TW200410439A - Binder composition for electrode of nonaqueous electrolyte battery, and use thereof - Google Patents

Binder composition for electrode of nonaqueous electrolyte battery, and use thereof Download PDF

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TW200410439A
TW200410439A TW092132611A TW92132611A TW200410439A TW 200410439 A TW200410439 A TW 200410439A TW 092132611 A TW092132611 A TW 092132611A TW 92132611 A TW92132611 A TW 92132611A TW 200410439 A TW200410439 A TW 200410439A
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Taiwan
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electrode
polymer
battery
vinylidene fluoride
aqueous electrolyte
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TW092132611A
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Chinese (zh)
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TWI330902B (en
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Mitsuyasu Sakuma
Nobuo Ahiko
Tomoaki Kawakami
Takumi Katsurao
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Kureha Chemical Ind Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A composition comprising at least a functional group-containing vinylidene fluoride polymer and a polar polymer having a hydroxyl group and/or a carbonyl group in the molecule is used as a binder for an electrode (a positive or negative electrode) active material. Consequently, a nonaqueous electrolyte battery can have improved performance stability and improved safety at the time of internal short-circuiting while maintaining a necessary large capacity.

Description

200410439 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係有關非水電解 用之電極用黏合劑，使用其 用其之非水電解液電池。 【先前技術】 近年電子技術發展驚人 此電子機器之小型輕量化相 量化之要求非常大。作爲小 之電池，爲使用鋰之非水系 電話或個人電腦、錄影機等 〇 鋰電池用電極結構體係 保持集電物之狀態使用，正 負極活性物質爲碳元素材料 合劑，主要使用偏氟乙烯系 日本特開平1 1 - 3 2 9 4 4 3 烯系聚合物與纖維素系聚合 不充分，亦未完全考慮其安 但是，機器之小型輕量 要求’鋰電池更要高容量化 部裝入電極等之增加容量之 大之電流流向局部，招致電 液電池，特別是製造鋰電池使 之電極去極化合劑、電極及使 ，各種機器可小型輕量化。與 結合，其電源之電池之小型輕 容積及重量，可得到更大能量 二次電池，主要可使用於行動 之家庭用小型電子機器之電源 由活性物質、導電劑以黏合劑 極活性物質爲鋰複合氧化物， ’又爲結合此等活性物質之黏 聚合物。 號公報以不具官能基之偏氟乙 物之混合物爲例示，其結合性 全性。 化與增長電池持續時間之市場 ’與向來品比較，由於電池內 反面’電池內部發生短路時過 池急激的溫度上昇，引起電池 -5- (2) (2)200410439 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 及非水電解液電池。 φ 本發明係爲解決上述之課題，其有關之第1觀點，爲 提供使用具備可吸藏·放出鋰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 - (3) 200410439 電池內部溫度因短路等而上昇對熱不安定之鋰化 抑制分解發熱同時亦抑制活性物質內之鋰離子與 接反應之活動。又，有關爲預先發現後述之內部 溫度上昇而進行之釘刺試驗之溫度上昇，與黏合 接合強度顯不逆相關來看，提高內部短路時之安 低溫度上升）與黏合劑所持之接合性亦爲重要。 持，（甲）鋰離子之選擇穿透性，及（乙）提高 爲相剩效果，提高內部短路時之安全性。 〔用以實施發明之最佳型態〕 本發明之含官能基偏氟乙烯系聚合物係偏氟 之單獨、或偏氟乙烯單體與可能與其共聚合之其 例如乙烯、丙烯等之烴素單體，或氟乙烯、三氟 化三氟乙烯、四氟乙烯、六氟乙烯、六氟丙烯、 乙烯基醚等之偏氟乙烯以外之含氟單體（理想爲 烯之合計量20重量％以下）之混合物，相對於〕 量份，使用加入0.1〜3重量份具有官能基之單量 共聚物爲理想。具官能基之單體爲具有羧基者例 、丁烯酸等之不飽和-鹼酸，馬來酸、檸康酸等；^ 二鹼酸，或其等之單烷基酯之馬來酸單甲基酯、 乙基酯、檸康酸單甲基酯、檸康酸單乙基酯等， 氧丙基之單體，例如烯丙基環氧丙基醚、甲基烯 丙基醚、丁烯酸環氧丙基酯、烯丙基醋酸環氧丙 使用至少與其中一種以上共聚合所得之含官能基 合物量少 電解液直 短路時之 劑所持之 全性（降 黏合劑所 接合強度 乙烯單體 他單體， 乙烯、氯 氟化院基 與偏氟乙 ί 1 00 重 體所得之 如丙烯酸 :不飽和-馬來酸單 又，含環 丙基環氧 基酯等。 偏截乙稀 (4) (4)200410439 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。 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 90 23號公報揭示，其標準爲對數比濃粘度（樹脂4g 以1L之N，N-三甲基甲醯胺溶解之溶液於30°C之對數濃度 )爲 0.8〜2 0dl/g，理想爲 1 .0〜20dl/g，更理想爲 1 .0〜1 5 dl/g，再理想爲1.2〜15dl/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10〜99重量％ -8- (5) (5)200410439 、理想爲20〜95重量％，極性聚合物爲1〜90重量％，理想 爲5〜80重量％。極性聚合物低於上述範圍時，活性物質 表面之被覆狀態不充分，活性物質表面與電解液之接觸面 積變廣電池安全性變差。更且，聚合物之電極與集電物之 接合性或電極活性物質之間之接合性下降，重複充放電之 放電容量有降低之疑慮。 本發明之黏合劑組成物，通常，構成黏合劑組成物之 含官能基偏氟乙烯系聚合物及極性聚合物溶解於溶劑，更 分散正極或負極活性物質及因應必要添加之導電補助劑等 之助劑，形成泥漿狀之電極去極化合劑，可使用於電極之 製造。溶劑理想爲具極性之有機溶劑，可列舉如N-甲基-2-吡咯烷酮、Ν，Ν·二甲基甲醯胺、N，N-二甲基乙醯胺、 N，N-二甲基亞碼、六甲基膦胺、三乙基磷、丙酮等，此等 有機溶劑不僅可單獨使用亦可二種以上混合使用。 有關本發明，作爲鋰之二次電池用活性物質，爲正極 時，一般式 LiMY2(M 至少爲 Co、Ni、Fe、Mn、Cr、V 等過渡金屬之一種：Y爲0、S等之硫族元素）所示之複 合金屬硫族化合物，爲負極時，使用天然石墨、人造石墨 、焦碳、活性碳、酚樹脂或瀝青等之燒結碳化者等之粉末 碳元素材料、金屬氧化物系GeO、Geo2、SO、Sn02、PbO 、Pb〇2等或其複合金屬氧化物，Si、SiSn等之砂元素及 矽元素化合物等。 黏合劑組成物，係相對於1 00重量份電極（正極或 負極）及導電助劑（此等槪括以「粉末電極材料」稱）， -9- (6) (6)200410439 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。 又’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 〇 〇重量份溶劑，黏合劑組成 物爲0.1〜30重量份，特別以1〜20重量份之比例爲理想。 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 於集電物。