1330902 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關非水電解液電池，特別是製造鋰電池使 用之電極用黏合劑，使用其之電極去極化合劑、電極及使 用其之非水電解液電池。 【先前技術】 近年電子技術發展驚人，各種機器可小型輕量化。與 ·· 此電子機器之小型輕量化相結合，其電源之電池之小型輕 量化之要求非常大。作爲小容積及重量，可得到更大能量 之電池，爲使用鋰之非水系二次電池，主要可使用於行動 電話或個人電腦、錄影機等之家庭用小型電子機器之電源 〇 鋰電池用電極結構體係由活性物質、導電劑以黏合劑 保持集電物之狀態使用，正極活性物質爲鋰複合氧化物， 負極活性物質爲碳元素材料，又爲結合此等活性物質之黏 φφ 合劑’主要使用偏氟乙烯系聚合物。 曰本特開平11_329443號公報以不具官能基之偏氟乙 稀系聚合物與纖維素系聚合物之混合物爲例示，其結合性 不充分’亦未完全考慮其安全性。 但是’機器之小型輕量化與增長電池持續時間之市場 要求’鋰電池更要高容量化，與向來品比較，由於電池內 部裝入電極等之增加容量之反面，電池內部發生短路時過 大之電流流向局部’招致電池急激的溫度上昇，引起電池 -5- (2) 1330902 破裂、發煙 '發火等之危險狀態，增大危險性的問題 【發明內容】 〔發明之揭示〕 因此’本發明主要之課題爲提供維持非水解液電池必 要之高容量’且提高其性能安定性及內部短路時之安全性 之非電解液電池之電極用黏合劑組成物，並使用其之電極1330902 (1) Field of the Invention [Technical Field] The present invention relates to a non-aqueous electrolyte battery, particularly an electrode adhesive for use in a lithium battery, an electrode depolarizing mixture, an electrode thereof, and a use thereof Non-aqueous electrolyte battery. [Prior Art] In recent years, the development of electronic technology has been amazing, and various machines can be compact and lightweight. In combination with the small size and light weight of this electronic device, the battery for power supply is very small and lightweight. A battery that can obtain more energy as a small volume and weight. It is a non-aqueous secondary battery using lithium. It can be used as a power source for small-sized electronic devices for mobile phones, personal computers, video recorders, etc. The structural system is used in the state in which the active material and the conductive agent hold the current collector with the binder, the positive electrode active material is a lithium composite oxide, the negative electrode active material is a carbon element material, and the adhesive φφ mixture which is combined with the active materials is mainly used. A vinylidene fluoride polymer. Japanese Laid-Open Patent Publication No. Hei 11-329443 is exemplified by a mixture of a vinylidene-based polymer having no functional group and a cellulose-based polymer, and its bonding property is insufficient. The safety is not fully considered. However, 'the market demand for small and light weight of the machine and the growth of the battery life' requires a higher capacity of the lithium battery. Compared with the conventional product, the battery is internally overloaded with a large amount of current due to the increased capacity of the internal electrode. The flow to the local 'causes the temperature rise of the battery, causing the dangerous state of the battery-5-(2) 1330902 rupture, fuming, igniting, etc., and increasing the risk [invention] [disclosure of the invention] The problem is to provide an electrode binder composition for a non-electrolyte battery that maintains the high capacity required for a non-hydrolyzate battery and improves the safety of the performance and internal short-circuit, and uses the electrode thereof.
