group-modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 3000) 1 g, LiBF 4 1.5 mol / L, EC: PC: DEC = 5: 2: 13 (volume ratio) electrolysis The liquid 97g was melt | dissolved and 3 wt% of polymers were adjusted. Furthermore, 0.2 wt% of organic peroxide (4-t-butylcyclohexyl) peroxydicarbonate as a thermal polymerization initiator was dissolved to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例６〉
［正極の作製］
正極活物質であるＬｉＮｉ０．８Ｃｏ０．２Ｏ２１００ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）７ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ２３．６ｇで希釈し固形分６５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 6>
[Production of positive electrode]
The positive electrode active material LiNi 0 . 8 Co 0 . 2 O 2 100 g, 7 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, 41.7 g of PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder, 5 g as a solid content, dispersion A positive electrode coating solution was prepared so as to be diluted with 23.6 g of NMP as a medium to a solid content of 65 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質として平均粒径２８μｍ、比表面積１．５ｍ２／ｇ の人造黒鉛を用いた以外は実施例４と同様に作製した。
[Production of negative electrode]
A negative electrode active material was prepared in the same manner as in Example 4 except that artificial graphite having an average particle size of 28 μm and a specific surface area of 1.5 m 2 / g was used.
［硬化前溶液の調整］
化合物１の出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％のランダム共重合体（分子量１００００）２．５ｇと化合物６の出発物質にメタノールを用いた１官能性末端アクリロイル基変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％、ランダム共重合体（分子量２８００）０．５ｇ、ＬｉＰＦ６１．５ｍｏｌ／Ｌ、ＥＣ：ＰＣ：ＥＭＣ＝５：２：１３（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．２ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Random copolymer (molecular weight 10000) of tetrafunctional terminal acryloyl modified ethylene oxide 80wt%, propylene oxide 20wt% using diglycerin as starting material of compound 1 and methanol as starting material of compound 1 Functional terminal acryloyl group-modified ethylene oxide 80 wt%, propylene oxide 20 wt%, random copolymer (molecular weight 2800) 0.5 g, LiPF 6 1.5 mol / L, EC: PC: EMC = 5: 2: 13 (volume ratio) ) 97 g of the electrolytic solution was dissolved to adjust 3 wt% of the polymer. Furthermore, 0.2 wt% of organic peroxide (4-t-butylcyclohexyl) peroxydicarbonate as a thermal polymerization initiator was dissolved to prepare a pre-curing solution.
［リチウム電池の作製］
上記得られた正極と負極の間にセパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み２５μｍのセパリオンＳ２４０Ｐ２５（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P25 (Degussa Japan Co., Ltd.) having a thickness of 25 μm obtained by coating PET with SiO 2 and Al 2 O 3 was used as a separator between the obtained positive electrode and negative electrode.
〈実施例７〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２３０ｇ／ＬｉＭｎ２Ｏ４７０ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ３．６ｇで希釈し固形分７０ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 7>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 30g / LiMn 2 O 4 70g, acetylene black (Denki Kagaku Kogyo Co., Denka Black) as a conductive agent 5 g, PVDF as a binder ((Co. ) Kureha KF Binder # 1120 NMP 12 wt% solution) A positive electrode coating solution was prepared so that it was diluted with NMP 3.6 g as a dispersion medium to a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質である、ＭＣＭＢ（大阪ガスケミカル（株）ＭＣＭＢ２５−２８）１００ｇ、気相成長炭素（昭和電工（株）ＶＧＣＦ）２ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）３ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
MCg (Osaka Gas Chemical Co., Ltd. MCMB25-28) 100g, vapor-grown carbon (Showa Denko Co., Ltd. VGCF) 2g, acetylene black (Electrochemical Industry Co., Ltd. Denka Black) 3g as a conductive agent 41.7 g (5 g as a solid content) of PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder and 36.7 g of NMP as a dispersion medium are mixed with a planetary mixer, and negative electrode coating with a solid content of 60 wt% A liquid was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.4 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物２の出発物質にグリセリンを用いた３官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％のランダム共重合体（分子量８０００）２．５ｇと化合物７の出発物質にソルビトールを用いた６官能性メタクリロイル基変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％ランダム共重合体（分子量２０００）０．５ｇ、ＬｉＢＦ４１．５ｍｏｌ／Ｌ、ＥＣ：ＧＢＬ＝３：７（体積比）、電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．２ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Trifunctional terminal acryloyl-modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 8000) 2.5 g using glycerin as the starting material for compound 2 and hexafunctional using sorbitol as the starting material for compound 7 Methacryloyl group-modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 2000) 0.5 g, LiBF 4 1.5 mol / L, EC: GBL = 3: 7 (volume ratio), electrolyte solution 97 g dissolved Then, 3 wt% of the polymer was adjusted. Furthermore, 0.2 wt% of organic peroxide (4-t-butylcyclohexyl) peroxydicarbonate as a thermal polymerization initiator was dissolved to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例８〉
［正極の作製］
正極活物質であるＬｉＮｉ０．８Ｃｏ０．２Ｏ２／ＬｉＭｎ２Ｏ４ ７０ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ３．６ｇで希釈し固形分７０ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 8>
[Production of positive electrode]
The positive electrode active material LiNi 0 . 8 Co 0 . 70 g of 2 O 2 / LiMn 2 O 4 , 5 g of acetylene black (Electrochemical Industry Co., Ltd. Denka Black) as a conductive agent, 50 g of PVDF (Kureha KF Binder 1120 NMP 12 wt% solution) as a binder (6 g as a solid content) A positive electrode coating solution was prepared so as to be diluted with 3.6 g of NMP as a dispersion medium so as to have a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質として平均粒径１４μｍ 比表面積１．３ｇ／ｃｍ２ の人造黒鉛１００ｇを用いた以外は実施例１と同様に作製した。
[Production of negative electrode]
A negative electrode active material was prepared in the same manner as in Example 1 except that 100 g of artificial graphite having an average particle size of 14 μm and a specific surface area of 1.3 g / cm 2 was used.
