TW482723B - Method for laminating solid polymer electrolyte film - Google Patents
Method for laminating solid polymer electrolyte film Download PDFInfo
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- TW482723B TW482723B TW086103536A TW86103536A TW482723B TW 482723 B TW482723 B TW 482723B TW 086103536 A TW086103536 A TW 086103536A TW 86103536 A TW86103536 A TW 86103536A TW 482723 B TW482723 B TW 482723B
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- film
- solid electrolyte
- polymer solid
- laminating
- layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Secondary Cells (AREA)
- Laminated Bodies (AREA)
Abstract
Description
經濟部中央標準局員工消費合作社印製 482723 A7 B7 五、發明説明(1 ) 〔發明之詳細說明〕 〔發明所屬之技術領域〕 本發明爲關於高分子固體電解質薄膜電 極上層合之方法。 〔先前之技術〕 高分子固體電解質(以下稱爲「SPEj:) , ^ ^ g, 體狀態下顯示出高離子導電度之高分子材料, 現在各種感應器、燃料電池等之應用。 又,亦可能用於第二代電池、光電池、電鉻元件等之 應用,且在世界中乃嘗試進行開發。 爲了在S P E上賦與高的離子導電度,乃要求其玻璃 態化溫度爲低,但若玻璃態化溫度低,則因令薄膜強度降 低,而具有工業上操作困難之缺點。 又,爲了改良離子導電度,亦常進行添加有機溶劑之 方法,但其導致強度降低,且漸令操作變爲困難。 因此,目前之狀況一般爲在電極上直接塗布S P E預 聚合物,並使其交聯固化之方法。 〔發明所欲解決之課題〕 然而,此類方法,於S P E聚合度或者s p E薄膜之 厚度管理上困難,且在取得均質且均勻之S P E薄膜上乃 爲困難。 因此,由玻璃態化溫度低,且具有高離子導電度之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-4 - -裝-- (請先閱讀背面之注意事項再填寫本頁) -訂· 482723 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(2 ) S P E材料所構成之S P E薄膜,且離子導電度爲均質且 膜厚均勻之S P E薄膜之取得困難。又,將S P E層與電 極之電化性接觸極爲良好之S P E層,以於電極上均質且 密黏之狀態下層合複合乃爲困難。 又,依據S P E之種類,亦具有吸濕性之物質,於令 S P E與電極複合時,亦具有必須爲了控制水分而進行複 合工程之氛圍氣控制之問題。 本發明爲鑑於此類狀況,以提供均質之S P E複合薄 膜及其製造方法,及使用此類S P E複合薄膜,以簡便之 方法將S P E薄膜層合於電極上之方法及s P E複合電極 之製造方法爲其目的。 〔解決課題之手段〕 本發明者等人重覆致力研究,結果成功地以簡易之方 法將S P E複合薄膜化及其至電極上之層合化,並基於此 發現而完成本發明。 即,本發明者等人乃開發出,藉由令玻璃態化溫度低 且具有高離子導電度之S P E材料所構成之S P E層,與 基材薄膜複合,而製造出離子導電度爲均質且膜厚爲均勻 之S P E複合薄膜之方法,及以來自此類s P E複合薄膜 之S P E薄膜作爲構成材料之保存性優異的s P E複合薄 膜,以簡便方法製造之方法。又,開發使用此類S P E層 合薄膜將S P E薄膜層合於電極上之方法及s P E複合電 極之製造方法。 (請先閲讀背面之注意事 • IKI. •項再填. 裝-- 寫本頁) 訂 本紙張尺度適用中國國家標準(CNS)A4規格U10X297公釐)一 5 _ 482723 A7 _______B7 _ 五、發明説明(3 ) 特別地,依據本發明,爲提供令塑料製等之基材薄膜 與s P E層所層合之s P E層合薄膜(以下單稱「複合薄 」)之簡便的製造方法,爲此類複合薄膜之一種的基材 «膜與S P E層與覆蓋薄膜所層合之複合薄膜之簡便的製 造方法。又提供使用本發明之複合薄膜製造S P E複合電 極之方法,即將複合薄膜之基材薄膜與對面側之S P E面 ’或者於複合薄膜爲具有覆蓋薄膜之情形中將覆蓋薄膜除 去之S P E面,令於預先塗布硬化性膠黏劑之電極上接觸 層合後,令該膠黏劑硬化而製造出附有基材薄膜之S P E 薄膜爲層合於電極之S P E複合電極之方法。再者,本發 明爲開發藉由使用該複合薄膜,如前述製造令附有基材薄 膜之SPE薄膜層合於電極之SPE複合電極後,剝離基材薄膜 ’並在S P E表面上層合其他之構成材料例如其他之電極 ’製造SPE複合電極之方法。 .即,依據本發明,提供下述之S P E薄膜的層合方法 (複合薄膜之製造方法)及S P E複合電極之製造方法: 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) (1 )高分子固體電解質薄膜之層合方法,其特徵爲 包含在基材薄膜上,或者具有金屬或金屬氧化物薄膜層之 基材薄膜的該薄膜層上,層合高分子固體電解質之工程及 在所得層合物之上下面加壓之工程, (2 )高分子固體電解質薄膜之層合方法,其特徵爲 包含在基材薄膜上,或者具有金屬或金屬氧化物薄膜層之 基材薄膜的該薄膜層上,層合高分子固體電解質液狀物之 工程,續在此類層合物之高分子固體電解質液狀物表面上 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-6 - "' 482723 A7 B7 五、發明説明(4 ) 層合覆蓋薄膜之工程及在所得層合物之上下面加壓之工程 9 (3 )高分子固體電解質薄膜之層合方法,其特徵爲 包含在基材薄膜上,或者具有金屬或金屬氧化物薄膜層之 基材薄膜的該薄膜層上,層合含有聚合性化合物之高分子 固體電解質液狀物之工程,令該聚合性化合物引起聚合反 應並使高分子固體電解質層呈現實質上非流動狀態之工程 ,及在所得層合物之上下面加壓之工程, (4 )高分子固體電解質薄膜之層合方法,其特徵爲 包含在基材薄膜上,或者具有金屬或金屬氧化物薄膜層之 基材薄膜的該薄膜層上,層合含有聚合性化合物之高分子 固體電解質液狀物之工程,在此類層合物之高分子固體電 解質液狀物表面,層合覆蓋薄膜之工程,令該聚合性化合 物引起聚合反應並使高分子固體電解質層呈現實際上非流 動狀態之工程,及在所得層合物之上下面加壓之工程, 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) (5 )如前述(1 )〜(4 )記載之之高分子固體電 解質薄膜之層合方法,其中高分子固體電解質薄膜之導電 度爲1 O-dQ-icm-1以上, (6 )高分子固體電解質複合電極之製造方法,#特 徵爲包含在依據前述(1 )或(3 )記載之層合方法,將 高分子固體電解質作成由高分子固體電解質層與基材薄膜 層所構成之層合物,或製造由高分子固體電解質層與附有 該薄膜層之基材薄膜層所構成之層合物後,令該層合物之 高分子固體電解質面接觸預先塗布硬化性膠黏劑之電極而 本紙張尺度適用中國國家標準(CNS)A4規格UlOX297公釐_ 482723 A7 B7 五、發明説明(5 ) 層合之工程,及令該膠黏劑硬化之工程, (7 )高分子固體電解質複合電極之製造方法,#特 徵爲包含在依據前述(2)或(4)記載之層合方法,將 高分子固體電解質薄膜作成由覆蓋薄膜與高分子固體電解 質層與基材薄膜層所構成之層合物、或製造由覆蓋薄膜與 高分子固體電解質層與附有該薄膜層之基材薄膜層所構成 之層合物後,將層合物之覆蓋薄膜由高分子固體電解質層 剝離之工程,令高分子固體電解質面接觸預先塗布硬化性 膠黏劑之電極而層合之工程,令該膠黏劑硬化之工程。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) (8 )高分子固體電解質複合電極之製造方法,其特 徵爲包含在依據前述(1 )或(3 )記載之層合方法,將 高分子固體電解質薄膜作成由高分子固體電解質層與基材 薄膜層所構成之層合物、或製造高分子固體電解質層與附 有該薄膜層之基材薄膜層所構成之層合體後,令該層合物 之高分子固體電解質面接觸預先塗布硬化性膠黏劑之電極 而層合之工程,及令該膠黏劑硬化之工程,續令基材薄膜 、或者在附有該薄膜層之基材薄膜情形中令該薄膜層與基 材薄膜整體地由高分子固體電解質層剝離之工程,及在高 分子固體電解質面上令其他之構成材料層合之工程。 (9 )高分子固體電解質複合電極之製造方法,其特 徵爲包含在依據前述(2 )或(4 )記載之層合方法,將 高分子固體電解質薄膜作成由覆蓋薄膜與高分子固體電解 質層與基材薄膜層所構成之層合體,或製造由覆蓋薄膜與 高分子固體電解質層與附有該薄膜層之基材薄膜所構成之 本紙張尺度適用中國國家標準(〇奶)八4規格(210\297公釐)_8 482723 A7 B7 五、發明説明(6 ) 層合物後,將層合物之覆蓋薄膜由高分子固體電解質層剝 離之工程,令高分子固體電解質面接觸預先塗布硬化性膠 黏劑之電極而層合之工竹程,令該膠黏劑硬化之工程,續 令基材薄膜、或者在附有該薄膜層之基材薄膜情形中令該 薄膜層與基材薄膜整體地由高分子固體電解質層剝離之工 程,及在高分子固體電解質面上令其他之構成材料層合之 工程。 (1 0 )高分子固體電解質複合電極之製造方法,其 特徵爲包含在依據前述(1 )或(3 )記載之層合方法, 將高分子固體電解質薄膜作成由高分子固體電解質層與基 材薄膜層所構成之層合物、或製造由高分子固體電解質層 與附有該薄膜層之基材薄膜層所構成之層合物後,令該層 合物之高分子固體電解質面接觸預先塗布硬化性膠黏劑之 電極而層合之工程,及令該膠黏劑硬化之工程,續令基材 薄膜、或者在具有該薄膜層之基材薄膜情形中令該薄膜層 與基材薄膜整體地由高分子固體電解質層剝離之工程,及 在高分子固體電解質面上令其他之電極層合之工程, 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 及, (1 1 )高分子固體電解質複合電極之製造方法,其 特徵爲包含在依據前述(2)或(4)記載之層合方法, 將高分子固體電解質薄膜作成由覆蓋薄膜與高分子固體電 解質層與基材薄膜層所構成之層合物、或製造由覆蓋薄膜 與高分子固體電解質層與附有該薄膜層之基材薄膜層所構 成之層合物後,令層合物之覆蓋薄膜由高分子固體電解質 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)_ 9 一 經濟部中央標準局員工消費合作社印製 482723 A7 B7 五、發明説明(7 ) 層剝離之工程,令高分子固體電解質面接觸預先塗布硬化 性膠黏劑之電極而層合之工程,令該膠黏劑硬化之工程, 續令基材薄膜、或者在附有該薄膜層之基材薄膜情形中令 該薄膜層與基材薄膜整體地高分子固體電解質層剝離之工 程,及在高分子固體電解質面上令其他之電極層合之工程 〇 本發明中作爲基材薄膜爲塑膠製之薄膜,以具有耐水 性者爲合適使用。例如,可使用聚乙烯、聚丙烯等之聚烯 烴、聚氯乙烯、聚對酞酸乙烯酯(P ET)等之聚酯、耐 龍6、耐龍6 — 6等之聚醯胺等一般之熱塑性樹脂。又, 基材薄膜可爲無延伸薄膜及延伸薄膜均可。薄膜之厚度爲 1〜5000从111,較佳1〜1 000//111,特別以5〜 100//m爲較佳。 又,本發明之基材薄膜,亦可適當使用在上述薄膜上 將鋁、氧化鋁、二氧化矽等之金屬或金屬氧化物以澱積等 任意公知之方法層合之層合薄膜ί乍爲基材薄膜。 再者基材薄膜若爲與S Ρ Ε之剝離性良好者,則即使 非爲塑膠製之物質亦可,例如鋁、不銹鋼、銅等之金屬箔 亦可。 本發明中所使用之s Ρ Ε,爲由聚合性化合物於電解 質鹽存在下或非存在下聚合所得之高分子物質所構成之材 料。本發明中特佳使用之S Ρ Ε爲此類材料,較佳使用爲 在至少一種電解質鹽存在下電解質離子之易動度高,即離 子導電性爲1 — c m-1以上,較佳爲 -裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準(CNS ) A4規格(2!0X297公釐)一 — 482723 Α7 Β7 經濟部中央標隼局員工消費合作社印裝 五、發明説明(8 )1 〇-5Ω -1 cm-1,更佳爲 1 〇-4Ω -1 cm-1 以上之 s p E。此處,所謂「至少一種電解質鹽存在下.........以 上之SPE」,意指本發明複合薄膜中作爲SPE材料者 ,爲已含有電解質鹽之S P E,意指不僅具有上述離子導 電度之物質,且亦包含在使用複合薄膜所製造之S P E複 合電極或使用該電極所製造之電池、電容器等電化性裝置 中,於來自本發明複合薄膜之S P E上,其後藉由添加電 解質鹽和/或溶劑而賦予上述離子導電度之S P E材料。 聚合除了以熱聚合以外,可使用光、紫外線、電子射 線、r射線、X射線等之活性光線依公知方法進行。 聚合性化合物可列舉至少具有1個雜原子之官能性單 體或低聚物。 具體例可列舉具有甲基丙烯酸ω —甲基低聚氧基乙酯 等之具有氧化烯鏈之(甲基)丙烯酸酯及二(甲基)丙烯 酸酯;甲基丙烯酸甲酯,丙烯酸正丁酯等之(甲基)丙烯 酸烷酯;丙烯醯胺、甲基丙烯醯胺、Ν,Ν -二甲基丙烯 醯胺、Ν,Ν—二甲基甲基丙烯醯胺、丙烯醯馬福啉、甲 基丙烯醯馬福啉、Ν,Ν -二甲基胺丙基(甲基)丙烯醯 胺等之(甲基)丙烯醯胺系化合物;Ν —乙烯基乙醯胺、 Ν—乙烯基甲醯胺等之Ν-乙烯基醯胺系化合物;乙基乙 烯基醚等之烷基乙烯基醚;三羥甲基丙烷三(甲基)丙烯 酸酯、季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲 基)丙烯酸酯等之多官能性(甲基)丙烯酸酯;苯基縮水 甘油基醚丙烯酸酯已二異氰酸酯尿烷預聚物、苯基縮水甘 (請先閱讀背面之注意事項再填寫本頁) 4 •項再填> 裝· 訂 本紙張尺度適用中國國家標準(CNS>A4規格( 210X297公釐)_ 11 一 482723 A7 B7 五、發明説明(9 ) 油基醚丙烯酸酯異佛爾酮二異氰酸酯尿烷預聚物等各種尿 烷丙烯酸酯預聚物等。 再者,可列舉下式所示之單位於1分子中至少具有1 個氧化綠鏈之尿院(甲基)丙嫌酸酯。 C H 2 = C ( R 1 ) CO〔0 ( C Η 2 ) x (C H ( C H a ) )y〕zNHC00R2 -(式中,R1爲氫或甲基,R2爲含有氧化烯基之二價有機 基,可爲直鏈狀、分支狀、環狀構造之任一種所構成者均 可,且即使含有碳、氫及氧以外之元素亦可;X及Y爲各 別獨立爲0或1〜5之整數;Z爲0或1〜10之整數。 但,X及Y同爲0時則Z亦爲〇或1〜5之整數;Z爲0 或1〜1 0之整數。但,X及Y同爲0時則Z亦爲0 ; (C Η 2 )與(C H ( C Η 3 ))爲不規則排列亦可。又, 同一分子中複數個以上述式所表示之單位中的R1、R 2及 X、Υ、Ζ之值爲在各別之單位中各爲獨立,並無必要相 同)。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 上式所示化合物之具體例可列舉Ν —甲基丙烯醯胺甲 酸ω —甲基低聚氧基乙酯、甲基丙烯醯氧乙基胺甲酸、ω 一甲基低聚氧基乙酯等。此些聚合性化合物可爲1種,且 可混合使用2種以上。 以上之聚合性化合物亦以含有氧乙烯鏈之(甲基)丙 烯酸尿烷酯、丙烯酸尿烷酯、令有氧化烯鏈之(甲基)丙 烯酸酯、(甲基)丙烯醯胺系化合物爲較佳,特別以含有 氧化烯鏈之(甲基)丙烯酸尿烷酯爲合適。 