及非水電解液電池。 本發明係爲解決上述之課題，其有關之第1觀點，爲 ίζΕ供使用具備可吸藏·放出鍾之正極及負極之作爲非水電 解液電池之正極及/或負極結合劑之非水電解液電池電極 用黏合劑組成物。 又’有關本發明之另外觀點，爲提供含上述黏合劑組 成物與電極活性物質之電極去極化合劑、集電物上具有上 述電極去極化合劑層之電極及正極及負極之至少一方爲含 該電極之非水電解液電池。 提高上述黏合劑組成物，維持非水電解液電池必要之 高容量，且其性能安定性及內部短路時之安全性之理由並 未明確，可考慮爲含官能基偏氟乙烯之聚合物中之羧基或 環氧丙基及極性聚合物之羥基及羰基，集電物表面或電極 活性物質表面之羥基與氫元素結合所形成之黏合劑提高接 合性，同時電極活性物質表面形成遮斷非水電解液之穿透 ，鋰離子之選擇透過性皮膜，抑制電極活性物質表面充放 電時電解液與鋰離子之反應合成鋰化合物之生成，充電之 -6- (4) 1330902 系聚合物爲理想。此等之含官能基偏氟乙烯系聚合物可由 公知之懸浮聚合、乳化聚合 '溶液聚合等之方法而得。又 ，官能基之導入方法可由偏氟乙烯系聚合物以鹼加熱脫氟 酸後，以有機酸或氧化劑處理，得到官能基聚合物。And non-aqueous electrolyte batteries. In order to solve the above-mentioned problems, the present invention provides a non-aqueous electrolysis using a positive electrode and/or a negative electrode binder as a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing a clock. A binder composition for a liquid battery electrode. Further, another aspect of the present invention is to provide an electrode depolarization mixture containing the binder composition and the electrode active material, an electrode having the electrode depolarization mixture layer on the current collector, and at least one of a positive electrode and a negative electrode. A non-aqueous electrolyte battery containing the electrode. The reason for improving the above-mentioned binder composition, maintaining the high capacity necessary for the non-aqueous electrolyte battery, and the safety of the performance and the safety of the internal short-circuit is not clear, and may be considered as a polymer containing a functional group of vinylidene fluoride. The carboxyl group or the epoxy group and the hydroxyl group and the carbonyl group of the polar polymer, the binder formed on the surface of the collector or the surface of the electrode active material and the hydrogen element are combined to improve the bonding property, and the surface of the electrode active material forms a non-aqueous electrolysis. The penetration of the liquid and the selection of the lithium ion permeable membrane suppress the formation of the lithium compound by the reaction of the electrolyte with the lithium ion during the charge and discharge of the surface of the electrode active material, and it is preferable to charge the -6-(4) 1330902 polymer. These functional group-containing vinylidene fluoride-based polymers can be obtained by a known suspension polymerization, emulsion polymerization, solution polymerization or the like. Further, the method of introducing a functional group may be carried out by heating a defluorinated acid with a base of a vinylidene fluoride-based polymer, followed by treatment with an organic acid or an oxidizing agent to obtain a functional group polymer.