［硬化前溶液の調整］
化合物８の出発物質にグリセリンを用いた３官能性末端メチル変性エチレンオキサイド５０ｗｔ％、プロピレンオキサイド２０ｗｔ％、アリルグリシジルエーテル１０ｗｔ％、エチレンオキサイド２０ｗｔ％の順に付加重合したブロック共重合体（分子量１５０００）３ｗｔ％、ＬｉＰＦ６１．５ｍｏｌ／Ｌ、ＥＣ：ＰＣ：ＤＥＣ＝３：３：４（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、１ｗｔ％のアゾ化合物である２，２’−アゾビスイソブチロニトリルを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Block copolymer (molecular weight 15000) 3 wt% of addition-polymerized in the order of trifunctional terminal methyl-modified ethylene oxide 50 wt%, propylene oxide 20 wt%, allyl glycidyl ether 10 wt%, ethylene oxide 20 wt% using glycerin as the starting material of compound 8 %, LiPF 6 1.5 mol / L, EC: PC: DEC = 3: 3 (volume ratio) 97 g of an electrolytic solution was dissolved to prepare 3 wt% of a polymer. Furthermore, 2,2′-azobisisobutyronitrile, which is 1 wt% of an azo compound, was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例９〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２１００ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ４．０ｇで希釈し固形分７０ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 9>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 100g, acetylene black (Denki Kagaku Kogyo Co., Denka Black) as a conductive agent 6 g, PVDF as a binder (Ltd. Kureha KF Binder # 1120 A positive electrode coating solution was prepared so as to be diluted with 50 g of NMP (12 wt% solution) (6 g as a solid content) and 4.0 g of NMP as a dispersion medium to a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質に平均粒径２５μｍ、比表面積３．１ｇ／ｃｍ２の人造黒鉛１００ｇを用い、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダー成分としてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１００ｇ（固形分として２ｇ）、スチレンブタジエンゴム（ＳＢＲ）ＢＭ−４００Ｂ（日本ゼオン（株））４０ｗｔ％溶液５ｇ（固形分として２ｇ）、分散媒として蒸留水８ｇを遊星型ミキサーで混合し、固形分５０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２の両面塗工負極を得た。
[Production of negative electrode]
Artificial graphite 100 g having an average particle size of 25 μm and a specific surface area of 3.1 g / cm 2 was used as the negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and carboxymethyl cellulose WS-C (as a binder component) Daiichi Kogyo Seiyaku Co., Ltd.) 2 wt% solution 100 g (2 g as solid content), styrene butadiene rubber (SBR) BM-400B (Nippon Zeon Co., Ltd.) 40 wt% solution 5 g (2 g as solid content), distilled as dispersion medium 8 g of water was mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 50 wt%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and a double-side coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2. Got.
［硬化前溶液の調整］
化合物９の出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド６０ｗｔ％、プロピレンオキサイド４０ｗｔ％のランダム共重合（分子量２００００）３ｗｔ％、ＬｉＰＦ６ １．５ｍｏｌ／Ｌ、ＥＣ：ＤＥＣ＝３：７（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．３ｗｔ％の有機過酸化物であるイブチリルパーオキサイドを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Random copolymerization (molecular weight 20000) of tetrafunctional terminal acryloyl-modified ethylene oxide 60 wt%, propylene oxide 40 wt% using diglycerin as the starting material of compound 9, LiPF 6 1.5 mol / L, EC: DEC = 3 : 7 (volume ratio) 97 g of the electrolytic solution was dissolved to adjust 3 wt% of the polymer. Furthermore, 0.3% by weight of organic peroxide ibutyryl peroxide was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例１０〉
［正極の作製］
正極活物質であるＬｉＮｉ０．８Ｃｏ０．２Ｏ２／ＬｉＭｎ２Ｏ４ ７０ｇと、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ４．０ｇで希釈し固形分７０ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 10>
[Production of positive electrode]
The positive electrode active material LiNi 0 . 8 Co 0 . 70 g of 2 O 2 / LiMn 2 O 4, 6 g of acetylene black (Electrochemical Industry Co., Ltd. Denka Black) as a conductive agent, and 50 g of PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder 6 g), a positive electrode coating solution was prepared so that the dispersion medium was diluted with 4.0 g of NMP to a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質に平均粒径２５μｍ、比表面積３．１ｇ／ｃｍ２の人造黒鉛１００ｇを用い導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダー成分としてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１０ｇ、スチレンブタジエンゴム（ＳＢＲ）エマルジョン（日本ゼオン（株）ＢＭ−４００Ｂ）４０ｗｔ％溶液５ｇ、分散媒として蒸留水８ｇを遊星型ミキサーで混合し、固形分５０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２の両面塗工負極を得た。
[Production of negative electrode]
Artificial graphite 100 g having an average particle diameter of 25 μm and a specific surface area of 3.1 g / cm 2 is used for the negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and carboxymethyl cellulose WS-C (No. 1) as a binder component. Ichi Kogyo Seiyaku Co., Ltd.) 10 g of 2 wt% solution, 5 g of 40 wt% solution of styrene butadiene rubber (SBR) emulsion (Nippon ZEON Co., Ltd. BM-400B), 8 g of distilled water as a dispersion medium are mixed with a planetary mixer, and the solid content A 50 wt% negative electrode coating solution was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and a double-side coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2. Got.