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)一 12 - 482723 經濟部中央標準局員工消費合作社印裝Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 482723 A7 B7 V. Description of the invention (1) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to a method for laminating a polymer solid electrolyte film electrode. [Previous Technology] Polymer solid electrolytes (hereinafter referred to as "SPEj:"), ^ ^ g, polymer materials that exhibit high ionic conductivity in the bulk state, and are now used in various inductors, fuel cells, etc. May be used in second-generation batteries, photovoltaic cells, electrochromic components, etc., and development is being tried in the world. In order to impart high ionic conductivity on SPE, its glass transition temperature is required to be low, but if If the glass transition temperature is low, the strength of the film is reduced, which has the disadvantage of being difficult to handle industrially. In addition, in order to improve the ion conductivity, a method of adding an organic solvent is also often performed, but it causes a reduction in strength and gradually changes the operation. It is difficult. Therefore, the current situation is generally a method of directly coating an SPE prepolymer on an electrode and curing it by cross-linking. [Problems to be Solved by the Invention] However, such a method depends on the degree of SPE polymerization or sp E It is difficult to manage the thickness of the film, and it is difficult to obtain a homogeneous and uniform SPE film. Therefore, the glass transition temperature is low and the ion conductivity is high. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)-4--installed-(Please read the precautions on the back before filling out this page)-Order · 482723 A7 B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (2) It is difficult to obtain a SPE thin film made of SPE material and having a uniform ionic conductivity and a uniform film thickness. Furthermore, the SPE layer having excellent electrochemical contact with the electrode It is difficult to laminate and combine the electrode in a homogeneous and dense state on the electrode. In addition, depending on the type of SPE, it also has a hygroscopic substance. When SPE and the electrode are compounded, it is necessary to control the moisture. The problem of atmosphere control of composite engineering. In view of such situations, the present invention provides a homogeneous SPE composite film and a manufacturing method thereof, and uses such SPE composite film to laminate SPE film on an electrode in a simple and convenient way. The method and the manufacturing method of the s PE composite electrode are for the purpose. [Means for Solving the Problem] The inventors and the like have repeatedly made intensive studies, and the results have been successfully simplified. A method is to form an SPE composite thin film and laminate it onto an electrode, and complete the present invention based on this finding. That is, the inventors have developed a method that reduces the glass transition temperature and has high ionic conductivity. A method for manufacturing an SPE layer composed of an SPE material and a base film to produce a SPE composite film having a uniform ion conductivity and a uniform film thickness, and an SPE film from such an s PE composite film as a constituent material A method for manufacturing an s PE composite film with excellent storage properties by a simple method. Furthermore, a method of laminating an SPE film on an electrode using such an SPE laminate film and a method for manufacturing an s PE composite electrode have been developed. (Please read the notes on the back first • IKI. • Fill in the items again. Pack-write this page) The size of the paper used in this edition applies to the Chinese National Standard (CNS) A4 specification U10X297 mm) 1 5 _482723 A7 _______B7 _ V. Invention Explanation (3) In particular, in accordance with the present invention, a simple manufacturing method for providing an s PE laminated film (hereinafter simply referred to as "composite thin") in which a substrate film made of plastic or the like and an s PE layer are laminated is provided. A simple method for manufacturing a composite film in which a substrate «film, an SPE layer and a cover film is one of such composite films. A method for manufacturing an SPE composite electrode using the composite film of the present invention is also provided, that is, the substrate film of the composite film and the SPE surface on the opposite side, or the SPE surface in which the cover film is removed when the composite film is a cover film, so that After the contact-layering of the hardening adhesive is pre-coated on the electrode, the adhesive is hardened to produce a SPE film with a substrate film as a method of laminating the SPE composite electrode on the electrode. Furthermore, in the present invention, by using the composite film, as described above, the SPE film with the base film is laminated to the SPE composite electrode of the electrode, the base film is peeled off, and other components are laminated on the surface of the SPE. Materials such as other electrodes' methods for making SPE composite electrodes. That is, according to the present invention, the following methods of laminating SPE films (manufacturing methods of composite films) and methods of manufacturing SPE composite electrodes are provided: printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page again) (1) A method for laminating a polymer solid electrolyte film, which is characterized in that it is contained on a substrate film, or on a film layer of a substrate film having a metal or metal oxide film layer, and the layer is Engineering of molecular solid electrolyte and engineering of pressing under and above the obtained laminate, (2) Laminating method of polymer solid electrolyte film, which is characterized by being contained on a base film or having a metal or metal oxide film The project of laminating polymer solid electrolyte liquid on this film layer of the base film of the layer is continued on the surface of the polymer solid electrolyte liquid of such laminates. This paper applies the Chinese national standard (CNS). A4 specification (210X297 mm) -6-" 482723 A7 B7 V. Description of the invention (4) Project of laminating cover film and pressing process on top and bottom of the obtained laminate 9 (3) A method for laminating a polymer solid electrolyte film, characterized in that a polymer film containing a polymerizable compound is laminated on a base film or a base film having a metal or metal oxide thin film layer. A project of a polymer solid electrolyte liquid, a process in which the polymerizable compound causes a polymerization reaction and the polymer solid electrolyte layer assumes a substantially non-flowing state, and a project in which pressure is applied above and below the obtained laminate, (4 A method for laminating a polymer solid electrolyte film, characterized in that a polymer solid containing a polymerizable compound is laminated on the base film or the thin film layer of the base film having a metal or metal oxide film layer The process of electrolyte liquid substance, the process of laminating a covering film on the surface of such a polymer solid electrolyte liquid substance, so that the polymerizable compound causes a polymerization reaction and makes the polymer solid electrolyte layer appear virtually non-flowing. Projects in the state and projects pressurized above and below the obtained laminate are printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ( (Read the precautions on the back before filling this page) (5) The method for laminating polymer solid electrolyte films as described in (1) to (4) above, where the conductivity of the polymer solid electrolyte film is 1 O-dQ -icm-1 or more, (6) A method for manufacturing a polymer solid electrolyte composite electrode, # is characterized in that the polymer solid electrolyte is