含官能基偏氟乙烯系聚合物之分子量，依日本特開平 9-2 8 902 3號公報揭示，其標準爲對數比濃粘度（樹脂4g 以1 L之Ν,Ν-三甲基甲醯胺溶解之溶液於30°C之對數濃度 )爲 0.8〜20dl/g，理想爲 1.0〜20dl/g，更理想爲 1.0〜15 dl/g，再理想爲1 .2〜1 5dl/g者爲理想範圍。偏氟乙烯系聚 合物之對數比濃粘度低於上述範圍時，電極去極化合劑之 粘度過低塗工有困難，超過上述範圍時對有機溶劑之溶解 有困難不適當。 ·· 有關本發明所使用之極性聚合物係含具有羥基之聚合 物與具有羰基之聚合物。具有羥基之聚合物例如包含乙烯 乙烯基醇共聚物、纖維素系聚合物、乙烯基苯酚系聚合物 。又，具有羰基之聚合物爲聚丙烯酸系聚合物，具體的包 含如聚丙烯酸、聚丙烯酸交聯聚合物及此等之金屬鹽類。 又聚乙烯基吡咯烷酮亦適用於極性聚合物。 因應必要，含官能基偏氟乙烯系聚合物、具有羥基或 羰基之極性聚合物之外，可添加偏氟乙烯之單獨聚合物' 偏氟乙烯與氟乙烯、三氟乙烯、氯化三氟乙烯、四氟乙烯 、六氟丙烯等之可與偏氟乙烯共聚合之單體之共聚物等。 有關本發明含官能基偏氟乙烯系共聚物與極性聚合物 之混合比率，含官能基偏氟乙烯系共聚物爲1 〇〜99重量％ -8- (6) 1330902 以使用0.1〜30重量份，特別以使用0.5〜20重量份之比例 爲理想。 Χ ’黏合劑組成物預先以有機溶劑溶解使用時，溶劑 爲單獨或二種以上混合，每1 00重量份溶劑，黏合劑組成 物爲0_]〜30重量份，特別以1〜20重量份之比例爲理想。The molecular weight of the functionally-containing vinylidene fluoride-based polymer is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-2 8 902 3, the standard of which is a logarithmic viscosity (resin 4 g of L, Ν-trimethylformamide) The dissolved solution has a logarithmic concentration at 30 ° C of 0.8 to 20 dl / g, preferably 1.0 to 20 dl / g, more preferably 1.0 to 15 dl / g, and more preferably 1.2 to 15 dl / g. range. When the logarithmic reduced viscosity of the vinylidene fluoride-based polymer is less than the above range, the viscosity of the electrode depolarizing mixture is too low to coat, and when it exceeds the above range, it is difficult to dissolve the organic solvent. The polar polymer used in the present invention contains a polymer having a hydroxyl group and a polymer having a carbonyl group. The polymer having a hydroxyl group includes, for example, an ethylene vinyl alcohol copolymer, a cellulose polymer, or a vinyl phenol polymer. Further, the polymer having a carbonyl group is a polyacrylic polymer, and specifically contains, for example, polyacrylic acid, a polyacrylic acid crosslinked polymer, and the like. Polyvinylpyrrolidone is also suitable for polar polymers. If necessary, a functional polymer based vinylidene fluoride-based polymer, a polar polymer having a hydroxyl group or a carbonyl group, may be added as a separate polymer of vinylidene fluoride's vinylidene fluoride and vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene And a copolymer of a monomer copolymerizable with vinylidene fluoride such as tetrafluoroethylene or hexafluoropropylene. The mixing ratio of the functional group-containing vinylidene fluoride copolymer to the polar polymer of the present invention, the functional group-containing vinylidene fluoride copolymer is 1 〇 to 99% by weight -8-(6) 1330902 to be used in an amount of 0.1 to 30 parts by weight. It is particularly preferable to use a ratio of 0.5 to 20 parts by weight. Χ When the binder composition is dissolved in an organic solvent in advance, the solvent is used alone or in combination of two or more kinds, and the binder composition is 0 to] to 30 parts by weight, particularly 1 to 20 parts by weight, per 100 parts by weight of the solvent. The ratio is ideal.