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50〜17(TC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 。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i〇75g，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)200410439 (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 80 °C乾燥 20小時，得到收率89%，對數比濃粘度爲 l.ldl/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1 075 g，甲基纖 鲁 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 8 0 °C乾燥 2 0小時，得到收率 9 0 %，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） φ 內容積2L之加壓器投入離子交換水l〇75g，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 合。 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 l.ldl/g之本發明之偏氟乙烯系聚合物C (聚偏氟乙烯）。 -11 - (8) (8)200410439 <實施例1> (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重纛份添 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 // m之鋁 箔上，均勻塗覆得到乾燥後約爲1 〇〇 # m之膜厚，於1 3〇 °C乾燥25分鐘，得到正極結構體（活性物質量： 291g/m2) ° (負極之製造） 相對於含官能基偏氟乙烯系聚合物A 1 1重量份，乙 烯乙烯基醇共聚物（EVOH，日本KURARE公司製「EP-G156B」，乙烯莫耳含量47 % ) 1重量份，混合平均粒子 徑30//m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100 // m之膜厚，於130°C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@ 化合劑層由集電物剝離強度，依Π S K 6 8 5 4爲準測定 180°剝離試驗。 -12· 200410439 Ο) (剝離強度之測定） 測疋上述負極結構體A之剝離強度結果爲3 · 8 g f / m m (電池之製作） 切取48mmx 4 8mm安裝充放電用簧片之正極結構體 ，及切取50mmx5 0mm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20//m之聚乙稀 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（9/13/13體積比）混合溶 劑中添加含1M濃度LiPF6之電解液lg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 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 〇 (釘刺試驗） 上述充電之電池A，於保持23C室溫之室內，負極朝 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) (10)200410439 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 °C。 <實施例2> 負極之製作，使用聚丙烯酸（PAA)( 「AQUPEC HV-5 0 1」日本住友精化製）代替EV Ο Η外，與實施例1同樣 進行，得到負極結構體Β，電池Β。 負極結構體Β之剝離強度爲1 .Ogf/mm，電池β之充 電容量爲135m Ah，釘刺試驗之最大溫度上昇爲3. 5°C。 <實施例3> 負極之製作，使用含官能基偏氟乙烯聚合物B取代含 官能基偏氟乙烯聚合物A外，與實施例1同樣進行，得 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C之充 電容量爲130mAh，釘刺試驗之最大溫度上昇爲。 <實施例4> 負極之製作，使用羥基乙基纖維素（HEC) ( 「 MARUKALINKER EP-850」日本DAICEL化學工業製）代 替EVOH外，與實施例1同樣進行，得到負極結構體〇， 電池D。 負極結構體D之剝離強度爲0.9gf/mm，電池D之充 電容量爲1 3 3 mAh，釘刺試驗之最大溫度上昇爲3 °C。 -14- (11) 200410439 <實施例5 > 負極之製作，使用聚 P-乙烯基苯酚（pPv p) ( 「 MARUKALINKER S-2P」曰本DAICEL化學工業制 灸）代替 EVOH外，與實施例1同樣進行，得到負極結擒於 哀H ’電 池Η。 負極結構體Η之剝離強度爲5.4gf/mm，鼇池μ 電容量爲134mAh，釘刺試驗之最大溫度上昇爲4 〇200410439 ⑴ 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a binder for electrodes for non-aqueous electrolysis, and a non-aqueous electrolyte battery using the same. [Previous technology] The development of electronic technology in recent years has been amazing. As a small battery, it is used for non-aqueous phones, personal computers, and video recorders that use lithium. The electrode structure system for lithium batteries is used to maintain the current collector. The positive and negative active materials are carbon material mixtures, and vinylidene fluoride is mainly used. Japanese Unexamined Patent Publication No. 1 1-3 2 9 4 4 3 Insufficient polymerization of olefinic polymers and celluloses has not been fully considered. However, the small size and light weight of the machine require that the lithium battery should be equipped with a high capacity part. When the large current that increases the capacity flows to the local area, it is used in liquid batteries, especially in the manufacture of lithium batteries to depolarize the electrodes, the electrodes, and the electrodes. Various devices can be small and lightweight. Combined with the small, light volume and weight of the battery of the power supply, a larger energy secondary battery can be obtained, which can mainly use the active material, conductive agent, binder, and extremely active material of lithium as the power source of small electronic devices for household use in mobile applications. The complex oxide, 'is again a viscous polymer incorporating these active substances. Japanese Patent Publication No. exemplifies a mixture of vinylidene fluoride having no functional group, and its binding property is comprehensive. Compared with conventional products, the market of battery growth and battery duration is compared with conventional products. Because of