composed of a polymer solid electrolyte in accordance with the lamination method according to (1) or (3) above. Layer and substrate thin film layer, or a polymer solid electrolyte layer and a substrate thin film layer with the film layer The surface is in contact with the electrode pre-coated with a hardening adhesive and the paper size is applicable to the Chinese National Standard (CNS) A4 specification UlOX297 mm_ 482723 A7 B7 V. Description of the invention (5) The process of lamination and curing the adhesive Project, (7) Manufacturing method of polymer solid electrolyte composite electrode, #Characterized by the method of lamination according to (2) or (4) above, the polymer solid electrolyte film is made of a cover film and a polymer A laminate composed of a daughter solid electrolyte layer and a substrate film layer, or a laminate composed of a cover film, a polymer solid electrolyte layer, and a substrate film layer to which the film layer is attached, and then the laminate is laminated. The process of peeling the cover film from the polymer solid electrolyte layer, the process of bringing the polymer solid electrolyte surface into contact with the electrode coated with a hardening adhesive in advance, and laminating it, the process of hardening the adhesive. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (8) The manufacturing method of polymer solid electrolyte composite electrodes, which is characterized by being included in accordance with (1) or (3) above The described lamination method includes forming a polymer solid electrolyte film into a laminate composed of a polymer solid electrolyte layer and a base film layer, or manufacturing a polymer solid electrolyte layer and a base film layer with the thin film layer. After the laminated body is constituted, the process of laminating the polymer solid electrolyte surface of the laminate in contact with the electrode coated with a hardening adhesive in advance, and the process of hardening the adhesive, continuing to make the base film, or In the case of the base film with the thin film layer attached thereto, a process in which the thin film layer and the base film are integrally peeled off from the polymer solid electrolyte layer, and a process in which other constituent materials are laminated on the polymer solid electrolyte surface. (9) A method for manufacturing a polymer solid electrolyte composite electrode, characterized in that the polymer solid electrolyte film is formed by a lamination method according to the above (2) or (4), and the polymer solid electrolyte film is composed of a cover film and a polymer solid electrolyte layer and The laminated body composed of the base film layer, or the paper size made of the cover film, the polymer solid electrolyte layer, and the base film with the thin film layer is applicable to the Chinese national standard (0 milk) 8 (4) (210 \ 297mm) _8 482723 A7 B7 V. Description of the invention (6) After laminating, the process of peeling the cover film of the laminate from the polymer solid electrolyte layer, so that the polymer solid electrolyte surface contacts the pre-coated hardening glue. The process of laminating the electrodes of the adhesive to harden the adhesive continues the substrate film, or in the case of the substrate film with the film layer attached, the film layer and the substrate film are integrally formed. The process of peeling off the polymer solid electrolyte layer and the process of laminating other constituent materials on the surface of the polymer solid electrolyte. (1) A method for manufacturing a polymer solid electrolyte composite electrode, characterized in that the polymer solid electrolyte film is made of a polymer solid electrolyte layer and a base material by a lamination method according to the above (1) or (3). After a laminate composed of a thin film layer or a laminate composed of a polymer solid electrolyte layer and a base film thin film layer with the thin film layer produced, the polymer solid electrolyte surface of the laminate is brought into contact with the coating in advance The process of laminating the electrode of the hardening adhesive, and the process of hardening the adhesive, continue to make the base film, or in the case of the base film having the thin film layer, make the thin film layer and the base film integral The process of peeling off the polymer solid electrolyte layer and the process of laminating other electrodes on the surface of the polymer solid electrolyte are printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) ) And, (1 1) A method for manufacturing a polymer solid electrolyte composite electrode, characterized in that the method includes the lamination method according to (2) or (4) above, and polymerizes the polymer solid electrolyte. A thin film made of a cover film, a polymer solid electrolyte layer, and a base film layer, or a layer made of a cover film, a polymer solid electrolyte layer, and a base film layer with the thin film layer After the composition, the covering film of the laminate is made of polymer solid electrolyte. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 9-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 482723 A7 B7 5 7. Description of the invention (7) The process of layer peeling, the process of making the polymer solid electrolyte contact the electrode coated with a hardening adhesive in advance and laminating it, the process of hardening the adhesive, and continuing to make the base film, or In the case of the base film with the thin film layer attached, the process of peeling the polymer solid electrolyte layer between the thin film layer and the base film, and the process of laminating other electrodes on the polymer solid electrolyte surface. In the present invention The base film is a plastic film, and it is suitable for those who have water resistance. For example, polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinyl terephthalate (P ET), polyamide 6, such as nylon 6, nylon 6, 6 and the like can be used Thermoplastic resin. The base film may be an unstretched film or a stretched film. The thickness of the film is 1 to 5000 and 111, preferably 1 to 1 000 // 111, and particularly preferably 5 to 100 // m. In addition, the base film of the present invention can also be suitably used as a laminated film in which a metal, such as aluminum, alumina, silicon dioxide, or a metal oxide, is laminated on the film by any known method such as deposition. Substrate film. Furthermore, as long as the substrate film has good releasability from SP, it may be made of a material other than plastic, such as metal foils such as aluminum, stainless steel, and copper. The sPE used in the present invention is a material composed of a polymer substance obtained by polymerizing a polymerizable compound in the presence or absence of an electrolytic salt. The SPE which is particularly preferably used in the present invention is such a material, it is preferably used because the mobility of electrolyte ions is high in the presence of at least one electrolyte salt, that is, the ion conductivity is 1-c m-1 or more, preferably -Installation-(Please read the precautions on the back before filling this page) The size of the paper used in the edition is applicable to the Chinese National Standard (CNS) A4 (2! 