使用於由黏合劑組成物、粉末電極材料、有機溶劑所 成之去極化合劑之混合裝置，可使用均質機或多軸衛星方 式之分散 混合 混練機或乳化機。此等無特別限制。 以上述方法調製之去極化合劑泥漿係均勻分散 混合 之粉末電極材料、黏合劑組成物，具良好之塗覆性，塗覆 方令集電物。塗覆之方法以公知者即可，其中亦以使用括刀 法爲理想。集電物上之去極化合劑以5 0〜1 7 0艺乾燥溶劑 ’因應必要以熱壓步驟形成非水系二次電池用之電極結構 體 本發明之黏合劑組成物及電極去極化合劑，至少可使 用於正極及負極一方之形成，以使用於負極之一方爲理想 φφ 。此係構成負極之粉末電極材料要求較高接合性之黏合劑 ，本發明之黏合劑組成物特別適合使用。 【實施方式】 以下以實施例及比較例更具體的說明本發明。 (含官能基偏氟乙烯系共聚物Α之製造） 內容積2L之加壓器投入離子交換水1075g，甲基纖 維素〇.4g，偏氟乙烯單體（VDF) 398g，馬來酸單甲基酯 -10- (7) (7)1330902 (MMM) 2g，異丙基過氧化二碳酸酯 2.5g，醋酸乙酯5g ，於2 8 °C進行2 7小時懸浮聚合。 聚合終了後，將聚合物泥漿脫水，經水洗，脫水後於 8 0 °C乾燥 2 0小時，得到收率 8 9 %，對數比濃粘度爲 1 . 1 dl/g之本發明之含官能基偏氟乙烯系聚合物A。 (含官能基偏氟乙烯系聚合物B之製造） 內容積2L之加壓器投入離子交換水1 0 7 5 g，甲基纖 維素〇.4g，偏氟乙烯單體（VDF) 400g，二甲基環氧丙基 甲基丙烯酸酯（2M-GMA ) 3g，異丙基過氧化二碳酸酯 2.5 g，醋酸乙酯 5 g，於2 8 t進行2 5小時懸浮聚合。 聚合終了後，將聚合物泥漿脫水，水洗，脫水後於 80 °C乾燥 20小時，得到收率 90%，對數比濃粘度爲 2.4 dl/g之本發明之含官能基偏氟乙烯系聚合物B。 (偏氟乙烯系聚合物C之製造） ·_ 內容積2L之加壓器投入離子交換水1 0 7 5 g，甲基纖 維素〇.4g，偏氟乙烯單體（VDF) 400g，異丙基過氧化二 碳酸酯2.5g，醋酸乙酯 5g，於26°C進行20小時懸浮聚 聚合終了後，將聚合物泥漿脫水，水洗，脫水後於 8 0 °C乾燥 2 0小時，得到收率 9 1 %，對數比濃粘度爲 1.1 dl/g之本發明之偏氟乙烯系聚合物C (聚偏氟乙烯）。 -11 - (8) (8)1330902 〈實施例】〉 (正極之製造） 於琥珀酸鋰（「SELSEED C-5」，日本化學工業製） 94重量份，偏氟乙烯聚合物C3重量份，碳黑3重量份添 加N·甲基·2_吡咯烷酮（NMP) 43重量份，混合調製正極 用極去極化合劑。得到之電極去極化合劑於1 0 V m之鋁 箔上，均勻塗覆得到乾燥後約爲100/zm之膜厚，於130 °C乾燥 25分鐘，得到正極結構體（活性物質量： 29 1 g/m2)。 (負極之製造） 相對於含官能基偏氟乙烯系聚合物A 11重量份，乙 烯乙烯基醇共聚物（EVOH，日本 KURARE公司製「£卩-G 1 5 6 B」’乙烯莫耳含量4 7 % ) 1重量份，混合平均粒子 徑30/im之球狀天然石墨粉末（中國大陸製）88重量份 ’及NMP 67重量份，調製本發明之負極電極去極化合劑 組成物A。得到之電極去極化合劑於8 // m之鋁銅上，均 勻塗覆得到乾燥後約爲lOOym之膜厚，於130t乾燥25 分鐘’得到負極結構體A (活性物質量：163 g/m2)。 (有關電極結構體電極去極化合劑層之剝離強度測定方法） 於集電物塗覆乾燥之負極結構體作爲試料，電極去極 化合劑層由集電物剝離強度，依ns K 6854爲準測定 1 80°剝離試驗。 -12 - (9) (9)1330902 (剝離強度之測定） 測定上述負極結構體A之剝離強度結果爲3 8gf/ (電池之製作） 切取48mmx48mm安裝充放電用簧片之正極結構體 ，及切取50mmx50mm安裝充放電用簧片之負極結構體 A’電極面相對介入52mmx52mm厚度2〇ym之聚乙嫌 製之鋁層合包裝材’將簧片露出外部組合，乙烯碳酸酯/ 甲基乙基碳酸酯/二甲基碳酸酯（9/]3/]3體積比）混合溶 劑中添加含1 Μ濃度L i P F 6之電解液1 g後，封閉聚乙烯製 之鋁層合包裝材，得到本發明之電池A。 (充放電） 上述電池A以0.2mA之定電流充電至4.2V後，以 修籲 0_2mA之定電流放電至3.0V，再以1mA之定電流充電至 4.37V。電池充電2次之充電容量（充電電流値之積分値 )爲 1 3 3 m A。 (釘刺試驗） 上述充電之電池A，於保持23 C室溫之室內，負極窣月 上放於木板上靜置後，以直徑1 mm釘刺穿貫通’以紅外 線溫度記錄器（日本AVIONIX公司製「TVS-100」）測 -13· (10) 1330902 定電池表面溫度之上昇。 電池A釘刺後之最大溫度上昇爲3 t。 <實施例2 > 負極之製作，使用聚丙烯酸（PAA)( 「AQUPEC HV-501」日本住友精化製）代替EVOH外，與實施例1同樣 進行，得到負極結構體B，電池B。 負極結構體B之剝離強度爲1 . 0 g f / m m，電池b之充 電容量爲135m Ah，釘刺試驗之最大溫度上昇爲3.5。(：。 ·· <實施例3 > 負極之製作，使用含官能基偏氟乙烯聚合物B& 官能基偏氟乙烯聚合物A外，與實施例1同樣進行 到負極結構體C，電池C。 負極結構體C之剝離強度爲4.3gf/mm，電池^ 電容量爲1 30mAh，釘刺試驗之最大溫度上昇爲3 t。 代含，得 ·· <實施例4 > 負極之製作，使用羥基乙基纖維素（HEq ( MARUKALINKER EP- 8 5 0 j 日本 DAICEL 化學工業製 > 代 替E V Ο Η外，與實施例1同樣進行，得到負極結構|| D 電池D。 負極結構體D之剝離強度爲〇_9gf/mm，電池^ 電容量爲133 mAh，釘刺試驗之最大溫度上昇爲3亡。 -14 - (11) 1330902 <實施例5 > 負極之製作，使用聚 P-乙烯基苯酚（PPVP) ( 「 MARUKALINKER S-2P」日本DA1CEL化學工業製）代替 EVOH外，與實施例1同樣進行，得到負極結構體Η，電 池Η。For the mixing device of the depolarizing mixture composed of the binder composition, the powder electrode material, and the organic solvent, a homomixer or a multi-axis satellite type dispersion mixing kneader or emulsifier can be used. These are not particularly limited. The depolarized mixture slurry prepared by the above method uniformly disperses and mixes the mixed powder electrode material and the binder composition, has good coating properties, and coats the collector. The method of coating is well known, and it is also desirable to use a knife method. The depolarization mixture on the current collector is a 50~1 70 art drying solvent. The electrode structure for the nonaqueous secondary battery is formed by a hot pressing step as necessary. The binder composition and the electrode