the reverse side of the battery, the battery ’s rapid temperature rise when a short circuit occurs inside the battery, causing the battery to -5- (2) (2) 200410439 rupture, smoke, ignition, etc. The dangerous state increases the problem of danger. [Summary of the Invention] [Disclosure of the Invention] Therefore, the main object of the present invention is to provide a non-electrolyte battery for electrode bonding, which provides a high capacity necessary for maintaining a non-hydrolyzed liquid battery and improves the performance stability and safety during internal short circuit. Agent composition, and uses its electrode and non-aqueous electrolyte battery. φ The present invention is to solve the above-mentioned problem. A first aspect of the present invention is to provide non-aqueous electrolysis using a positive electrode and / or a negative electrode binder as a non-aqueous electrolyte battery using a positive electrode and a negative electrode capable of occluding and releasing lithium. Adhesive composition for liquid battery electrode. In another aspect of the present invention, at least one of an electrode depolarization mixture including the above-mentioned binder composition and an electrode active material, an electrode having the above-mentioned electrode depolarization mixture layer on a current collector, and at least one of a positive electrode and a negative electrode is A non-aqueous electrolyte battery containing the electrode. · The reasons for improving the above-mentioned adhesive composition to maintain the necessary high capacity of non-aqueous electrolyte batteries, and the stability of its performance and safety during internal short circuits are not clear. It can be considered as a polymer containing functional vinylidene fluoride. The carboxyl group or the epoxy group and the hydroxyl group and carbonyl group of the polar polymer, the binder formed by the combination of the hydroxyl group and the hydrogen on the surface of the current collector or the electrode active material improves the bonding, and at the same time, the surface of the electrode active material forms a barrier to non-water The penetration of the electrolyte, the selective permeability of lithium ions, inhibits the formation of lithium compounds from the reaction between the electrolyte and lithium ions when the surface of the electrode active material is charged and discharged, and the charge is -6-(3) 200410439 The internal temperature of the battery due to a short circuit, etc. The rising lithium that is unstable to heat suppresses decomposition and heat generation, and also suppresses the activity of lithium ions in the active material to interact with the contact. In addition, the temperature rise of the nail penetration test performed in order to find the internal temperature rise described later in advance has an irreversible correlation with the bonding strength, which improves the low temperature rise during internal short circuit) and the bonding property held by the adhesive. Is important. (A) Selective penetrability of lithium ions, and (B) increase the residual effect to improve safety during internal short circuit. [The best form for carrying out the invention] The functional group-containing vinylidene fluoride-based polymer of the present invention alone or a vinylidene fluoride monomer may be copolymerized with other hydrocarbons such as ethylene and propylene. Monomers, or fluorine-containing monomers other than vinylidene fluoride such as vinyl fluoride, trifluoroethylene trifluoroethylene, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, vinyl ether (ideally 20% by weight of the total amount of olefins) The mixture of the following) is preferably used in the amount of 0.1 to 3 parts by weight of a single-unit copolymer having a functional group with respect to the amount of parts. Functional monomers are those with carboxyl groups, unsaturated-alkanoic acids such as butenoic acid, maleic acid, citraconic acid, etc .; ^ dibasic acids, or maleic acid monoesters thereof Methyl ester, ethyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, etc., oxypropyl monomers, such