0X297 mm) 1 — 482723 Α7 Β7 Staff Consumption of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative print 5. V. Description of the invention (8) Sp0 above 10-0Ω-1 cm-1, more preferably 10-4Ω-1 cm-1. Here, the so-called "SPE above in the presence of at least one electrolyte salt" means that the SPE material in the composite film of the present invention is an SPE that already contains an electrolyte salt, which means that it has not only the above Substances with ionic conductivity are also included in SPE composite electrodes manufactured using a composite film or electrochemical devices such as batteries and capacitors manufactured using the electrodes, on the SPE from the composite film of the present invention, and thereafter by adding An electrolyte salt and / or a solvent which imparts the ionic conductivity to the SPE material. The polymerization can be carried out by a known method using active light such as light, ultraviolet rays, electron rays, r rays, or X-rays, in addition to thermal polymerization. Examples of the polymerizable compound include a functional monomer or oligomer having at least one hetero atom. Specific examples include (meth) acrylates and di (meth) acrylates having an oxyalkylene chain, such as ω-methyl oligooxyethyl methacrylate; methyl methacrylate, and n-butyl acrylate. Alkyl (meth) acrylates; acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, acrylmafolin, methyl (Meth) acrylamide compounds such as acryl-mafolin, N, N-dimethylaminopropyl (meth) acrylamide; N—vinylacetamide, Ν—vinylformamide and the like Ν-vinylamidate-based compounds; alkyl vinyl ethers such as ethyl vinyl ether; trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (methyl) ) Multifunctional (meth) acrylates such as acrylates; phenylglycidyl ether acrylate, diisocyanate urethane prepolymer, phenylglycidyl (please read the precautions on the back before filling this page) 4 • Item Refill > Binding · Paper Sizes Applicable National standard (CNS > A4 specification (210X297 mm) _ 11 482723 A7 B7 V. Description of the invention (9) Oil-based ether acrylate isophorone diisocyanate urethane prepolymer and other urethane acrylate prepolymers In addition, examples include a urinary (meth) propionic acid ester unit having at least one oxidized green chain in a molecule represented by the following formula: CH 2 = C (R 1) CO [0 (C Η 2) x (CH (CH a)) y] zNHC00R2-(where R1 is hydrogen or methyl, R2 is a divalent organic group containing an oxyalkylene group, and may be a linear, branched, or cyclic structure Any of them may be used, and even if it contains elements other than carbon, hydrogen, and oxygen; X and Y are each independently an integer of 0 or 1 to 5; Z is an integer of 0 or 1 to 10. However, When X and Y are both 0, Z is also an integer of 0 or 1 to 5. Z is an integer of 0 or 1 to 10. However, when X and Y are 0, Z is also 0; (C Η 2) And (CH (C Η 3)) may be arranged in an irregular manner. In addition, the values of R1, R2, and X, Υ, and Z in a plurality of units represented by the above formula in the same molecule are in separate units. Each of them is independent and need not be the same) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Specific examples of the compounds shown in the above formula include N—methacrylamidocarboxylic acid ω—methyl oligooxyethyl Esters, methacryloxyethylcarbamic acid, ω monomethyl oligooxyethyl, etc. These polymerizable compounds may be used alone or in combination of two or more. The above polymerizable compounds may also contain The urethane (meth) acrylate and urethane acrylate of the oxyethylene chain, the (meth) acrylate and the (meth) acrylamidonium compound having an oxyalkylene chain are preferable, and the oxyalkylene chain is particularly preferable. Among them, urethane (meth) acrylate is suitable. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 1 12-482723 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs
五、發明説明 又,爲 多官能性聚 爲較佳。 尙,在 ......」意指 總稱表示, 互爲同樣詞 本發明 S P E材料 璃態化溫度 度,而爲意 合性化合物 合之材料情 此,由前述 丙烯睛之物 高之物質, 化溫度降低 S P E材料 1 〇 -6 Ω -1 更佳爲1 0 又,電 L i A s F A7 __ B7_ 了將所得之高分子作成交聯體,而以至少1種 合性化合物與其他之聚合性化合物混合供使用V. Description of the invention It is more preferable that the polymer is polyfunctional. "Hey, in ..." means the general term indicates that the SPE material of the present invention has the same glass transition temperature, but is a material that is a desirable compound. In this case, the acryl-containing material is high. The temperature of the SPE material is reduced by 1 〇-6 Ω -1, more preferably 10, and the electricity L i A s F A7 __ B7_ is obtained by using the obtained polymer as a cross-linked body, and at least 1 type of compound and other Polymerizable compound for use
L i B N a IL i B N a I
L 本發明之詳細說明中所謂的「(甲基) 將「甲基丙烯.........」或「丙烯......... 又所謂的「烯化氧」與「氫化烯」爲實 使用。 之在玻璃態化溫度低,且具有高離子導 所構成之SPE薄膜中,所謂SPE材 ,並非構成該材料之高分子物質的玻璃 指例如高分子物質以外之令增塑劑、溶 或其低聚物、或電解質鹽等至少任何一 形中,作爲被複合之材料的玻璃態化溫 聚合性化合物所得之聚合物以外,例如 質本身即使玻璃態化溫度爲較常溫(2 若爲經由增塑劑、溶劑等之添加而可令 至室溫以下之材料,則被包含於本發明 。又,所謂高的離子導電度,一般若爲 c m-1以上即可,較佳爲1 - 4Ω-icm-1以上。 解質鹽可列舉L i C 1 04、L i BF4 e、LiCF3S03、LiPFe、Li LiSCN、LiN(CF3S02)2' i2BloCllo、LiCF3C02、Ns 丙烯… 」予以 質上以 電度之 料之玻 態化溫 劑、聚 種所複 度。因 ’如聚 〇 °c ) 玻璃態 之L In the detailed description of the present invention, the so-called "(meth)" "methacrylic ..." or "propylene ..." and the so-called "alkylene oxide" and "Hydrogenene" is actually used. In the SPE thin film with low glass transition temperature and high ion conductivity, the so-called SPE material, which is not a polymer material constituting the material, refers to, for example, a plasticizer other than a polymer material, or a solvent that is low. Polymers, or electrolyte salts, in at least any form, other than polymers obtained as glassy-temperature-temperature polymerizable compounds of the material being compounded, for example, even if the glass-state temperature is higher than normal temperature (2 if plasticized Materials such as agents, solvents, etc. that can be kept below room temperature are included in the present invention. In addition, the so-called high ionic conductivity is generally more than c m-1, preferably 1-4Ω- icm-1 or more. Examples of decomposing salts include Li C 1 04, Li BF4 e, LiCF3S03, LiPFe, Li LiSCN, LiN (CF3S02) 2 'i2BloCllo, LiCF3C02, Ns propylene ... " The glassy temperature warming agent and polymer species are reinstated. Because of 'such as poly 0 ° c) glassy
B (請先閱讀背面之注意事項再填寫本頁) -裝- 本紙張尺度適用中國國家標準(CNS)A4規格( 210X 297公釐)_ 13 _ 經濟部中央標準局員工消費合作社印製 482723 五、發明説明(11 、NaSCN、KSCN、MgCl2、 M g ( C 1 〇 4 ) 2 ' (CH3)4NBF4、 (C Η 3) 4N B r、(C2H5)4NCl〇4. (C 2H 5 ) 4N I、( C 3H 7) 4N B r、 (n - C4H9) 4NC 1 0 4 ' (n~ 〇4Η〇)4ΝΙ (n — CsHii) 4N I 等。其中亦以 l i c i 〇4、 L i PF6等之L i鹽、(C2H5) 4Nc 1 〇4等之四級 銨鹽爲較佳。 此些電解質鹽之配合比例,相對於聚合性化合物 100重量份,一般爲0 · 1〜70重量份,以1〜5〇 重量份爲較佳’特別以1〜3 0重量份爲合適β 再者’於本發明之S Ρ Ε中,亦可視所需配合以增塑 劑、溶劑、聚合引發劑等。增塑劑或溶劑可列舉四氫呋喃 、2 —甲基四氫呋喃、1 ,3 —二噚茂烷、4,4 一二甲 基—1 ’ 3 —一 Β号院、丁內酯、碳酸乙烯酯、碳酸丙 烯酯、碳酸丁烯酯、四氫_吩碩、3 —甲基四氫_吩碼、 第三丁基醚、異丁基醚、1 ,2 —二甲氧基乙烷、1 ,2 一二乙氧基甲氧基乙烷、甲基二甘醇二甲醚、甲基三甘醇 二申醚、甲基四甘醇二甲醚、乙基甘醇二甲醚、乙基二甘 醇二甲醚等。此些可爲一種,且亦爲混合二種以上供使用 〇 聚合引發劑可列舉偶氮雙異丁烯睛、過氧化苯甲醯等 之自由基加熱聚合引發劑,笮甲基縮酮、二苯酮等之自由 本紙張尺度適用中國國家標準(CNS ) Α4規格( 14 - ----l-----^批衣—— (請先閱讀背面之注意事項再填寫本頁) -訂 4· 482723 經濟部中央標準局員工消費合作社印策 A7 B7 五、發明説明(12 ) " 基光聚合引發劑,cf3cooh等之質子酸、bf3、 a 1 C 13等之路易士酸等之陽離子聚合觸媒、丁基鋰、 某基鈉、烷醇鋰等之陰離子聚合觸媒等。 本發明中SPE薄膜層之厚度通常爲0 · 1〜 1000/zm,較佳爲〇 · 1〜300//m,特別以 0 · 1〜50//m爲合適。 再者,本發明複合薄膜中所使用之基材薄膜,乃被要 求複合薄膜形成時S P E或S P E液狀物之濕潤性爲良好 。又,本發明之S P E複合電極爲在表面具有基材薄膜之 S P E複合電極,於使用於在剝離基材薄膜露出之S P E 面上,層合其他電極等之其他構成材料之情形中,乃必須 令基材薄膜層與S P E薄膜層之剝離性良好,即必須可在 不損及S P E薄膜形狀狀下剝離。因此,以使用層合S P E之基材薄膜面上,形成金屬或金屬氧化物薄膜層(層合 )者爲特佳。 