depolarization mixture of the present invention. It can be used at least for the formation of the positive electrode and the negative electrode, and is used for one of the negative electrodes as the ideal φφ. This is a binder which constitutes a powder electrode material of a negative electrode which requires a high bonding property, and the binder composition of the present invention is particularly suitable for use. [Embodiment] Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples. (Production of functional group-containing vinylidene fluoride copolymer Α) The pressure device with a volume of 2L was charged with 1075 g of ion-exchanged water, methyl cellulose 〇.4 g, vinylidene fluoride monomer (VDF) 398 g, maleic acid monomethyl Base ester-10-(7)(7)1330902 (MMM) 2 g, isopropyl peroxydicarbonate 2.5 g, ethyl acetate 5 g, suspension polymerization at 28 ° C for 27 hours. After the end of the polymerization, the polymer slurry is dehydrated, washed with water, dehydrated, and dried at 80 ° C for 20 hours to obtain a functional group of the present invention having a yield of 89% and a logarithmic viscosity of 1.1 dl/g. Vinylidene-based polymer A. (Production of functional group-containing vinylidene fluoride-based polymer B) The pressurizer containing 2 L of internal volume was charged with ion-exchanged water of 10.7g, methylcellulose 〇.4g, vinylidene fluoride monomer (VDF) of 400g, two 3 g of methyl glycidyl methacrylate (2M-GMA), 2.5 g of isopropyl peroxydicarbonate and 5 g of ethyl acetate were subjected to suspension polymerization for 24 hours at 28 t. After the end of the polymerization, the polymer slurry was dehydrated, washed with water, dried, and dried at 80 ° C for 20 hours to obtain a functional vinylidene fluoride-containing polymer of the present invention having a yield of 90% and a logarithmic viscosity of 2.4 dl/g. B. (Production of vinylidene fluoride-based polymer C) ·_ Pressurizer with an internal volume of 2L was charged with ion-exchanged water 1 0 7 5 g, methylcellulose 〇.4g, vinylidene fluoride monomer (VDF) 400g, isopropyl After the base of the oxidized dicarbonate (2.5 g, ethyl acetate 5 g), the suspension polymerization was carried out at 26 ° C for 20 hours, the polymer slurry was dehydrated, washed with water, dehydrated, and dried at 80 ° C for 20 hours to obtain a yield. 9 1 %, a vinylidene fluoride-based polymer C (polyvinylidene fluoride) of the present invention having a logarithmic viscosity of 1.1 dl/g. -11 - (8) (8) 1330902 <Examples> (Production of positive electrode) 94 parts by weight of lithium succinate ("SELSEED C-5", manufactured by Nippon Chemical Industry Co., Ltd.), part by weight of vinylidene fluoride polymer C3, To 3 parts by weight of carbon black, 43 parts by weight of N-methyl-2-pyrrolidone (NMP) was added, and a polar depolarization mixture for a positive electrode was mixed and prepared. The obtained electrode was depolarized on an aluminum foil of 10 V m, uniformly coated to obtain a film thickness of about 