as allyl epoxypropyl ether, methallyl ether, butyl Holistic properties of epoxy propylene acrylate and allylic acetic acid propylene using at least one copolymerized with at least one of the functional groups containing a small amount of functional group-containing compounds when the electrolyte is short-circuited (reducing the bonding strength of the adhesive) Ethylene monomers, other monomers, ethylene, chlorofluorinated base and vinylidene fluoride are obtained from heavy weights such as acrylic acid: unsaturated-maleic acid monomer, containing cyclopropyl epoxy ester, etc. The dilute (4) (4) 200410439-based polymer is ideal. Such functional group-containing vinylidene fluoride-based polymers can be obtained by known methods such as suspension polymerization, emulsion polymerization, and solution polymerization. In addition, the introduction method of the functional group After the defluorinated acid is heated from the vinylidene fluoride polymer by alkali, it can be treated with organic acid or oxidant to obtain the function. Polymer The molecular weight of vinylidene fluoride polymer containing functional groups is disclosed in Japanese Patent Application Laid-Open No. 9-2 8 90 23. Its standard is logarithmic reduced viscosity (4 g of resin with 1 L of N, N-trimethyl methyl The logarithmic concentration of the amidine solution at 30 ° C) is 0.8 ~ 2 0dl / g, ideally 1.0 ~ 20dl / g, more preferably 1.0 ~ 15 dl / g, and even more preferably 1.2 ~ 15dl / g is the ideal range. When the logarithmic concentrated viscosity of the vinylidene fluoride polymer is lower than the above range, the viscosity of the electrode depolarizing mixture is too low, and coating is difficult, and if it exceeds the above range, it is difficult to dissolve the organic solvent. Appropriate. The polar polymer used in the present invention is 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, and a vinyl phenol polymer. In addition, the polymer having a carbonyl group is a polyacrylic polymer, and specifically includes polyacrylic acid, a polyacrylic acid crosslinked polymer, and metal salts thereof. Polyvinylpyrrolidone is also suitable for polar polymers. Necessary, functional In addition to vinylidene polymers, polar polymers with hydroxyl or carbonyl groups, individual polymers of vinylidene fluoride, vinylidene fluoride and vinyl fluoride, trifluoroethylene, trifluoroethylene chloride, tetrafluoroethylene, six Copolymers of monomers such as fluoropropylene that can be copolymerized with vinylidene fluoride. For the mixing ratio of the functional group-containing vinylidene fluoride-based copolymer to the polar polymer, the functional group-containing vinylidene fluoride-based copolymer is 10 ~ 99% by weight -8- (5) (5) 200410439, ideally 20 to 95% by weight, polar polymers 1 to 90% by weight, ideally 5 to 80% by weight. When the polar polymer is below the above range, The covering state of the surface of the active material is insufficient, and the contact area between the surface of the active material and the electrolyte is widened, and the safety of the battery is deteriorated. Furthermore, the adhesiveness between the polymer electrode and the current collector or the electrode active material is reduced, and there is a concern that the discharge capacity due to repeated charge and discharge may be reduced. In the binder composition of the present invention, generally, the functional group-containing vinylidene fluoride-based polymer and the polar polymer constituting the binder composition are dissolved in a solvent, and the positive or negative electrode active material and the conductive auxiliary agent added as necessary are dispersed. Additives to form a slurry-like electrode depolarization mixture, which can be used in the manufacture of electrodes. The solvent is preferably a polar organic solvent, and examples thereof include N-methyl-2-pyrrolidone, N, N · dimethylformamide, N, N-dimethylacetamide, and N, N-dimethyl Sub-code, hexamethylphosphine amine, triethyl phosphorus, acetone, etc. These organic solvents can be used not only alone but also as a mixture of two or more. In the