金屬或金屬氧化物薄膜,可使用一般用於改良塑膠薄 膜之阻氣性所用之薄膜。具體而言,可列舉鋁、不銹鋼、 銅等之金屬箔或澱積膜、二氧化矽、氧化鋁等金屬氧化物 之澱積膜等。其中亦以鋁箔、鋁澱積膜、二氧化矽澱積膜 、氧化鋁澱積膜爲較佳。 對對薄膜之厚度並無特別限定,但於箔之情形爲5〜 1 00//m,澱積膜之情形爲50〜2000埃爲較佳。 (請先閱讀背面之注意事 4 項再填. 裝—— :寫本頁) 訂 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)一 15 - 482723 經濟部中央標準局員工消費合作社印製 A7 ___B7_五、發明説明(13 ) 本發明之複合薄膜爲(a )具有基材薄膜面上,層合 SPE薄膜層構造之複合薄膜,(b)具有基材薄膜上之 金屬或金屬氧化物薄膜層上,層合S P E薄膜層構造之複 合薄膜,及具有將具有此類(a) 、(b)任一種構造之 複合薄膜的S P E薄膜層夾層,並在與基材薄膜之對面側 之面上,層合覆蓋薄膜構造之薄膜之任一種均可,且可依 其用途而適當選擇任一種。 於製造S P E複合電極之方法中,較佳使用之複合薄 膜可藉由在基材薄膜或附有金屬或金屬氧化物薄膜之基材 薄膜的薄膜上,例如,將S P E液狀物(或者液狀S P E 前驅材料)依塗布、噴霧、浸漬等任意方法層合,並視需 要引起聚合反應而令S P E爲實質上非流動狀態層合而製 造。又,複合薄膜爲具有覆蓋薄膜構造之情形中,可藉由 (i )於基材薄膜或附有金屬或金屬氧化物薄膜層之基材 薄膜上,依上述方法層合以S P E薄膜層後,層合覆蓋薄 膜之方法、(i i)於覆蓋薄膜上依同上述之方法,將 S P E爲以實質上非流動狀態層合後,將基材薄膜或附加 金屬或金屬氧化物薄膜之基材薄膜層合之方法,或者( i i i)將SPE液狀物(或者液狀SPE前驅材料)層 合於基材薄膜或附加金屬或金屬氧化物薄膜之基材薄膜與 覆蓋薄膜之間後,並視需要引起聚合反應而令S P E作成 爲以實質上非流動狀態之薄膜狀S P E之方法之任一種而 製造。 此處,所謂「SPE液狀物」或「液狀SPE前驅材 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)一 16 一 — — (請先閲讀背面之注意事_ 4 >項再填. :寫本頁) 裝· 訂 482723 經濟部中央標準局員工消費合作社印製 A7 ___B7五、發明説明(14 ) 料」,不僅分別指在常溫(2 0 °C ),常壓下具有流動性 之物質,且亦包含在常溫,50kg f/cm2以下之 低壓加壓下具有流動性之物質。但,本發明之在前述(1 )或(2 )記載之層合方法中所用之S P E液狀物,於基 材薄膜上,或附有金屬或金屬氧化物薄膜層之基材薄膜的 該薄膜層上層合之情形中,在常溫、常壓下1小時間不會 流動,但於更長之時間爲流動,或者在比常壓更高之5 0 kg f/cm2以下之加壓下具有流動性者爲佳。 於S P E爲具有吸濕性之情形中,例如以使用壓料滾 筒等將覆蓋薄膜層合爲較佳。該覆蓋薄膜並無特別限制, 且可適當使用可作爲前述基材薄膜之塑膠薄膜,又若爲與 S P E薄膜之剝離性爲更良好之薄膜則可較佳使用。 於本發明之複合薄膜爲具有覆蓋薄膜之複合薄膜之情 形中,於依上述(i)至(i i i)之方法製造之工程中 ,因爲經由在S P E層合薄膜之上下面加壓,可將複合薄 膜中之S P E薄膜厚度控制均勻,故以加壓爲較佳。加壓 之方法,以通常之壓榨法即可,但於連續製造複合薄膜之 情形中,例如可使用壓料滾筒等之一般的加壓成形法,而 複合薄膜以連續製造乃爲本發明之特佳的實施態樣之一。 加壓之壓力若爲通常進行層合成形之壓力即可,並無 特別限定,但若以通常低壓成形所使用之5 0 kg f/cm 2以下加壓下進行即可,且若可將S PE 薄膜之膜厚控制在所欲厚度之壓力即可。例如,即使於使 用壓料滾筒之情形中,若可提供所欲之膜厚、對所欲之複 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)-17 - (請先閱讀背面之注意事 4 •項再填· 裝— :寫本頁) 訂 482723 A7 B7 五、發明説明(15 ) 合薄膜特性無不良影響之壓力即可,並無特別限定,例如 滾筒壓力爲1〜30kg f/cm2之範圍爲較佳,以 5〜1 0kg f/cm2之範圍爲特佳。 本發明所使用之電極,於負極之例可列舉鋰金屬、鋰 /鋁合金、鋰/鉻合金、鋰/銻合金等之鋰合金,再者於 使用L i離子作爲載體之情形中可列舉碳材料等。 又,正極之例可列舉氧化鈷、氧化錳、氧化釩、氧化 鎳、氧化鉬等之金屬氧化物、硫化鉬、硫化鈦、硫化釩等 之金屬硫化物、聚苯胺、聚乙炔及其衍生物、聚對伸苯基 及其衍生物、聚吡咯及其衍生物、聚伸瞎吩及其衍生物等 之導電性高分子、天然黑鉛、人造黑鉛、氣相法黑鉛、石 油焦炭、石炭焦炭、氟化鉛、瀝青系碳、聚乙炔等之碳材 料等。 又,本發明所使用之硬化性膠黏劑,可使用前述之聚 合性化合物或含其之液體混合物。特別是,僅可能與 S P E薄膜成爲相同組成物之液體混合物,例如上述之 S P E液狀物,由電極上之S P E薄膜的均質性方面而言 爲特佳,但並不限定於此。 該膠黏劑對電極之塗布方法,可對上述電極使用塗布 、噴霧、浸漬等公知之方法,而可容易地進行。本發明中 ,所謂「預先塗布硬化性膠黏劑之電極」,爲意指電極之 其中一個表面爲預先經該膠黏劑所覆被,且此時電極材內 部爲被該膠黏劑所含浸與否均可。 使用本發明之複合薄膜將S P E薄膜於電極上層合之 本紙張尺度適用中國國家標準(CNS>A4規格( 210X297公釐)-18 - (請先閲讀背面之注意事 4 項再填. 裝-- :寫本頁) 經濟部中央標準局員工消費合作社印製 482723 經濟部中央榡準局員工消費合作社印裝 A7 B7五、發明説明(16 ) 方法及製造s P E複合電極之方法,爲經過將本發明複合 薄膜中之基材薄膜與對面側之S P E面(或者於複合薄膜 爲具有覆蓋薄膜之情形中令正在覆蓋薄膜剝離,並除去覆 蓋薄膜之S P E面)令以接觸預先塗布硬化性膠黏劑之電 極而層合之工程,並令該膠黏劑硬化之工程,則可製造附 有基材薄膜之S P E薄層爲於電極上層合之S P E複合電 極。又,在令該膠黏劑硬化之工程中,或由硬化前至硬化 後爲止之間,或硬化後,經由在所層合之S P E複合電極 的上下面依壓榨和滾筒法加壓,可取得在電極上將均勻厚 度之S P E薄膜層合的S P E複合電極·,以其作爲本發明 之S P E薄膜之層合方法及S P E複合電極之製造方法爲 特佳。 又,使用本發明之複合薄膜,如上述製造附有基材薄 膜之S P E薄膜爲在電極上層合之S P E複合電極後,經 過由該S P E複合電極剝離基材薄膜之工程,其次(或者 正在剝離基材薄膜)在露出之S P E表面上將其他之構成 才料,例如其他之電極層合之工程,可製造S P E複合電 極。此情形亦以經由在前述S P E表面層合以其他構成材 料之工程中,由層合物之上下面依壓榨和滾筒法加壓,可 取得在電極上將均勻厚度之S P E薄膜層合的S P E複合 電極,作爲本發明S P E複合電極之製造方法爲特佳。在 依據上述方法製造S P E複合電極之方法中,加壓工程中 的加壓條件,爲同於前述複合薄膜製造中所說明之考慮方 法設定即可。 (請先閱讀背面之注意事 1T 項再填. 裝— :寫本頁) 訂 本紙張尺度適用中國國家標準(CNS)A4規格(21〇><297公釐)一 19 - 482723 A7 ___B7_ 五、發明説明(17 ) 於本發明S P E薄膜之層合方法(複合薄膜之製造方 法)及S P E複合電極之製造方法中,各工程之氛圍氣因 一般S P E多具有吸濕性,故至少於s P E液狀物和 S P E材料層表面露出期間,於乾燥空氣、乾燥氮氣、乾 燥氬氣等乾燥氛圍氣下等之將氛圍氣中之水分視需要而控 鄱之氛圍氣中進行爲較佳。又,在含聚合性化合物之 S P E液狀物表面露出期間,以在氮、氬等惰性氣體氛圍 氣下進行爲較佳。 又,各工程之溫度,若爲特別對S P E薄膜之性質無 不良影響之溫度即可,並無特別限定,但通常於常溫下進 行即可。但,在經由加熱聚合令聚合性化合物聚合之工程 中,則在引起視需要之聚合反應所必要程度爲止地進行加 熱。 〔實施例〕 以下,本發明依實施例而更詳細說明。 經濟部中央標準局員工消費合作社印袋 (請先閱讀背面之注意事項再填寫本頁) 尙,水合爲依費歇爾法(Karl Fischer method)測 定。薄膜厚度爲使用peac〇k公司製之指針式厚度計測定。 離子導電度爲依交流阻抗法測定。 又,使用相對由下述多官能化合物3 0重量%作爲 S P E液狀物。 〔化1〕 本紙張尺度適用中國國家標準(CNS>A4規格( 210X297公.慶)一 2〇 _ 482723 A7 B7 五、發明説明(18B (Please read the precautions on the back before filling out this page) -Installation-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) _ 13 _ Printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 482723 5 Description of the invention (11, NaSCN, KSCN, MgCl2, Mg (C1〇4) 2 '(CH3) 4NBF4, (CΗ 3) 4N Br, (C2H5) 4NCl〇4. (C 2H 5) 4N I , (C 3H 7) 4N B r, (n-C4H9) 4NC 1 0 4 ′ (n ~ 〇4Η〇) 4ΝΙ (n — CsHii) 4N I, etc. Among them, Lici 〇4, L i PF6 and other L Quaternary ammonium salts such as i salt, (C2H5) 4Nc 1 0 4 and the like are preferred. The compounding ratio of these electrolyte salts is generally from 0.1 to 70 parts by weight relative to 100 parts by weight of the polymerizable compound, and 1 to 70 parts by weight. 50 parts by weight is preferably 'particularly 1 to 30 parts by weight is suitable β and further' in the SPE of the present invention, and plasticizers, solvents, polymerization initiators, etc. may be blended as required. Plasticization Examples of the agent or solvent include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4,4-dimethyl-1, 3 -'- 1B, butyrolactone, ethylene carbonate, and propylene carbonate , Butene carbonate, tetrahydrophenophen, 3-methyltetrahydropheno code, third butyl ether, isobutyl ether, 1,2-dimethoxyethane, 1,2-diethyl Oxymethoxymethoxyethane, methyl diglyme, methyl triglyme, methyl tetraglyme, ethylglyme, ethyl diglyme Ethers, etc. These may be one type, and two or more types may be mixed for use. Examples of the polymerization initiator include free radical heating polymerization initiators such as azobisisobutylene, benzamidine peroxide, and the like. Free of benzophenone, etc. The paper size is applicable to Chinese National Standard (CNS) Α4 specifications (14----- l ----- ^ batch clothing-(Please read the precautions on the back before filling this page)- Order 4 · 482723 Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (12) " Basic photopolymerization initiators, proton acids such as cf3cooh, bf3, a 1 C 13 and other Lewis acids Cationic polymerization catalysts, anionic polymerization catalysts such as butyllithium, sodium alkoxide, lithium alkoxide, etc. The thickness of the SPE film layer in the present invention is usually 0 · 1 ~ 1000 / zm is preferably from 0.1 to 300 // m, and particularly from 0.1 to 50 // m. Furthermore, the substrate film used in the composite film of the present invention is required to be SPE when the composite film is formed. Or the wettability of the SPE liquid is good. In addition, the SPE composite electrode of the present invention is an SPE composite electrode having a substrate film on the surface. When used on the SPE surface on which the substrate film is peeled off and other constituent materials are laminated, it is necessary to make The peelability of the base film layer and the SPE film layer is good, that is, it must be peelable without damaging the shape of the SPE film. Therefore, it is particularly preferable to form a metal or metal oxide thin film layer (laminate) on the surface of the substrate film using the laminated SP. As the metal or metal oxide film, a film generally used for improving the gas barrier property of a plastic film can be used. Specific examples include metal foils or deposited films of aluminum, stainless steel, copper, and the like, and metal oxide deposited films such as silicon dioxide and aluminum oxide. Among them, aluminum foil, aluminum deposition film, silicon dioxide deposition film, and aluminum oxide deposition film are also preferable. The thickness of the film is not particularly limited, but in the case of a foil, it is 5 to 100 // m, and in the case of a deposited film, it is preferably 