100/zm after drying, and dried at 130 ° C for 25 minutes to obtain a positive electrode structure (active material mass: 29 1 g/m2). (Production of Negative Electrode) Ethylene vinyl alcohol copolymer (EVOH, "K卩-G 1 5 6 B", manufactured by KURARE Co., Ltd., with an ethylene molar content of 4 parts by weight based on the functional group-containing vinylidene fluoride-based polymer A 7 %) 1 part by weight, a spherical natural graphite powder (manufactured by Continental) of 88 parts by weight ' and 67 parts by weight of NMP were mixed to prepare a negative electrode electrode depolarizing mixture composition A of the present invention. The obtained electrode depolarization mixture was applied to 8 // m aluminum copper, uniformly coated to obtain a film thickness of about 100 μm after drying, and dried at 130 t for 25 minutes to obtain a negative electrode structure A (active material mass: 163 g/m 2 ) ). (Method for Measuring Peel Strength of Electrode Structure Electrode Depolarization Mixture Layer) The negative electrode structure coated with the current collector is used as a sample, and the electrode depolarization mixture layer is peeled from the collector, according to ns K 6854 The 1 80 peel test was measured. -12 - (9) (9) 1330902 (Measurement of peel strength) The peel strength of the negative electrode structure A was measured and found to be 3 8 gf / (manufactured by a battery). The positive electrode structure of the 48 mm x 48 mm mounted charge and discharge reed was cut and cut. 50mmx50mm mounting charge and discharge reed negative electrode structure A' electrode surface relative to the intervention 52mmx52mm thickness 2〇ym poly-bine aluminum laminated packaging material 'will reed exposed external combination, ethylene carbonate / methyl ethyl carbonate After adding 1 g of an electrolyte containing 1 Torr of Li PF 6 to an ester/dimethyl carbonate (9/]3/] 3 volume ratio), the aluminum laminated packaging material made of polyethylene was sealed to obtain the present. Battery A of the invention. (Charge and Discharge) The above battery A was charged to 4.2 V at a constant current of 0.2 mA, discharged to 3.0 V at a constant current of 0 2 mA, and charged to 4.37 V at a constant current of 1 mA. The charging capacity (charging current 値 integral 値) of the battery charging 2 times is 1 3 3 m A. (Nail test) The above-mentioned charged battery A was placed in a room at room temperature of 23 C, and the negative electrode was placed on a wooden board for a month, and then pierced through a 1 mm nail. The infrared temperature recorder (AVIONIX, Japan) "TVS-100") Measure -13 (10) 1330902 The rise of the surface temperature of the battery. The maximum temperature rise after battery A nailing is 3 t. <Example 2> The negative electrode was produced in the same manner as in Example 1 except that polyacrylic acid (PAA) ("AQUPEC HV-501" manufactured by Sumitomo Seiko Co., Ltd.) was used instead of EVOH to obtain a negative electrode structure B and a battery B. The