present invention, when the lithium secondary battery active material is a positive electrode, the general formula LiMY2 (M is at least one of Co, Ni, Fe, Mn, Cr, V and other transition metals: Y is sulfur such as 0, S, etc. (Group element) composite metal chalcogenide, when used as a negative electrode, powdered carbon element materials such as natural graphite, artificial graphite, coke, activated carbon, phenol resin, or pitch sintered carbonizer, and metal oxide GeO , Geo2, SO, Sn02, PbO, Pb02, etc. or their composite metal oxides, sand elements such as Si and SiSn, and silicon element compounds. The binder composition is relative to 100 parts by weight of an electrode (positive or negative electrode) and a conductive additive (these are collectively referred to as "powder electrode materials"), -9- (6) (6) 200410439 to use 0. 1 to 30 parts by weight, and particularly preferably a ratio of 0.5 to 20 parts by weight. In addition, when the adhesive composition is dissolved and used in an organic solvent in advance, the solvent is singly or as a mixture of two or more kinds. For each 1,000 parts by weight of the solvent, the adhesive composition is 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight. The ratio is ideal. A mixing device for a depolarizing mixture made of a binder composition, a powder electrode material, and an organic solvent. A homogenizer or a multi-axis satellite type dispersion mixing kneader or emulsifier can be used. These are not particularly limited. The depolarizing mixture slurry prepared by the above method is a uniformly dispersed and mixed powder electrode material and a binder composition, which has good coating properties and is applied to a current collector. The coating method may be any known method, and it is also preferable to use a knife method. The depolarizing mixture on the current collector is 50 ~ 17 ° C dry solvent, and the electrode structure for non-aqueous secondary battery is formed by the hot pressing step if necessary. The binder composition and electrode depolarizing mixture of the present invention, It can be used to form at least one of the positive electrode and the negative electrode, and is preferably used in one of the negative electrodes. The powder electrode material constituting the negative electrode requires a high bonding agent, and the binder composition of the present invention is particularly suitable for use. [Form] The present invention will be described more specifically with reference to the following examples and comparative examples. (Production of functional group-containing vinylidene fluoride copolymer A) A pressurizer with an internal volume of 2 L was charged with 75 g of ion-exchanged water and methyl cellulose. .4g, 398g of vinylidene fluoride monomer (VDF), monomethyl maleate -10- (7) (7) 200410439 (MMM) 2g, isopropylperoxydicarbonate 2.5g, ethyl acetate 5g , Suspension polymerization was carried out for 2 7 hours at 2 8 ° C. After the polymerization was completed, the polymer slurry was dehydrated, washed with water, and dried at 80 ° C for 20 hours. The yield was 89%, and the log-concentrated viscosity was l.ldl. / g of the functional group-containing vinylidene fluoride-based polymer of the present invention Product A. (Production of functional vinylidene fluoride polymer B containing functional group) Pressurizer with an internal volume of 2L was charged with 1 075 g of ion-exchanged water, 0.4 g of methylcellulose, and vinylidene fluoride monomer (VDF). 400 g, 3 g of dimethyl epoxypropyl methacrylate (2M-GMA), 2.5 g of isopropyl peroxydicarbonate, and 5 g of ethyl acetate at 2 8 t: Suspension polymerization for 2 5 hours After the polymerization is completed, the polymer slurry is dehydrated, washed with water, and dried at 80 ° C for 20 hours. The yield is 90%, and the logarithmic reduced viscosity is 2.4 dl / g. Ethylene polymer B. (Manufacture of vinylidene fluoride polymer C) φ Internal pressure 2L pressurizer 1075g of ion-exchanged water, 0.4g of methyl cellulose, 400g of vinylidene fluoride monomer (VDF) , 2.5 g of isopropyl peroxydicarbonate and 5 g of ethyl acetate were subjected to