［硬化前溶液の調整］
化合物１０の出発物質にエチレングリコールを用いた２官能性末端ベンジル変性エチレンオキサイド５５ｗｔ％、ブチレンオキサイド１０ｗｔ％、ＭＥ２モノマー５ｗｔ％、アリルグリシジルエーテル１０ｗｔ％，エチレンオキサイド２０ｗｔ％の順に付加重合したブロック共重合体（分子量４９７６００）２ｗｔ％、ＬｉＰＦ６ １．５ｍｏｌ／Ｌ、ＥＣ：ＤＥＣ＝３：７（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．２ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Block copolymer of addition-polymerized in the order of 55 wt% bifunctional terminal benzyl-modified ethylene oxide, 10 wt% butylene oxide, 5 wt% ME2 monomer, 10 wt% allyl glycidyl ether, 20 wt% ethylene oxide Combined (molecular weight 497600) 2 wt%, LiPF 6 1.5 mol / L, EC: DEC = 3: 7 (volume ratio) 97 g of electrolytic solution was dissolved to prepare 3 wt% polymer. Furthermore, 0.2 wt% of organic peroxide (4-t-butylcyclohexyl) peroxydicarbonate as a thermal polymerization initiator was dissolved to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例１１〉
［正極の作製］
正極活物質である被覆炭素量２ｗｔ％のＬｉＦｅＰＯ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）８ｇ、バインダーとしてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１００ｇ（固形分として２ｇ）、スチレンブタジエンゴム（ＳＢＲ）エマルジョンＢＭ−４００Ｂ（日本ゼオン（株））４０ｗｔ％水溶液５ｇ（固形分として２ｇ）、分散媒として蒸留水６０ｇを遊星型ミキサーで混合し、固形分４１ｗｔ％の正極塗工液を調製した。
<Example 11>
[Production of positive electrode]
100 g of LiFePO 4 having a coating carbon amount of 2 wt% as a positive electrode active material, 8 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, 2 wt. Of carboxymethyl cellulose WS-C (Daiichi Kogyo Seiyaku Co., Ltd.) as a binder 100 g of 2% solution (2 g as solid content), 5 g of styrene butadiene rubber (SBR) emulsion BM-400B (Nippon Zeon Co., Ltd.) 40 wt% aqueous solution (2 g as solid content), and 60 g of distilled water as a dispersion medium are mixed with a planetary mixer. A positive electrode coating solution having a solid content of 41 wt% was prepared.
［負極の作製］
負極活物質に平均粒径２５μｍ、比表面積３．１ｇ／ｃｍ２の人造黒鉛１００ｇを用い、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダー成分としてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２％溶液１０ｇ、スチレンブタジエンゴム（ＳＢＲ）エマルジョン（日本ゼオン（株）ＢＭ−４００Ｂ）４０ｗｔ％溶液５ｇ、分散媒として蒸留水８ｇを遊星型ミキサーで混合し、固形分５０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２の両面塗工負極を得た。
[Production of negative electrode]
Artificial graphite 100 g having an average particle size of 25 μm and a specific surface area of 3.1 g / cm 2 was used as the negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and carboxymethyl cellulose WS-C (as a binder component) Daiichi Kogyo Seiyaku Co., Ltd.) 2% solution 10g, styrene butadiene rubber (SBR) emulsion (Nippon ZEON Co., Ltd. BM-400B) 40wt% solution 5g, distilled water 8g as a dispersion medium are mixed with a planetary mixer and solid A negative electrode coating solution of 50 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and a double-side coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2. Got.
［硬化前溶液の調整］
化合物１１の出発物質にエチレングリコールを用いた２官能性末端メチル変性エチレンオキサイド７５ｗｔ％、プロピレンオキサイド１５ｗｔ％、アリルグリシジルエーテル１０ｗｔ％のランダム共重合体（分子量２５００００）２ｗｔ％、ＬｉＰＦ６１．５ｍｏｌ／Ｌ、ＥＣ：ＤＥＣ＝３：７（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．３ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Random copolymer (molecular weight 250,000) of bifunctional terminal methyl-modified ethylene oxide 75 wt%, propylene oxide 15 wt%, allyl glycidyl ether 10 wt% using ethylene glycol as a starting material of compound 11, LiPF 6 1.5 mol / L, EC: DEC = 3: 7 (volume ratio) 97 g of an electrolytic solution was dissolved to adjust 3 wt% of the polymer. Furthermore, (4-t-butylcyclohexyl) peroxydicarbonate which is an organic peroxide of 0.3 wt% was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例１２〉
［正極の作製］
正極活物質である被覆炭素量６％のＬｉＦｅＰＯ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）６６．７ｇ（固形分として８ｇ）、分散媒としてＮＭＰ７９．４ｇで希釈し固形分４５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度１．ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 12>
[Production of positive electrode]
100 g LiFePO 4 with 6% coated carbon as a positive electrode active material, 5 g acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder A positive electrode coating solution was prepared so that it was diluted with 66.7 g (8 g as a solid content) and 79.4 g of NMP as a dispersion medium to a solid content of 45 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm by a coating machine, dried at 130 ° C., and subjected to a roll press treatment. A double-side coated positive electrode with g / cm 3 and positive electrode active material 13 mg / cm 2 (per one side) was obtained.
［負極の作製］
負極活物質に平均粒径２５μｍ、比表面積３．１ｇ／ｃｍ２の人造黒鉛１００ｇを用い、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダー成分としてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１０ｇ、スチレンブタジエンゴム（ＳＢＲ）エマルジョン（日本ゼオン（株）ＢＭ−４００Ｂ）４０ｗｔ％溶液５ｇ、分散媒として蒸留水８ｇを遊星型ミキサーで混合し、固形分５０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２の両面塗工負極を得た。
[Production of negative electrode]
Artificial graphite 100 g having an average particle size of 25 μm and a specific surface area of 3.1 g / cm 2 was used as the negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and carboxymethyl cellulose WS-C (as a binder component) Daiichi Kogyo Seiyaku Co., Ltd.) 10 g of 2 wt% solution, 5 g of styrene butadiene rubber (SBR) emulsion (Nippon ZEON Co., Ltd. BM-400B) 40 wt% solution, and 8 g of distilled water as a dispersion medium are mixed with a planetary mixer and solid A negative electrode coating solution of 50 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and a double-side coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2. Got.