peel strength of the negative electrode structure B was 1.0 g f / m m , the charge capacity of the battery b was 135 m Ah, and the maximum temperature rise of the nail test was 3.5. (Example: <Example 3 > Preparation of a negative electrode, using a functional group-containing vinylidene fluoride polymer B& functional group vinylidene fluoride polymer A, the negative electrode structure C was carried out in the same manner as in Example 1, and the battery was used. C. The peeling strength of the negative electrode structure C was 4.3 gf/mm, the battery capacity was 1 30 mAh, and the maximum temperature rise of the nail penetration test was 3 t. Substituting, obtaining ···<Example 4 > Production of negative electrode In the same manner as in Example 1, except that hydroxyethyl cellulose (HEq (MARUKALINKER EP-85 5 j Japan DAICEL Chemical Industry Co., Ltd.) was used instead of EV Η 负极, a negative electrode structure was obtained || D battery D. Negative electrode structure D The peeling strength was 〇_9gf/mm, the battery capacity was 133 mAh, and the maximum temperature rise of the nail test was 3 deaths. -14 - (11) 1330902 <Example 5 > Preparation of the negative electrode, using poly P A vinyl phenol (PPVP) ("MARUKALINKER S-2P" manufactured by Nippon DA1CEL Chemical Co., Ltd.) was used in the same manner as in Example 1 except that EVOH was used, and a negative electrode structure Η and a battery Η were obtained.
負極結構體Η之剝離強度爲5.4 g f/m m，電池Η之充 電容量爲134m Ah，釘刺試驗之最大溫度上昇爲4°C。 <比較例1> 負極之製作，使用含官能基偏氟乙烯聚合物A由1 1 g 增加至12g，不使用EVOH外，與實施例1同樣進行，得 到負極結構體E，電池E。 負極結構體E之剝離強度爲0.9g f/mm，電池E之充 電容量爲I 3 3 m A h，釘刺試驗之最大溫度上昇爲1 2X。 ·· <比較例2 > 負極之製作，使用含官能基偏氟乙烯聚合物B由]lg 增加至】2g，不使用EVOH外，與實施例3同樣進行，得 到負極結構體F，電池F。 負極結構體F之剝離強度爲3.1gf/mm，電池E之充 電容量爲124mAh，釘刺試驗之最大溫度上昇爲6.5°C。 <比較例3 > -15- (12) 1330902 代含 ，得 負極之製作，使用含官能基偏氟乙烯聚合物C取 官能基偏氟乙烯聚合物A外，與實施例]同樣進行 到負極結構體G，電池G。 負極結構體G之剝離強度爲0.7gf/mm，電池g 4〜 β充 電容量爲134mAh，釘刺試驗之最大溫度上昇爲6t。 <比較例4 >The peel strength of the negative electrode structure was 5.4 gf/m m, the charge capacity of the battery crucible was 134 m Ah, and the maximum temperature rise of the nail penetration test was 4 °C. <Comparative Example 1> The preparation of the negative electrode was carried out in the same manner as in Example 1 except that the functional group-containing vinylidene fluoride polymer A was increased from 11 g to 12 g, and EVOH was used, to obtain a negative electrode structure E and a battery E. The peel strength of the negative electrode structure E was 0.9 gf/mm, the charge capacity of the battery E was I 3 3 m A h , and the maximum temperature rise of the nail penetration test was 12 2X. <Comparative Example 2> The negative electrode was produced by using the functional group-containing vinylidene fluoride polymer B from [lg] to 2 g, and the negative electrode structure F was obtained in the same manner as in Example 3 except that EVOH was not used. F. The peel strength of the negative electrode structure F was 3.1 gf/mm, the charge capacity of the battery E was 124 mAh, and