suspension polymerization at 26 ° C for 20 hours. After the polymerization was completed, the polymer slurry was dehydrated, washed with water, and dried at 80 ° C for 20 hours. To obtain a vinylidene fluoride polymer C (polyvinylidene fluoride) of the present invention in a yield of 91% and a log-concentrated viscosity of 1.1 l / g. -11-(8) (8) 200410439 < Example 1 > (Production of positive electrode) 94 parts by weight of lithium succinate ("SELSEED C-5", manufactured by Japan Chemical Industry Co., Ltd.), 3 parts by weight of vinylidene fluoride polymer C, and 3 parts by weight of carbon black 43 parts by weight of N-methyl-2-pyrrolidone (NMP) was added to prepare a depolarizing mixture for a positive electrode. The obtained electrode depolarizing mixture was coated on an aluminum foil of 10 m and uniformly dried. A film thickness of about 100 mm was dried at 130 ° C for 25 minutes to obtain a positive electrode structure (active material mass: 291 g / m2) ° (manufactured of a negative electrode) Polymerized with vinylidene fluoride containing functional groups A 1 1 part by weight of ethylene vinyl alcohol copolymer (EVOH, "EP-G156B" manufactured by Japan Kurare Co., Ltd., 47% ethylene mole content) 1 part by weight, mixed with spherical natural graphite with an average particle diameter of 30 // m 88 parts by weight of powder (made in China) and 67 parts by weight of NMP were used to prepare the negative electrode depolarizing mixture composition A of the present invention. The obtained electrode depolarizing mixture was uniformly coated on 8 // m aluminum and copper, uniformly coated to obtain a film thickness of about 100 // m after drying, and dried at 130 ° C for 25 minutes to obtain a negative electrode structure A (active substance mass : 163 g / m2). (Measurement method of peeling strength of the electrode structure electrode depolarizing mixture layer) The current collector is coated with a dried negative electrode structure as a sample, and the electrode de @ compound layer is peeled off by the current collector according to SK 6 8 5 4 refers to the 180 ° peel test. -12 · 200410439 〇) (Measurement of peeling strength) As a result of measuring the peeling strength of the above negative electrode structure A, the result was 3 · 8 gf / mm (manufacturing of the battery). A 48 mm x 4 8 mm positive electrode structure with a reed for charging and discharging was cut. And cut out 50mmx50mm negative electrode structure A for charging and discharging reeds, the electrode surface is relatively interposed with 52mmx52mm thickness 20 // m aluminum laminate packaging material, the reeds are exposed to the outside, vinyl carbonate / form After adding an electrolytic solution lg containing 1M concentration of LiPF6 to a mixed solvent of ethyl ethyl carbonate / dimethyl carbonate (9/13/13 volume ratio), the aluminum laminated packaging material made of polyethylene was sealed to obtain the battery of the present invention. A. (Charging and Discharging) After the above battery A is charged to a constant current of 0.2 mA to 4.2 V, it is discharged to a constant current of 0.2 mA to 3.0 V, and then charged to a constant current of 1 mA to 4.37 V. The charging capacity (integral of charging current 値) of the battery for two recharges is 1 3 3 m A 〇 (nail penetration test) The above-mentioned charged battery A is placed in a room maintained at a room temperature of 23C, and the negative electrode is placed on a wooden board to stand still. Then, pierce it with a nail with a diameter of 1 mm, and measure the temperature rise of the battery surface with an infrared temperature recorder ("TVS-100" made by AVIONIX Corporation, Japan) -13- (10) (10) 200410439. The maximum temperature rise after battery A was spiked was 3 ° C. < Example 2 > Production of a negative electrode was performed in the same manner as in Example 1 except that polyacrylic acid (PAA) ("AQUPEC HV-5 0 1" manufactured by Sumitomo Refinery, Japan) was used in place of EV 0 to obtain a negative electrode structure B, Battery B. 5 ° C。 