［硬化前溶液の調整］
化合物１２の出発物質にペンタエリスリトールを用いた４官能性末端アクリロイル変性エチレンオキサイド６０ｗｔ％、ＭＥ１モノマー２０ｗｔ％、ＭＥ３モノマー２０ｗｔ％のランダム共重合体（分子量１１０００）２ｗｔ％、ＬｉＰＦ６１．５ｍｏｌ／Ｌ、ＥＣ：ＤＥＣ＝３：７（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、熱重合開始剤として溶液重量に対して、０．３ｗｔ％の有機過酸化物である（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
Random copolymer (molecular weight 11000) 2 wt% of tetrafunctional terminal acryloyl-modified ethylene oxide 60 wt%, ME1 monomer 20 wt%, ME3 monomer 20 wt% using pentaerythritol as a starting material of compound 12, LiPF 6 1.5 mol / L EC: DEC = 3: 7 (volume ratio) The electrolyte solution 97g was melt | dissolved and 3 wt% of polymers were adjusted. Furthermore, (4-t-butylcyclohexyl) peroxydicarbonate which is an organic peroxide of 0.3 wt% was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例１３〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ１６．３ｇで希釈し、固形分６５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 13>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 100g, acetylene black as a conductive agent (Denki Kagaku Kogyo Co., Denka Black) 6 g, PVDF as a binder (Ltd. Kureha KF Binder # 1120 NMP 12 wt% solution) 50 g (6 g as solid content) and NMP 16.3 g as a dispersion medium were diluted to prepare a positive electrode coating solution so that the solid content was 65 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるメソカーボンマイクロビーズ（ＭＣＭＢ）（大阪ガスケミカル（株）ＭＣＭＢ２５−２８）９５ｇ、ハードカーボン（（株）クレハ化学 カーボトロンＰ Ｓ（Ｆ））５ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of mesocarbon microbeads (MCMB) (Osaka Gas Chemical Co., Ltd. MCMB25-28) as a negative electrode active material, 5 g of hard carbon (Kureha Chemical Co., Ltd. Carbotron PS (F)), acetylene black (electrochemistry) as a conductive agent Industrial (Denka Black) 5g, PVDF (Kureha KF Binder # 1120 NMP 12wt% solution) 41.7g (5g as solid content) as a binder, NMP 36.7g as a dispersion medium is mixed with a planetary mixer, A negative electrode coating solution having a solid content of 60 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１３の出発物質にジエチレングリコールを用いた１６官能性末端（アクリロイル変性２官能、メチル変性１４官能）エチレンオキサイド５４ｗｔ％と２，３−エポキシ−１−プロパノール４６ｗｔ％、付加重合体（分子量２３００）２ｇと化合物１である出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％ランダム共重合体（分子量１００００）２ｇ、１．５ｍｏｌ／Ｌ、エチレンカーボネート（ＥＣ）：ジエチルカーボネート（ＤＥＣ）＝３：７（体積比）電解液９６ｇを溶解し、ポリマー４ｗｔ％を調整した。さらに、熱重合開始剤として上記溶液重量に対して、１ｗｔ％のアゾ化合物である２，２’−アゾビスイソブチロニトリルを溶解し、硬化前溶液を調整した。
[Preparation of solution before curing]
16 functional end (diacryloyl modified bifunctional, methyl modified 14 functional) ethylene oxide 54 wt%, 2,3-epoxy-1-propanol 46 wt%, addition polymer (molecular weight 2300) 2 g using diethylene glycol as starting material of compound 13 And a tetrafunctional terminal acryloyl-modified ethylene oxide 80 wt%, propylene oxide 20 wt% random copolymer (molecular weight 10,000) 2 g, 1.5 mol / L, ethylene carbonate (EC): 96 g of diethyl carbonate (DEC) = 3: 7 (volume ratio) electrolyte was dissolved to prepare 4 wt% polymer. Further, 1 wt% of 2,2′-azobisisobutyronitrile as an azo compound was dissolved as a thermal polymerization initiator with respect to the weight of the solution to prepare a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
（紫外線硬化でゲル電解質の場合）
〈実施例１４〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ１６．３ｇで希釈し、固形分６５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
(In the case of gel electrolyte with UV curing)
<Example 14>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 100g, acetylene black as a conductive agent (Denki Kagaku Kogyo Co., Denka Black) 6 g, PVDF as a binder (Ltd. Kureha KF Binder # 1120 NMP 12 wt% solution) 50 g (6 g as solid content) and NMP 16.3 g as a dispersion medium were diluted to prepare a positive electrode coating solution so that the solid content was 65 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるメソカーボンマイクロビーズ（ＭＣＭＢ）（大阪ガスケミカル（株）ＭＣＭＢ２５−２８）９５ｇ、ハードカーボン（（株）クレハ化学 カーボトロンＰ Ｓ（Ｆ））５ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of mesocarbon microbeads (MCMB) (Osaka Gas Chemical Co., Ltd. MCMB25-28) as a negative electrode active material, 5 g of hard carbon (Kureha Chemical Co., Ltd. Carbotron PS (F)), acetylene black (electrochemistry) as a conductive agent Industrial (Denka Black) 5g, PVDF (Kureha KF Binder # 1120 NMP 12wt% solution) 41.7g (5g as solid content) as a binder, NMP 36.7g as a dispersion medium is mixed with a planetary mixer, A negative electrode coating solution having a solid content of 60 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１の出発物質にジグリセリンを用いた４官能性末端アクリロイル変性エチレンオキサイド８０ｗｔ％、プロピレンオキサイド２０ｗｔ％ランダム共重合体（分子量１００００）３ｇと、ＬｉＰＦ６１．２ｍｏｌ／Ｌ、エチレンカーカーボネート（ＥＣ）：ジエチルカーボネート（ＤＥＣ）＝３：７（体積比）電解液９７ｇを溶解し、ポリマー３ｗｔ％を調整した。さらに、光重合開始剤として上記溶液重量に対して、０．１ｗｔ％の２，２−ジメトキシ−２−フェニルアセトフェノンを溶解した。
[Preparation of solution before curing]
80% by weight of tetrafunctional terminal acryloyl-modified ethylene oxide using diglycerin as a starting material of compound 1, 20% by weight of propylene oxide random copolymer (molecular weight 10,000), LiPF 6 1.2 mol / L, ethylene carbonate (EC ): Diethyl carbonate (DEC) = 3: 7 (volume ratio) An electrolyte solution of 97 g was dissolved to adjust 3 wt% of the polymer. Further, 0.1 wt% of 2,2-dimethoxy-2-phenylacetophenone was dissolved as a photopolymerization initiator with respect to the weight of the solution.