50 to 2000 Angstroms. (Please read the 4 notes on the back before filling. Pack-: Write this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm)-15-482723 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative A7 ___B7_ V. Description of the invention (13) The composite film of the present invention is (a) a composite film having a substrate film surface laminated with an SPE film layer structure, and (b) a metal or On the metal oxide film layer, a composite film having an SPE film layer structure and an SPE film layer having a composite film having any of the structures (a) and (b) are sandwiched and opposite to the substrate film Any one of the films having a laminated cover film structure may be used on the side surface, and any one may be appropriately selected depending on the application. In the method for manufacturing an SPE composite electrode, a composite film that is preferably used may be formed on a substrate film or a film of a substrate film attached with a metal or metal oxide film, for example, SPE liquid (or liquid SPE precursor materials) are laminated by any method such as coating, spraying, dipping, etc., and the polymerization reaction is caused if necessary, so that SPE is laminated in a substantially non-flowing state. In the case where the composite film has a cover film structure, (i) the SPE film layer can be laminated on the substrate film or the substrate film with a metal or metal oxide film layer according to the above method, The method of laminating the cover film, (ii) following the above method on the cover film, laminating the SPE to a substantially non-flowing state, then laminating the substrate film or the substrate film layer to which the metal or metal oxide film is added Combination method, or (iii) laminating the SPE liquid (or liquid SPE precursor material) between the base film or the base film of the additional metal or metal oxide film and the cover film, and causing as required The SPE is produced by any one of the methods of making the SPE into a substantially non-flowing state by a polymerization reaction. Here, the so-called "SPE liquid" or "liquid SPE precursor material" The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-16 1-(Please read the precautions on the back _ 4 > Fill in the items again .: Write this page) Binding and binding 482723 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ___B7 V. Invention Description (14) Materials ", not only at normal temperature (20 ° C), normal pressure Substances that have fluidity, and also include substances that have fluidity under normal pressure at a low pressure of 50 kg f / cm2 or less. However, the SPE liquid used in the lamination method according to the above (1) or (2) of the present invention is on a base film or a base film with a metal or metal oxide film layer attached to the film. In the case of lamination on the layer, it will not flow for 1 hour at normal temperature and pressure, but it will flow for a longer time, or it will flow under a pressure of 50 kg f / cm2 higher than normal pressure. Sex is better. In the case where SP is hygroscopic, for example, a cover film is preferably laminated using a pressure roller or the like. The cover film is not particularly limited, and a plastic film that can be used as the aforementioned substrate film can be appropriately used, and a film with better peelability from the SP film is preferably used. In the case where the composite film of the present invention is a composite film having a cover film, in the process manufactured according to the methods (i) to (iii) above, since the composite film can be laminated by pressing on the top and bottom of the SPE laminated film The thickness of the SPE film in the film is uniformly controlled, so it is better to apply pressure. The pressing method may be a common pressing method, but in the case of continuous production of a composite film, for example, a general pressure forming method such as a press roller can be used, and continuous production of a composite film is a feature of the present invention. One of the best implementation styles. The pressing pressure is not particularly limited as long as the pressure is usually used for lamination, but it may be performed under a pressure of 50 kg f / cm 2 or less used for ordinary low-pressure forming, and if S The thickness of the PE film can be controlled at the desired thickness. For example, even in the case of using a pressure roller, if you can provide the desired film thickness and apply the Chinese National Standard (CNS) A4 specification (210X297 mm) to the desired copy paper size -17-(Please read the back first Note 4 • Refilling and loading of items —: Write this page) Order 482723 A7 B7 V. Description of the invention (15) There is no particular limitation on the pressure of the film properties without adverse effects. For example, the roller pressure is 1 ~ 30kg The range of f / cm2 is more preferable, and the range of 5 to 10 kg f / cm2 is particularly preferable. Examples of the electrode used in the present invention include lithium metals, lithium / aluminum alloys, lithium / chromium alloys, lithium / antimony alloys, and the like as examples of the negative electrode. In the case where Li ions are used as a carrier, carbon can be cited. Materials, etc. Examples of the positive electrode include metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, metal sulfides such as molybdenum sulfide, titanium sulfide, and vanadium sulfide, polyaniline, polyacetylene, and derivatives thereof. , Conductive polymers such as polyparaphenylene and its derivatives, polypyrrole and its derivatives, polyphenylene and its derivatives, natural black lead, artificial black lead, gas phase black lead, petroleum coke, Carbon materials such as coke, lead fluoride, pitch-based carbon, and polyacetylene. As the hardening adhesive used in the present invention, the aforementioned polymerizable compound or a liquid mixture containing the same can be used. In particular, a liquid mixture which may only have the same composition as the SPPE film, such as the above-mentioned SPPE liquid, is particularly excellent in terms of the homogeneity of the SPPE film on the electrode, but is not limited thereto. The method for applying the adhesive to the electrode can be easily performed by using a known method such as coating, spraying, or dipping on the electrode. In the present invention, the "electrode pre-coated with a hardening adhesive" means that one surface of the electrode is covered with the adhesive in advance, and the inside of the electrode material is impregnated with the adhesive. Or not. The paper size of the SPE film laminated on the electrode using the composite film of the present invention is applicable to the Chinese national standard (CNS > A4 specification (210X297 mm) -18-(Please read the 4 notes on the back before filling.) (Write this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 482723 Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economics A7 B7 V. Description of the Invention (16) Method and method of manufacturing s PE composite electrodes Invent the composite film in the composite film and the SPE surface on the opposite side (or in the case where the composite film has a cover film, peel the cover film and remove the SPE surface of the cover film) to apply a hardening adhesive in advance The process of laminating electrodes and