The peel strength of the negative structure B is 1. Ogf / mm, the charging capacity of the battery β is 135m Ah, and the maximum temperature rise of the nail penetration test is 3.5 ° C. < Example 3 > The production of a negative electrode was carried out in the same manner as in Example 1 except that the functional group-containing vinylidene fluoride polymer B was used instead of the functional group-containing vinylidene fluoride polymer A to obtain a negative electrode structure C and a battery C. The peel strength of the negative electrode structure C was 4.3 gf / mm, the charge capacity of the battery C was 130 mAh, and the maximum temperature rise of the nail penetration test was. < Example 4 > Production of a negative electrode was performed in the same manner as in Example 1 except that hydroxyethyl cellulose (HEC) ("MARUKALINKER EP-850" manufactured by Japan DAICEL Chemical Industry) was used instead of EVOH. A battery was obtained. D. The peel strength of the negative electrode structure D was 0.9 gf / mm, the charge capacity of the battery D was 1 3 3 mAh, and the maximum temperature rise of the nail penetration test was 3 ° C. -14- (11) 200410439 < Example 5 > Production of a negative electrode using poly-p-vinylphenol (pPv p) ("MARUKALINKER S-2P" Japanese Daicel Chemical Industry Moxibustion) instead of EVOH, and implementation Example 1 was performed in the same manner, and a negative electrode was obtained from the battery H ′. The peeling strength of the anode structure Η was 5.4 gf / mm, the capacitance of Aochi μ was 134 mAh, and the maximum temperature rise of the nail penetration test was 4 〇

<比較例 負極之製作，使用含官能基偏氟乙烯聚合牛勿< Comparative Example The production of a negative electrode, using functionalized vinylidene fluoride polymerized

A 由 得 增加至12g，不使用EVOH外，與實施例1同樣進行 到負極結構體E，電池E。 負極結構體E之剝離強度爲0 · 9 g f/mm，電、池$ & 電容量爲133mAh，釘刺試驗之最大溫度上昇爲l2fA was increased to 12 g, except that EVOH was not used. The procedure was carried out in the same manner as in Example 1 to the negative electrode structure E and the battery E. The peel strength of the negative electrode structure E is 0 · 9 g f / mm, the electric capacity and the battery capacity are 133mAh, and the maximum temperature rise of the nail penetration test is l2f

<比較例2 > 負極之製作，使用含官能基偏氟乙烯聚合物B _ 增加至12g，不使用EV OH外，與實施例3同樣進行 到負極結構體F，電池F。 負極結構體F之剝離強度爲3 · 1 g f / m m，電池g 電容量爲1 2 4 m A h，釘刺試驗之最大溫度上昇爲6.5 ^ 1 1 g 得 之充 ο <比較例3 > -15- (12) (12)200410439 負極之製作，使用含官能基偏氟乙烯聚合物C 1 收代含 官能基偏氟乙烯聚合物A外，與實施例1同樣進^ 仃，得 到負極結構體G，電池G。< Comparative Example 2 > The production of a negative electrode was increased to 12 g using functional group-containing vinylidene fluoride polymer B_, and EV OH was not used. The negative electrode structure F had a peeling strength of 3.1 Gf / mm, a battery g with a capacitance of 124 mAh, and a maximum temperature rise of a nail penetration test of 6.5 ^ 1 1 g. ≪ Comparative Example 3 & gt -15- (12) (12) 200410439 Production of negative electrode, using functional group-containing vinylidene fluoride polymer C 1 instead of functional group-containing vinylidene fluoride polymer A, the same as in Example 1 was used to obtain a negative electrode Structure G, battery G.

負極結構體G之剝離強度爲0.7 g f / m m，電池G 之充 電容量爲134mAh，釘刺試驗之最大溫度上昇爲6t：。 <比較例4 > 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Α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。The peeling strength of the negative electrode structure G was 0.7 g f / m m, the charging capacity of the battery G was 134 mAh, and the maximum temperature rise of the nail penetration test was 6 t :. < Comparative Example 4 > Production of a negative electrode was carried out in the same manner as in Comparative Example 1 except that the functional group-containing vinylidene fluoride polymer C was used to obtain # ^ functional group vinylidene fluoride polymer A. A negative electrode structure Η and a battery Η were obtained. The peeling strength of the negative electrode structure G was 0.7 g f / mm, the charging capacity of the battery G was 132 m A h, and the maximum temperature rise of the nail penetration test was 9 ° c. The summary and evaluation results of the adhesive composition used in the above examples and comparative examples are shown in Table 1 below.