［リチウム電池の作製］
上記正極と負極とセパレーターとしてＰＥＴ素材の不織布にＳｉＯ２とＡｌ２Ｏ３を被覆した厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を硬化前溶液に別の容器で含浸し、負極上にセパレーターを積層し、正極はセパレーターを積層せず、それぞれ波長３６５ｎｍ、強度３０ｍＷ／ｃｍ２の紫外線を３分照射し、負極、セパレーター、ゲル電解が一体化したゲル状電解質層と正極とゲル電解が一体化したゲル電解質層を形成した。さらにそれらを正極と負極の間にセパレーターが存在するように積層し、アルミラミネートで封入し、試験用のセルを作製した。
[Production of lithium battery]
Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating a non-woven fabric of PET material with SiO 2 and Al 2 O 3 as a positive electrode, a negative electrode, and a separator is impregnated in a pre-curing solution in another container, and a separator is formed on the negative electrode The positive electrode is not laminated with a separator, and each of them is irradiated with ultraviolet rays having a wavelength of 365 nm and an intensity of 30 mW / cm 2 for 3 minutes, and the negative electrode, separator, and gel electrolysis are integrated with the positive electrode and the gel electrolysis. A gel electrolyte layer was formed. Furthermore, they were laminated so that a separator existed between the positive electrode and the negative electrode, and sealed with an aluminum laminate to produce a test cell.
（ドライ系電解質の場合）
〈実施例１５〉
［正極の作製］
実施例１と同様の方法で作製し、活物質密度２．６ｇ／ｃｍ３、正極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
(For dry electrolytes)
<Example 15>
[Production of positive electrode]
A double-coated positive electrode having an active material density of 2.6 g / cm 3 and a positive electrode active material of 8 mg / cm 2 (per one side) was obtained in the same manner as in Example 1.
［負極の作製］
実施例１と同様の方法で作製し、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
A double-coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side) was obtained in the same manner as in Example 1.
［硬化前溶液の調整］
化合物１の代わりに化合物１３の出発物質にジエチレングリコールを用いた１６官能性末端（アクリロイル変性２官能、メチル変性１４官能）エチレンオキサイド５４ｗｔ％と２，３−エポキシ−１−プロパノール４６ｗｔ％の付加重合体（分子量２３００）を使用した以外は実施例１と同様の方法で作製し、硬化前溶液を調整した。
[Preparation of solution before curing]
Addition polymer of 16 functional end (acryloyl modified bifunctional, methyl modified 14 functional) ethylene oxide 54 wt% and 2,3-epoxy-1-propanol 46 wt% using diethylene glycol as the starting material of compound 13 instead of compound 1 A solution before curing was prepared by the same method as in Example 1 except that (molecular weight 2300) was used.
［リチウム電池の作製］
実施例１と同様の方法で作製し、試験用のセルを作製した。
[Production of lithium battery]
A test cell was manufactured in the same manner as in Example 1.
〈実施例１６〉
［正極の作製］
実施例１と同様の方法で作製し、活物質密度２．６ｇ／ｃｍ３、正極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 16>
[Production of positive electrode]
A double-coated positive electrode having an active material density of 2.6 g / cm 3 and a positive electrode active material of 8 mg / cm 2 (per one side) was obtained in the same manner as in Example 1.
［負極の作製］
実施例１と同様の方法で作製し、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
A double-coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side) was obtained in the same manner as in Example 1.
［硬化前溶液の調整］
化合物１の代わりに化合物１４の出発物質にグリセリンを用いた２１官能性末端（メタクリロイル変性３官能、エチル基１８官能）エチレンオキサイド５０ｗｔ％と２，３−エポキシ−１−プロパノール５０ｗｔ％の付加重合体（分子量２９００）を使用した以外は実施例１と同様の方法で作製し、硬化前溶液を調整した。
[Preparation of solution before curing]
Addition polymer of 21 functional end (methacryloyl-modified trifunctional, ethyl group 18 functional) ethylene oxide 50 wt% and 2,3-epoxy-1-propanol 50 wt% using glycerin as the starting material of compound 14 instead of compound 1 A pre-curing solution was prepared by the same method as in Example 1 except that (molecular weight 2900) was used.
［リチウム電池の作製］
実施例１と同様の方法で作製し、試験用のセルを作製した。
[Production of lithium battery]
A test cell was manufactured in the same manner as in Example 1.
〈実施例１７〉
［正極の作製］
正極活物質であるＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）６ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ１６．３ｇで希釈し、固形分６５ｗｔ％になるように、正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 17>
[Production of positive electrode]
As a cathode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 100g, acetylene black as a conductive agent (Denki Kagaku Kogyo Co., Denka Black) 6 g, PVDF as a binder (Ltd. Kureha KF Binder # 1120 NMP 12 wt% solution) 50 g (6 g as solid content) and NMP 16.3 g as a dispersion medium were diluted to prepare a positive electrode coating solution so that the solid content was 65 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるメソカーボンマイクロビーズ（ＭＣＭＢ）（大阪ガスケミカル（株）ＭＣＭＢ２５−２８）９５ｇ、ハードカーボン（（株）クレハ化学 カーボトロンＰ Ｓ（Ｆ））５ｇ、導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し、固形分６０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of mesocarbon microbeads (MCMB) (Osaka Gas Chemical Co., Ltd. MCMB25-28) as a negative electrode active material, 5 g of hard carbon (Kureha Chemical Co., Ltd. Carbotron PS (F)), acetylene black (electrochemistry) as a conductive agent Industrial (Denka Black) 5g, PVDF (Kureha KF Binder # 1120 NMP 12wt% solution) 41.7g (5g as solid content) as a binder, NMP 36.7g as a dispersion medium is mixed with a planetary mixer, A negative electrode coating solution having a solid content of 60 wt% was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１を６ｇと化合物６を４ｇにＬｉＴＦＳＩ２ｇと熱重合開始剤として２，２’−アゾビスイソブチロニトリル０．０５ｇを溶解させ、硬化前溶液を得た。
[Preparation of solution before curing]
6 g of Compound 1, 4 g of Compound 6 and 2 g of LiTFSI and 0.05 g of 2,2′-azobisisobutyronitrile as a thermal polymerization initiator were dissolved to obtain a pre-curing solution.