hardening the adhesive can produce SPE composite electrodes with a thin film of a substrate film laminated on the electrodes. In addition, the hardening of the adhesive In the process, from before hardening to after hardening, or after hardening, pressing on the top and bottom of the laminated SPE composite electrode by pressing and roller method can obtain the electrode An SPE composite electrode laminated with an SPE film of uniform thickness is particularly preferred as the method of laminating the SPE film of the present invention and the method of manufacturing the SPE composite electrode. In addition, the composite film of the present invention is used to manufacture the The SPE film with a base film is an SPE composite electrode laminated on the electrode, and after the process of peeling the base film from the SPE composite electrode, secondly (or the base film is being peeled off), other components are formed on the exposed SPE surface It is expected that, for example, other electrode lamination projects, SPE composite electrodes can be manufactured. In this case, in the process of laminating other constituent materials on the aforementioned SPE surface, the laminates are added by pressing and rollers above and below the laminate. The SPE composite electrode obtained by laminating an SPE thin film of uniform thickness on the electrode is particularly preferable as the manufacturing method of the SPE composite electrode of the present invention. In the method of manufacturing the SPE composite electrode according to the above method, The pressing conditions can be set in the same way as the method described in the production of the composite film. (Please read the note on the back first Refill the 1T item. Packing —: Write this page) The size of the paper used in the book is applicable to the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) 1 19-482723 A7 ___B7_ V. Description of the invention (17) In the laminating method of SPE film (manufacturing method of composite film) and the manufacturing method of SPE composite electrode of the present invention, the atmosphere of each project is generally hygroscopic because of SPE, so it is at least less than s PE liquid and SPE material layer. During the surface exposure, it is better to carry out the moisture in the atmosphere under a dry atmosphere such as dry air, dry nitrogen, dry argon, etc., if necessary, to control the moisture content. In addition, it is preferable to carry out under the atmosphere of an inert gas such as nitrogen or argon while the surface of the SP material containing the polymerizable compound is exposed. The temperature of each process is not particularly limited as long as it does not adversely affect the properties of the SPE film, but it is usually performed at normal temperature. However, in the process of polymerizing a polymerizable compound by heating polymerization, heating is performed to the extent necessary to cause a desired polymerization reaction. [Examples] Hereinafter, the present invention will be described in more detail according to examples. Printed bags for employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page)), hydration is measured according to the Karl Fischer method. The thickness of the film was measured using a pointer thickness meter manufactured by Peacok Corporation. Ionic conductivity was measured according to the AC impedance method. In addition, 30% by weight of the following polyfunctional compound was used as a liquid liquid of SPE. [Chemical 1] This paper size applies Chinese national standard (CNS > A4 specification (210X297). Celebrity) 1 20 _ 482723 A7 B7 V. Description of the invention (18
(式中,m=25,R爲甲基)(Where m = 25, R is methyl)
LiBF4(電解質)1〇重量%、碳酸·乙烯酯(增塑劑 )3 0重量%及碳酸丙烯酯(增塑劑)3 0重量%所組成 之混合物1 0 0重量份,添加Irgacure5 0 0 (Ciba Geigy公司製、聚合引發劑)1 · 5重量份作爲黏度 2 〇 0 c ρ之混合溶液。 使用下述薄膜作爲基材。 PET — 1 :聚酯(PET)薄膜(厚度12//m) ONg :雙軸延伸耐龍(一 6,6)薄膜(厚度15 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裳 β Ρ Ε Τ — 2 Ρ Ε Τ — 3 Ρ Ε Τ — 4 :於Ρ ΕΤ_ 1上澱積氧化鋁(厚度 1 0 0 0 A )之物質 ••於PET - 1上澱積二氧化矽(厚度 1000A)之物質 :於PET - 1上澱積鋁(厚度2 00A )之物質 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)一 21 一 482723 A7 B7 五、發明説明(19 ) 使用厚度5 0 //m之雙軸延伸聚丙烯薄膜(以下稱爲 「OPP」)或高密度聚乙烯薄膜(以下稱爲「PE」) 作爲覆蓋薄膜。 使用在厚度5 0 //m之鋁箔上塗布形成厚度7 0 鈷酸鋰之物質作爲電極。 實施例1 於露點一 50°C之大氣中,在PET — 1上將SPE 液狀物使用刮刀法之塗布機予以薄層塗布。其次,在氮氛 圍氣中照射紫外線令聚合性化合物(上述之多官能性化合 物)聚合交聯後,將〇P P使用壓料滾筒於S P E面重疊 層合後,於溫度2 0°C,濕度5 RH%之大氣中,捲取 SPE薄膜層(厚度45//m)之層合體(複合薄膜)。 將此層合層之S P E薄膜之在2 5 °C下的離子導電度 ,依公知之交流阻抗法測定時,爲2 X 1 0—3S/cm。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 其次,於露點一 5 0°C之大叙中將上述S P E液狀物 於表面塗布之電極的塗布面上,一邊令所得層合體(複合 薄膜)之覆蓋薄膜剝離,一邊使用壓料滾筒將層合體之 S P E面層合至電極面後,於溫度2 0°C,濕度5 RH% 之大氣中透過P E T薄膜地照射紫外線聚合(交聯)膠黏 電、極後,於溫度20 °C、濕度5RH%之大氣中捲取層合 體(SPE複合電極)。LiBF4 (electrolyte) 10% by weight, carbonate / vinyl carbonate (plasticizer) 30% by weight, and propylene carbonate (plasticizer) 30% by weight 100% by weight of the mixture, with Irgacure50 0 0 ( Ciba Geigy company, polymerization initiator) 1.5 parts by weight as a mixed solution with a viscosity of 2000 c ρ. The following films were used as substrates. PET — 1: Polyester (PET) film (thickness 12 // m) ONg: biaxially stretched Nylon (1-6) film (thickness 15 (Please read the precautions on the back before filling this page) Central of the Ministry of Economy Standards Bureau Consumer Cooperative Cooperative Print β Ρ Ε Τ — 2 Ρ Ε Τ — 3 Ρ Ε Τ — 4: Alumina (thickness 1 00 0 A) deposited on Ρ ET_ 1 •• on PET-1 Substances that deposit silicon dioxide (thickness 1000A): Substances that deposit aluminum (thickness 200A) on PET-1. The paper dimensions are applicable to China National Standard (CNS) A4 specifications (210X297 mm)-21-482723 A7 B7 5. Description of the invention (19) Use a biaxially stretched polypropylene film (hereinafter referred to as "OPP") or a high-density polyethylene film (hereinafter referred to as "PE") as a cover film with a thickness of 50 / m. An aluminum foil with a thickness of 50m / m is coated to form a material with a thickness of 70m lithium cobaltate as an electrode. Example 1 In an atmosphere with a dew point of 50 ° C, a SPE liquid substance is applied on a PET-1 coating machine using a doctor blade method. Apply a thin layer. Second, irradiate ultraviolet rays in a nitrogen atmosphere to make the polymerizable compound (Polymer compound) After polymerization and cross-linking, OPP is laminated on the SPE surface using a pressure roller, and then the SPE film layer (thickness 45 // m) is rolled up in the atmosphere at a temperature of 20 ° C and a humidity of 5 RH%. The laminated body (composite film). The ionic conductivity of the laminated SPE film at 25 ° C was 2 X 1 0-3 S / cm when measured by the well-known AC impedance method. Printed by the Consumer Bureau of Standards Bureau (please read the precautions on the back before filling out this page) Second, apply the above SPE liquid to the surface of the electrode coated on the surface in the dew point at 50 ° C. The cover film of the obtained laminate (composite film) was peeled off, and the SPE surface of the laminate was laminated to the electrode surface using a pressure roller, and then irradiated through the PET film in an atmosphere at a temperature of 20 ° C and a humidity of 5 RH%. After the ultraviolet polymerization (cross-linking) glued the electrode, the laminate (SPE composite electrode) was rolled up in the atmosphere at a temperature of 20 ° C and a humidity of 5RH%.