-16 - (13) 200410439 表1 黏合劑組成物 評價結果 項目 偏氟乙烯系 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 (°C) 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 M 3.4 130 12 比較例2 B A\ \ r. ml j\\\ 3.1 124 6.5 比較例3 C VDF=100 EVOH 0.7 134 6 比較例4 C M j\\\ 0.7 132 9-16-(13) 200410439 Table 1 Evaluation results of the adhesive composition Item Peel strength of vinylidene-based polymer Polar polymer (gf / mm) Charging capacity (mAh) Maximum temperature rise after nailing (° 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 AM 3.4 130 12 Comparative Example 2 BA \ \ r. Ml j \\\ 3.1 124 6.5 Comparative Example 3 C VDF = 100 EVOH 0.7 134 6 Comparative Example 4 CM j \\\ 0.7 132 9

〔產業上之利用領域〕 由上述表1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)200410439 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。[Application fields in the industry] As can be seen from the above Table 1, regarding a non-aqueous electrolyte battery including a positive electrode and a negative electrode capable of occluding and releasing lithium, a functional group-containing vinylidene fluoride polymer is used as the binder of the positive electrode and / or negative electrode. And polar polymer of non-aqueous electrolyte. -17- (14) 200410439 Adhesive composition for battery electrode. It is known that an electrode with excellent bonding and a battery with excellent safety can be obtained.

-18--18-

Claims (1)

200410439 (υ 拾、申請專利範圍 1 · 一種非水電解液電池電極用黏合劑組成物，係具 備可吸藏·放出鋰之正極及負極之非水電解液電池之正極 及/或負極之結合劑使用之黏合劑組成物，其特徵爲至少 含官能基之偏氟乙烯系聚合物及分子內含羥基及/或羰基 之極性聚合物所成。 2 ·如申請專利範圍第1項之非水電解液電池電極用 黏合劑組成物，其中負極係由碳元素材料所成。 馨 3 ·如申請專利範圍第1項之非水電解液電池電極用 黏合劑組成物，其中含官能基之偏氟乙烯系聚合物之官能 基至少係羧基及環氧丙基之一種。 4.如申請專利範圍第1至第3項中任一項之非水電 解液電池電極用黏合劑組成物，其中分子內含羥基及/或 羰基之極性聚合物係至少一種由乙烯乙烯基醇共聚物、纖 維素系聚合物、聚丙烯酸系聚合物、聚乙烯基吡咯烷酮及 乙烯基苯酚系聚合物所成者。 · 5 · —種非水電解液電池電極用電極去極化合劑，其 特徵爲含如申請專利範圍第1至第4項中任一項之黏合劑 組成物與電極活性物質。 6 · —種非水電解液電池電極用電極，其特徵爲集電 體上具有由如申請專利範圍第5項之電極去極化合劑所成 之電極去極化層。 7 · —種非水電解液電池，其特徵係正極及負極至少 一方爲含如申請專利範圍第6項之電極。 -19- 200410439 柒、（一）、本案指定代表圖為：無 (二）、本代表圖之元件代表符號簡單說明： 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：200410439 (υ, patent application scope 1) A binder composition for electrodes of non-aqueous electrolyte batteries, which is a binder for positive and / or negative electrodes of non-aqueous electrolyte batteries that can store and release lithium positive and negative electrodes The adhesive composition used is characterized by being made of a vinylidene fluoride polymer containing at least a functional group and a polar polymer containing a hydroxyl group and / or a carbonyl group in the molecule. 2 · Non-aqueous electrolysis as described in item 1 of the scope of patent application Adhesive composition for electrode of liquid battery, in which the negative electrode is made of carbon material. Xin 3 · As the adhesive composition for electrode of non-aqueous electrolyte battery according to item 1 of the patent application scope, the functional group contains vinylidene fluoride. The functional group of the polymer is at least one of a carboxyl group and an epoxy group. 4. The adhesive composition for a non-aqueous electrolyte battery electrode according to any one of claims 1 to 3, wherein the molecule contains At least one kind of polar polymer of hydroxyl group and / or carbonyl group is polymerized from ethylene vinyl alcohol copolymer, cellulose polymer, polyacrylic polymer, polyvinylpyrrolidone and vinylphenol · 5 · —A kind of electrode depolarizing agent for non-aqueous electrolyte battery electrodes, which is characterized by containing a binder composition as described in any one of claims 1 to 4 and an electrode active material 6 · An electrode for non-aqueous electrolyte battery electrodes, characterized in that the current collector has an electrode depolarizing layer formed of the electrode depolarizing mixture as described in item 5 of the patent application scope. 7 ·-Non-polar The water electrolyte battery is characterized in that at least one of the positive electrode and the negative electrode is an electrode including the item 6 in the scope of patent application. -19- 200410439 柒, (1), the representative representative of the case is: None (2), the representative representative of the Brief description of the component representative symbols: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention:
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