［リチウム電池の作製］
得られた正極と負極の間にセパレーターとしてＰＥＴ素材の不織布にＳｉＯ２とＡｌ２Ｏ３を被覆した厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を挟んだ構造の積層体を作製し、端子を取り出すためのタブリードを溶接したのち、アルミラミネート包材に入れ、３方向を熱融着し、１方向に開口部を作った袋状のプレ電池を作製した。プレ電池にあらかじめ調整したポリマー／電解液混合溶液３ｇを注入した後、開放部のアルミラミネートを真空ヒートシーラーで封止し、８０℃、２０時間かけてポリマーを硬化し、試験用のセルを作製した。
[Production of lithium battery]
A laminated body having a structure in which Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm in which a non-woven fabric of PET material is coated with SiO 2 and Al 2 O 3 as a separator is sandwiched between the obtained positive electrode and the negative electrode is prepared, and a terminal After welding the tab lead for taking out the film, it was put into an aluminum laminate packaging material, and heat-sealed in three directions to produce a bag-shaped pre-battery having openings in one direction. After injecting 3 g of polymer / electrolyte mixed solution prepared in advance into the pre-battery, the aluminum laminate in the open part was sealed with a vacuum heat sealer, and the polymer was cured at 80 ° C. for 20 hours to produce a test cell. did.
〈実施例１８〉
［正極の作製］
正極活物質であるＬｉＭｎ２Ｏ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５８．３ｇ（固形分として７ｇ）、分散媒としてＮＭＰ１．４ｇで希釈し固形分６８ｗｔ％になるように正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 18>
[Production of positive electrode]
LigMn 2 O 4 100 g as a positive electrode active material, acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) 5 g as a conductive agent, PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) 58.3 g as a binder A positive electrode coating solution was prepared so that the solid content was 7 g) and the dispersion medium was diluted with 1.4 g of NMP to a solid content of 68 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるＭＣＭＢ（大阪ガスケミカル（株）ＭＣＭＢ１０−２８）９５ｇ、難黒鉛化炭素（（株）クレハ カーボトロン Ｐ（Ｓ））５ｇ、導電剤としてアセチレンブラック５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ）、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し固形分５３．６％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of MCMB (Osaka Gas Chemical Co., Ltd. MCMB10-28), 5 g of non-graphitizable carbon (Kureha Carbotron P (S)), 5 g of acetylene black as a conductive agent, and PVDF as a binder Kureha KF Binder # 1120 NMP 12 wt% solution) 41.7 g (5 g as a solid content) and 36.7 g NMP as a dispersion medium were mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 53.6%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１５の出発物質にジエチレングリコールを用いた１６官能性末端（アクリロイル変性２官能、メチル変性１４官能）エチレンオキサイド５４ｗｔ％と２，３−エポキシ−１−プロパノール４６ｗｔ％の付加重合体（分子量２３００）１０ｇ、ＬｉＰＦ６２ｇと熱重合開始剤として２，２’−アゾビスイソブチロニトリル０．０５ｇを溶解させ、硬化前溶液を得た。
[Preparation of solution before curing]
Addition polymer (molecular weight 2300) of 16 functional end (acryloyl modified bifunctional, methyl modified 14 functional) ethylene oxide 54 wt% and 2,3-epoxy-1-propanol 46 wt% using diethylene glycol as starting material of compound 15 Then, 2 g of LiPF 6 and 0.05 g of 2,2′-azobisisobutyronitrile as a thermal polymerization initiator were dissolved to obtain a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例１９〉
［正極の作製］
正極活物質であるＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２ １００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）５０ｇ（固形分として６ｇ）、分散媒としてＮＭＰ３．６ｇで希釈し固形分７０ｗｔ％になるように正極塗工液を調製した。この塗工液を塗工機で厚み１５μｍのアルミニウム箔上にコーティングを行い、１３０℃で乾燥しロールプレス処理を行い、活物質密度２．６ｇ／ｃｍ３、正極活物質１３ｍｇ／ｃｍ２（片面あたり）の両面塗工正極を得た。
<Example 19>
[Production of positive electrode]
The positive electrode active material LiNi 0 . 8 Co 0 . 15 Al 0 . 05 O 2 100 g, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, 50 g of PVDF (Kureha KF Binder # 1120 NMP 12 wt% solution) as a binder, 6 g as a solid content, dispersion medium Was diluted with 3.6 g of NMP to prepare a positive electrode coating solution to a solid content of 70 wt%. This coating solution is coated on an aluminum foil having a thickness of 15 μm with a coating machine, dried at 130 ° C. and roll-pressed, an active material density of 2.6 g / cm 3 , a positive electrode active material of 13 mg / cm 2 (one side Per) was obtained.
［負極の作製］
負極活物質であるＭＣＭＢ（大阪ガスケミカル（株）ＭＣＭＢ１０−２８）９５ｇ、難黒鉛化炭素（（株）クレハ カーボトロン Ｐ（Ｓ））５ｇ、導電剤としてアセチレンブラック５ｇ、バインダーとしてＰＶＤＦ（（株）クレハ ＫＦバインダー＃１１２０ ＮＭＰ １２ｗｔ％溶液）４１．７ｇ（固形分として５ｇ） 、分散媒としてＮＭＰ３６．７ｇを遊星型ミキサーで混合し固形分５３．６％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２（片面あたり）の両面塗工負極を得た。
[Production of negative electrode]
95 g of MCMB (Osaka Gas Chemical Co., Ltd. MCMB10-28), 5 g of non-graphitizable carbon (Kureha Carbotron P (S)), 5 g of acetylene black as a conductive agent, and PVDF as a binder Kureha KF Binder # 1120 NMP 12 wt% solution) 41.7 g (5 g as solid content) and 36.7 g NMP as a dispersion medium were mixed with a planetary mixer to prepare a negative electrode coating solution having a solid content of 53.6%. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C., and then subjected to a roll press treatment, with an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2 (per one side). A double-sided coated negative electrode was obtained.