所得層合體(S P E複合電極)之S P E薄膜厚度爲 在5 0 em± 20%之範圍中具有薄的均勻性。在PET 本紙張尺度適用中國國家標準(CNS>A4規格( 210X297公釐)_ 22 _ 482723 A7 B7 五、發明説明(2Q ) 薄膜之剝離良好下’可不傷及S P E薄膜面地剝離。又, S P E複合電極之S P E薄膜的含水量亦爲2 〇 〇 p pm 以下。 實施例2 除了基材薄膜以ON y取代以外,同實施例1處理取 得S P E薄膜(複合薄膜)及s P E複合電極。所得之 S P E複合電極的S P E薄膜厚度及分布、剝離及含水量 爲與實施例1同等。 實施例3 除了基材薄膜以PET — 2取代,且不使用opp覆 蓋薄膜以外,同實施例1處理取得S P E薄膜(複合薄膜 )及SPE複合電極。所得之SPE複合電極的SPE薄 膜厚度爲在3 0 //m± 1 〇%之範圍中爲薄且均勻性優異 之薄膜。P E T薄膜之剝離亦極爲良好且可輕易剝離。又 ’ S P E薄膜之含水量爲5 0 0 p pm以下。 實施例4 除了基材薄膜以P E T — 3取代、使用p E作爲覆蓋 薄膜以外,同實施例1處理取得S P E薄膜(複合薄膜) 及S P E複合電極,所得之S P E複合電極的s P E薄膜 厚度爲在3 0 //m± 2 0%之範圍中爲薄且具均勻性。 P T薄膜之剝離及S P E薄膜之含水量爲與實施例i同等 本紙張尺度適用中國國家標隼(CNS ) A4規格(210X297公釐)〜23 (請先閱讀背面之注意事 裝II 一寫本頁) 、11 經濟部中央標隼局員工消費合作社印製 482723 A7 B7 五、發明説明(21 ) ^ — 0 實施例5 (請先閲讀背面之注意事項再填寫本頁) 除了基材以P E T — 4取代以外,同實施例1處理取 得S P E薄膜(複合薄膜)及3 p e複合電極。所得之 S P E複合電極的S P E薄膜厚度及分布、剝離及含水量 爲與實施例4同等。 實施例Θ 將實施例1所得之S P E複合電極的P E T薄膜,於 露點溫度一 50 °C之氬氛圍氣(20 °C)中剝離,且立即 將由剝離後之S P E/鈷酸鋰/鋁箔所構成之S P E複合 電極’於1M之L i B F4電解液(碳酸二乙酯/碳酸乙 烯酯(重量比1 : 1 )混合溶劑)中浸漬1小時後,於 經濟部中央標準局貝工消費合作杜印製 S P E複合電極之S P E面上,令預先層合銅箔之鋰箔( 其他之構成材料)的鋰面予以層合,並由層合體之上下面 加壓製作成由S P E複合電極(銅/鋰/S P E/鈷酸鋰 /鋁)所構成之二次電池元件,並將端部以環氧樹脂予以 封阻,製作成二次電池。 此電池即使爲在動作電壓2·0〜4·2V且電流密 度0 · 3mA/cm2下重覆15 0次充放電後,亦維持 初容量之50%以上。 比較例1 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-24 - 482723 經濟部中央標準局員工消費合作社印製The SPE film thickness of the obtained laminate (SPE composite electrode) was thin and uniform in the range of 50 em ± 20%. Chinese paper standard (CNS > A4 specification (210X297 mm) _ 22 _ 482723 A7 B7 applies to PET paper size. V. Description of the invention (2Q) The film is peeled off well without peeling the surface of the SPE film. Also, SPE The water content of the SPE film of the composite electrode is also less than 2000 p pm. Example 2 The SPE film (composite film) and the s PE composite electrode were obtained in the same manner as in Example 1 except that the substrate film was replaced with ON y. The SPE film thickness, distribution, peeling, and moisture content of the SPE composite electrode were the same as those in Example 1. Example 3 Except that the substrate film was replaced by PET-2 and no opp cover film was used, the SPE film was treated in the same manner as in Example 1 to obtain an SPE film. (Composite film) and SPE composite electrode. The SPE film thickness of the obtained SPE composite electrode is a thin film with excellent uniformity in the range of 30 // m ± 10%. The peeling of the PET film is also very good and can be peeled off. Easily peeled off. Also, the water content of the SPE film is below 500 p pm. Example 4 The same as Example 1 except that the base film is replaced by PET-3 and p E is used as the cover film. SPE film (composite film) and SPE composite electrode were obtained, and the s PE film thickness of the obtained SPE composite electrode was thin and uniform in the range of 30 / m + 20%. Peeling of PT film and SPE film The water content is the same as in Example i. The paper size is applicable to the Chinese National Standard (CNS) A4 size (210X297 mm) ~ 23 (Please read the precautions on the back II on the first page), 11 Central Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 482723 A7 B7 V. Description of the Invention (21) ^ — 0 Example 5 (Please read the precautions on the back before filling this page) Except that the substrate is replaced by PET-4, the same as Example 1 The SPE film (composite film) and the 3 pe composite electrode were obtained through processing. The thickness, distribution, peeling, and moisture content of the SPE film of the obtained SPE composite electrode were the same as those in Example 4. Example Θ The SPE composite electrode obtained in Example 1 was The PET film was peeled in an argon atmosphere (20 ° C) with a dew point of 50 ° C, and the SPE composite electrode composed of the peeled SPE / lithium cobaltate / aluminum foil was immediately electrolyzed at 1 M of L i B F4 Liquid (carbon After dipping for 1 hour in diethyl acid / ethylene carbonate (weight ratio of 1: 1) mixed solvent, the SPE surface of the SPE composite electrode printed by SPE Composite Co., Ltd. of the Central Standards Bureau of the Ministry of Economic Affairs was printed with copper in advance. The lithium surface of the lithium foil (other constituent materials) of the foil is laminated, and the laminate is pressed from the top and bottom of the laminate to form a secondary SPE electrode (copper / lithium / SPE / lithium cobaltate / aluminum). The battery element was sealed with an epoxy resin at the end to form a secondary battery. This battery maintains more than 50% of its initial capacity even after it has been repeatedly charged and discharged 150 times at an operating voltage of 2.0-4.2V and a current density of 0.3 mA / cm2. Comparative Example 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -24-482723 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
A7 ____ B7五、發明説明(22 ) 將電極於S P E液狀物中露點一 5 0°C之大氣中浸漬 ,並將壓料滾筒將多餘之液狀物除去後,以刮刀方式之塗 布機所儘可能薄地塗層,並在氮氛圍氣中照射紫外線令其 聚合(交聯)後,於溫度2 0°C、濕度5RH%之大氣中 捲取層合體。雖然儘可能薄地塗布,但厚度及其分布以 2 0 0 wm± 2 0%爲限度。又,立即捲取後之層合體中 S P E中的含水量爲1 〇 〇 〇 p pm。 〔發明之效果〕 本發明之層合方法因可依簡易的方法薄膜化,且薄膜 化後之操作亦比較容易,故可用於作爲電池用材料之製造 方法。 依據本發明之層合方法,可將大面積之S P E薄膜以 複合薄膜形式依簡便的方法連續成形。 又,依據本發明之複合薄膜,可將離子導電度爲均質 且膜厚爲均勻之S P E薄膜於保存安定性優異之狀態下操 作並保存。 再者,使用本發明之複合薄膜,可取得離子導電度爲 均質且膜厚爲均勻之S P E層,以S P E層與電極之電化 性接觸爲極良好的,即以對電極上均質密黏的狀態下層合 之SPE複合電極。 特別地,依據本發明之製造方法,可取得離子導電度 爲均質且膜厚爲均勻之S P E層對電極上以均質密黏之狀 態下層合之大面積的S P E複合電極,且經由將本S P E (請先閲讀背面之注意事 4 ▼項再填. 裝— >寫本1) - 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)-25 - 482723 A7 B7 五、發明説明(23 ) — ^ 複合電極以所欲大小之多數均質電極切斷供使用,於製造 品質均質之多數電化性裝置方面爲極有利。 又,經由使用本發明之在S P E層上下兩面令基材薄 膜、金屬或金屬氧化物薄膜層、覆蓋薄膜或電極等予以層 合之複合薄膜,於電極上形成S P E薄膜層之工程中,由 於而不需特別嚴格進行用於控制水分之工程的氛圍氣控制 ,具有令層合工程變爲簡易之優點。 (請先閲讀背面之注意事項再填寫本頁) -裝. 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格( 210X297公釐)-26 -A7 ____ B7 V. Description of the invention (22) The electrode is immersed in the SPE liquid with a dew point of 50 ° C in the atmosphere, and the excess liquid is removed by the pressure roller, and then coated by a doctor blade. After coating as thin as possible and irradiating ultraviolet rays in a nitrogen atmosphere to polymerize (crosslink) it, the laminate is rolled up in an atmosphere at a temperature of 20 ° C and a humidity of 5RH%. Although coated as thin as possible, the thickness and its distribution are limited to 200 wm ± 20%. Moreover, the water content in SPE in the laminate immediately after winding was 1000 ppm. [Effects of the Invention] Since the lamination method of the present invention can be made into a thin film by a simple method, and the operation after the thinning is relatively easy, it can be used as a method for manufacturing a battery material. According to the laminating method of the present invention, a large area SP PE film can be continuously formed in the form of a composite film by a simple method. In addition, according to the composite thin film of the present invention, an SPPE thin film having a uniform ionic conductivity and a uniform film thickness can be operated and stored in a state of excellent storage stability. Furthermore, using the composite film of the present invention, an SPE layer with uniform ionic conductivity and uniform film thickness can be obtained, and the electrochemical contact between the SPE layer and the electrode is excellent, that is, a state of homogeneous and dense adhesion on the electrode The underlying laminated SPE composite electrode. In particular, according to the manufacturing method of the present invention, a large-area SPE composite electrode laminated with a homogeneous and densely adhered SPE layer counter electrode having a uniform ion conductivity and a uniform film thickness can be obtained, and the present SPE ( Please read the note 4 on the back first and then fill in the items. Packing — > Manuscript 1)-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -25-482723 A7 B7 V. Description of the invention (23 ) — ^ The composite electrode is cut off for use with most homogeneous electrodes of a desired size, which is extremely advantageous in manufacturing most electrochemical devices with uniform quality. In addition, the process of forming an SPE film layer on an electrode by using a composite film in which a substrate film, a metal or metal oxide film layer, a cover film, or an electrode is laminated on the upper and lower sides of the SPE layer according to the present invention, It is not necessary to strictly control the atmosphere of the project for controlling moisture, and has the advantage of making the lamination process simple. (Please read the notes on the back before filling out this page)-Binding. Order Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm) -26-
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW086103536A TW482723B (en) | 1996-03-21 | 1997-03-20 | Method for laminating solid polymer electrolyte film |
Country Status (2)
Country | Link |
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TW (1) | TW482723B (en) |
WO (1) | WO1997035350A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1560019B1 (en) * | 2004-01-28 | 2008-01-09 | Mettler-Toledo AG | Polymeric electrolyte, half-cell for electrochemical measurements and its use |
EP2063478A4 (en) * | 2006-08-25 | 2010-08-04 | Sumitomo Chemical Co | Polymer electrolyte membrane, laminate thereof, and their production methods |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US4935317A (en) * | 1989-06-21 | 1990-06-19 | Mhb Joint Venture | Method for producing solid state electrochemical laminar cell utilizing cathode rolling step |
US5470357A (en) * | 1993-03-05 | 1995-11-28 | Bell Communications Research, Inc. | Method of making a laminated lithium-ion rechargeable battery cell |
US5376210A (en) * | 1994-03-23 | 1994-12-27 | Hydro-Quebec | Peeling aids for LPB electrolytes and method of use |
US5536278A (en) * | 1994-03-23 | 1996-07-16 | Hydro-Quebec | Process for assembling LPB batteries |
US5498489A (en) * | 1995-04-14 | 1996-03-12 | Dasgupta; Sankar | Rechargeable non-aqueous lithium battery having stacked electrochemical cells |
-
1997
- 1997-03-20 TW TW086103536A patent/TW482723B/en not_active IP Right Cessation
- 1997-03-21 WO PCT/JP1997/000945 patent/WO1997035350A1/en active Application Filing
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WO1997035350A1 (en) | 1997-09-25 |
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