the maximum temperature rise of the nail penetration test was 6.5 °C. <Comparative Example 3 > -15- (12) 1330902 The preparation of the negative electrode was carried out in the same manner as in Example 7 except that the functional group-containing vinylidene fluoride polymer C was used as the functional vinylidene fluoride polymer A. Negative electrode structure G, battery G. The peel strength of the negative electrode structure G was 0.7 gf/mm, the charge capacity of the battery g 4 to β was 134 mAh, and the maximum temperature rise of the nail penetration test was 6 t. <Comparative Example 4 >
負極之製作，使用含官能基偏氟乙烯聚合物C取代含_ 官能基偏氟乙烯聚合物A外，與比較例1同樣進行，得 到負極結構體Η，電池Η。 負極結構體G之剝離強度爲0.7g f/mm，電池G之充 電容量爲1 3 2 m A h，釘刺試驗之最大溫度上昇爲9 °C。 上述實施例與比較例所使用之黏合劑組成物之槪要及 評價結果彙集如以下表1所示。. ·· -16- (13)1330902The negative electrode was produced in the same manner as in Comparative Example 1, except that the functional group-containing vinylidene fluoride polymer C was used instead of the functional group-containing vinylidene fluoride polymer A, to obtain a negative electrode structure Η and a battery crucible. The peel strength of the negative electrode structure G was 0.7 gf/mm, the charge capacity of the battery G was 1 3 2 m A h, and the maximum temperature rise of the nail penetration test was 9 °C. The summary of the adhesive compositions used in the above examples and comparative examples and the evaluation results are summarized in Table 1 below. .·· -16- (13)1330902
表I 黏合劑組成物 評價結果 項目 偏氟乙嫌系 聚合物 極性 聚合物 剝離強度 (g-f/mm) 充電容量 (mAh) 釘刺後之最大 溫度上昇 CC) 實施例1 A VDF/MMM =99.5/0.5 EVOH 3.8 133 3 實施例2 A PAA 1.0 135 3.5 實施例3 B VDF/2M-GMA 100/0.75 EVOH 3.4 130 3 實施例4 A HEC 0.9 133 3.5 實施例5 A PPVP 5.4 134 4 比較例1 A te / » 3.4 130 12 比較例2 B M / * 3.1 124 6.5 比較例3 C VDF=100 EVOH 0.7 134 6 比較例4 C M *»\> 0.7 132 9Table I Adhesive Composition Evaluation Results Item Partial Fluoride Derivative Polymer Polar Polymer Peel Strength (gf/mm) Charging Capacity (mAh) Maximum Temperature Rise After Sting C) Example 1 A VDF/MMM = 99.5/ 0.5 EVOH 3.8 133 3 Example 2 A PAA 1.0 135 3.5 Example 3 B VDF/2M-GMA 100/0.75 EVOH 3.4 130 3 Example 4 A HEC 0.9 133 3.5 Example 5 A PPVP 5.4 134 4 Comparative Example 1 A te / » 3.4 130 12 Comparative Example 2 BM / * 3.1 124 6.5 Comparative Example 3 C VDF = 100 EVOH 0.7 134 6 Comparative Example 4 CM *»\> 0.7 132 9
·· 〔產業上之利用領域〕 由上述表I可知，有關具備可吸藏•放出鋰之正極及 負極之非水電解液電池，上述正極/或負極之結合劑使用 含官能基偏氟乙烯系聚合物及極性聚合物之非水電解液電 -17- (14) 1330902 池電極用黏合劑組成物，知道可得到接合性優之電極與安 全性優之電池。 ·· ·· -18-··In the field of industrial use, it can be seen from the above Table I that the non-aqueous electrolyte battery having the positive electrode and the negative electrode capable of absorbing and releasing lithium has a functional group-based vinylidene fluoride-based binder. Non-aqueous electrolyte of polymer and polar polymer -17- (14) 1330902 The composition of the binder for the pool electrode, it is known that the electrode with excellent bonding property and the battery with excellent safety can be obtained. ·· ·· -18-