［硬化前溶液の調整］
化合物１６の出発物質にグリセリンを用いた２１官能性末端（メタクリロイル変性３官能、エチル基１８官能）エチレンオキサイド５０ｗｔ％と２，３−エポキシ−１−プロパノール５０ｗｔ％の付加重合体（分子量２９００）１０ｇ、ＬｉＢＦ４２ｇと熱重合開始剤として２，２’−アゾビスイソブチロニトリル０．０５ｇを溶解させ、硬化前溶液を得た。
[Preparation of solution before curing]
10 g of 21-functional end (methacryloyl-modified trifunctional, ethyl group 18 functional) ethylene oxide 50 wt% and 2,3-epoxy-1-propanol 50 wt% (polymer weight 2900) using glycerin as a starting material for compound 16 LiBF 4 2 g and 2,2′-azobisisobutyronitrile 0.05 g as a thermal polymerization initiator were dissolved to obtain a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈実施例２０〉
［正極の作製］
正極活物質である被覆炭素量２ｗｔ％のＬｉＦｅＰＯ４１００ｇ、導電剤としてのアセチレンブラック（電気化学工業（株）デンカブラック）８ｇ、バインダーとしてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１００ｇ（固形分として２ｇ）、スチレンブタジエンゴム（ＳＢＲ）エマルジョンＢＭ−４００Ｂ（日本ゼオン（株））４０ｗｔ％水溶液５ｇ（固形分として２ｇ）、分散媒として蒸留水６０ｇを遊星型ミキサーで混合し、固形分４１ｗｔ％の正極塗工液を調製した。
<Example 20>
[Production of positive electrode]
100 g of LiFePO 4 having a coating carbon amount of 2 wt% as a positive electrode active material, 8 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, 2 wt. Of carboxymethyl cellulose WS-C (Daiichi Kogyo Seiyaku Co., Ltd.) as a binder 100 g of 2% solution (2 g as solid content), 5 g of styrene butadiene rubber (SBR) emulsion BM-400B (Nippon Zeon Co., Ltd.) 40 wt% aqueous solution (2 g as solid content), and 60 g of distilled water as a dispersion medium are mixed with a planetary mixer. A positive electrode coating solution having a solid content of 41 wt% was prepared.
［負極の作製］
負極活物質に平均粒径２５μｍ、比表面積３．１ｇ／ｃｍ２の人造黒鉛１００ｇを用い導電剤としてアセチレンブラック（電気化学工業（株）デンカブラック）５ｇ、バインダー成分としてカルボキシメチルセルロース ＷＳ−Ｃ（第一工業製薬（株））２ｗｔ％溶液１０ｇ、スチレンブタジエンゴム（ＳＢＲ）エマルジョン（日本ゼオン（株）ＢＭ−４００Ｂ）４０ｗｔ％溶液５ｇ、分散媒として蒸留水８ｇを遊星型ミキサーで混合し、固形分５０ｗｔ％の負極塗工液を調製した。この塗工液を厚み１０μｍの電解銅箔上にコーティングを行い、１３０℃で乾燥後ロールプレス処理を行い、活物質密度１．４５ｇ／ｃｍ３、負極活物質８ｍｇ／ｃｍ２の両面塗工負極を得た。
[Production of negative electrode]
Artificial graphite 100 g having an average particle diameter of 25 μm and a specific surface area of 3.1 g / cm 2 is used for the negative electrode active material, 5 g of acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) as a conductive agent, and carboxymethyl cellulose WS-C (No. 1) as a binder component. Ichi Kogyo Seiyaku Co., Ltd.) 10 g of 2 wt% solution, 5 g of 40 wt% solution of styrene butadiene rubber (SBR) emulsion (Nippon ZEON Co., Ltd. BM-400B), 8 g of distilled water as a dispersion medium are mixed with a planetary mixer, and the solid content A 50 wt% negative electrode coating solution was prepared. This coating solution is coated on an electrolytic copper foil having a thickness of 10 μm, dried at 130 ° C. and then subjected to a roll press treatment, and a double-side coated negative electrode having an active material density of 1.45 g / cm 3 and a negative electrode active material of 8 mg / cm 2. Got.
［硬化前溶液の調整］
化合物１７の出発物質にジエチレングリコールを用いた３２官能性末端（アクリロイル変性２官能、メチル基３０官能）エチレンオキサイド５４ｗｔ％と２，３−エポキシ−１−プロパノール４６ｗｔ％の付加重合体（分子量５０００）１０ｇ、ＬｉＰＦ６２ｇと熱重合開始剤として２，２’−アゾビスイソブチロニトリル０．０５ｇを溶解させ、硬化前溶液を得た。
[Preparation of solution before curing]
10 g of addition polymer (molecular weight 5000) of 32 functional ends (acryloyl-modified bifunctional, methyl group 30 functional) ethylene oxide 54 wt% and 2,3-epoxy-1-propanol 46 wt% using diethylene glycol as a starting material for compound 17 Then, 2 g of LiPF 6 and 0.05 g of 2,2′-azobisisobutyronitrile as a thermal polymerization initiator were dissolved to obtain a pre-curing solution.
［リチウム電池の作製］
セパレーターとしてＰＥＴにＳｉＯ２とＡｌ２Ｏ３をコーティングした厚み３０μｍのセパリオンＳ２４０Ｐ３０（デグサジャパン（株））を使用した以外は実施例１と同様に作製した。
[Production of lithium battery]
It was produced in the same manner as in Example 1 except that Separion S240P30 (Degussa Japan Co., Ltd.) having a thickness of 30 μm obtained by coating PET with SiO 2 and Al 2 O 3 as a separator was used.
〈比較例１〉
リチウム電池の作製において、実施例１のセパレーターに代えて、ポリオレフィン微多孔膜（空孔率３６％、厚さ２５μｍ）を使用した以外は、実施例１と同様に試験用のセルを作製した。
<Comparative example 1>
In the production of the lithium battery, a test cell was produced in the same manner as in Example 1 except that a polyolefin microporous membrane (porosity 36%, thickness 25 μm) was used instead of the separator of Example 1.
〈比較例２〉
リチウム電池の作製において、実施例１４のセパレーターに代えて、ポリオレフィン微多孔膜（空孔率３６％、厚さ２５μｍ）を使用した以外は、実施例１４と同様に試験用のセルを作製した。
<Comparative example 2>
In the production of the lithium battery, a test cell was produced in the same manner as in Example 14 except that a polyolefin microporous membrane (porosity 36%, thickness 25 μm) was used instead of the separator of Example 14.
〈比較例３〉
リチウム電池の作製において、実施例１６のセパレーターに代えて、ポリオレフィン微多孔膜（空孔率３６％、厚さ２５μｍ）を使用した以外は、実施例１６と同様に試験用のセルを作製した。
<Comparative Example 3>
In the production of the lithium battery, a test cell was produced in the same manner as in Example 16 except that a polyolefin microporous membrane (porosity 36%, thickness 25 μm) was used instead of the separator of Example 16.
［評価方法］
下記の条件でセルの評価を行い、結果を表３、４に示す。
[Evaluation methods]
The cells were evaluated under the following conditions, and the results are shown in Tables 3 and 4.
作製後のセルは、ゲル系のセルでは２０℃、ドライ系のセルは４０℃で充放電試験を行った。まず、各セルについて０．２Ｃの放電容量を確認後、ゲル系では１Ｃ充放電５００サイクル、ドライ系では０．５Ｃ充放電２００サイクルを行い、１サイクル目の放電容量に対する容量保持率を確認することにより、セパレーターの違いによる、硬化前溶液の含浸性の影響を確認した。セルの容量は１Ａｈになるように積層した。サイクル試験１サイクル目の容量はセル作製後の０．２Ｃ放電容量に対していずれも１％以内の容量減少範囲のセルを使用した。 The prepared cell was subjected to a charge / discharge test at 20 ° C. for a gel cell and 40 ° C. for a dry cell. First, after confirming the discharge capacity of 0.2C for each cell, 500C cycles of 1C charge / discharge are performed in the gel system, and 200C cycles of 0.5C charge / discharge are performed in the dry system to confirm the capacity retention rate with respect to the discharge capacity of the first cycle. Thus, the influence of the impregnation property of the pre-curing solution due to the difference in the separator was confirmed. The cells were stacked so that the capacity was 1 Ah. The capacity in the first cycle of the cycle test was a cell with a capacity reduction range of 1% or less with respect to the 0.2 C discharge capacity after cell preparation.
さらに、試験周囲温度２０℃±５℃において過充電試験を行った。充電条件３Ｃ ＣＣ−ＣＶ １２Ｖでの電池表面温度の最高温度を確認した。 Furthermore, an overcharge test was conducted at a test ambient temperature of 20 ° C. ± 5 ° C. The maximum temperature of the battery surface temperature under charging condition 3C CC-CV 12V was confirmed.
〈熱重合のゲル電解質の場合〉
硬化前溶液をプレ電池に注液後、真空シールし、１分後に６５℃で硬化開始したセルと２０分２０℃で放置後、６５℃で硬化開始したセルを作製した。
<In the case of gel electrolyte for thermal polymerization>
After injecting the pre-curing solution into a pre-battery, vacuum sealing was performed, and a cell that started curing at 65 ° C. after 1 minute and a cell that started curing at 65 ° C. after 20 minutes at 20 ° C. were prepared.
〈紫外線硬化のゲル電解質の場合〉
硬化前溶液に別の容器で含浸する時間を常圧状態で正極と負極は２０分、セパレーターのみ１分と２０分の２種類の条件で行った。
<In the case of UV-curing gel electrolyte>
The pre-curing solution was impregnated in a separate container under normal pressure conditions for 20 minutes for the positive electrode and the negative electrode, and for the separator only for 1 minute and 20 minutes.
〈熱重合でドライ系電解質の場合〉
硬化前溶液をプレ電池に注液後、真空シールし、１分後に８０℃で硬化開始したセルと２０分２０℃で放置後、８０℃で硬化開始したセルを作製した。
<In case of dry electrolyte by thermal polymerization>
The pre-curing solution was poured into a pre-battery, vacuum sealed, and a cell that started curing at 80 ° C. after 1 minute and a cell that started curing at 80 ° C. after 20 minutes at 20 ° C. were prepared.
本発明のリチウムポリマー電池は、携帯電話、ノートパソコン、携帯情報端末（ＰＤＡ）、ビデオカメラ、デジタルカメラなどの各種の携帯型機器に使用することができる。さらに、電動自転車や電動自動車に搭載する中型・もしくは大型のリチウム電池にも有用である。 The lithium polymer battery of the present invention can be used for various portable devices such as a mobile phone, a notebook computer, a personal digital assistant (PDA), a video camera, and a digital camera. Furthermore, it is also useful for medium-sized or large-sized lithium batteries mounted on electric bicycles and electric vehicles.
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| JP2012182130A (en) * | 2011-02-10 | 2012-09-20 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte for secondary battery, and nonaqueous electrolyte secondary battery including the same |
| JP2013504843A (en) * | 2009-09-14 | 2013-02-07 | リ−テック・バッテリー・ゲーエムベーハー | Electrochemical energy storage device with container |
| WO2013073012A1 (en) * | 2011-11-15 | 2013-05-23 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| JP2013152857A (en) * | 2012-01-25 | 2013-08-08 | Daiso Co Ltd | Separator for power storage device, power storage device and manufacturing method thereof |
| KR101840593B1 (en) * | 2013-10-29 | 2018-03-20 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery comprising the same |
| JP2019114390A (en) * | 2017-12-22 | 2019-07-11 | 日本ゼオン株式会社 | Electrolyte composition for electrochemical device and manufacturing method of electrode for electrochemical device |
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| JP2013504843A (en) * | 2009-09-14 | 2013-02-07 | リ−テック・バッテリー・ゲーエムベーハー | Electrochemical energy storage device with container |
| JP2012182130A (en) * | 2011-02-10 | 2012-09-20 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte for secondary battery, and nonaqueous electrolyte secondary battery including the same |
| WO2013073012A1 (en) * | 2011-11-15 | 2013-05-23 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| CN103947032A (en) * | 2011-11-15 | 2014-07-23 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| JPWO2013073012A1 (en) * | 2011-11-15 | 2015-04-02 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| US10446824B2 (en) | 2011-11-15 | 2019-10-15 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolyte secondary battery |
| JP2013152857A (en) * | 2012-01-25 | 2013-08-08 | Daiso Co Ltd | Separator for power storage device, power storage device and manufacturing method thereof |
| KR101840593B1 (en) * | 2013-10-29 | 2018-03-20 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery comprising the same |
| US11121404B2 (en) | 2013-10-29 | 2021-09-14 | Lg Chem, Ltd. | Gel polymer electrolyte and lithium secondary battery comprising the same |
| JP2019114390A (en) * | 2017-12-22 | 2019-07-11 | 日本ゼオン株式会社 | Electrolyte composition for electrochemical device and manufacturing method of electrode for electrochemical device |
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