TW480767B - Element, in particular an electrode, for use in a non-aqueous battery, a method of manufacturing such an element, the application of such an element as a cathode, an anode and a separator as well as a battery - Google Patents

Element, in particular an electrode, for use in a non-aqueous battery, a method of manufacturing such an element, the application of such an element as a cathode, an anode and a separator as well as a battery Download PDF

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TW480767B
TW480767B TW089117021A TW89117021A TW480767B TW 480767 B TW480767 B TW 480767B TW 089117021 A TW089117021 A TW 089117021A TW 89117021 A TW89117021 A TW 89117021A TW 480767 B TW480767 B TW 480767B
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Rifat Ata Mustafa Hikmet
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Koninkl Philips Electronics Nv
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/443Particulate material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497Ionic conductivity
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/40Printed batteries, e.g. thin film batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Description

480767 Α7
經濟部智慧財產局員工消費合作社印製 本發明係關於供使用於非水電池中之元件,特別是泰 二’此元件包括由無機,視需要之導電粒子、具有高分; 量之聚合物及含有烴類之化合物所組成之至少一 2二 板。本發明另外係關於製造此元件之方法以及應用此元件 ^作爲陰極、陽極和分離器。本發明另外係關於電池此 I,也係連續由一或數層的電流收集器、陽極、分離哭 極和電流收集器所組成。 ° " 如開頭-段中所述之元件就其本身而論自美國專利説明 曰5,143,8G5號中得知。其中所揭示之元件,特別是陰極電 玉包含微孔片板,它是由具有下列各項之一種&本上均句 組合物所組成之自撑式猪:大概7〇,重量%具有電化活性 且導電之顆粒物料,大概2_3〇重量%具有重量平均分子量 150,〇〇〇至大概5百萬之聚乙烯和〇至大概5重量%之聚乙烯 的有機柔軟劑’及由導電材料所組成之電流收集器,該電 流收集器與微孔片板的至少一面呈密切接觸。 此電極的缺點是少量的無機粒子在聚合物中。少量的無 機粒子降低最後所獲得之電極的活性。但是事實上,增加 無機粒子的數量導致減少微孔片㈣完整性而致使微孔片 板易於形成裂紋及散解。 因此之故,本發明的一個目的在提供一種元件,特別是 電極其中可處理甚大數量的無機粒子。 ' 本發明的另外目的是提供一種元件,特別是電極,儘管 具有高含量的無機粒子,它不易於形成裂紋和散解。 依照本發明,如開頭段中所述之元件其特徵爲:如果使 -4 - 本紙張尺度週用中國國家標準(CNS)A4規格⑽χ 297公楚) ^--------^---------^ (請先閱讀背面之注意事項再填寫本頁) 480767 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(2 ) .-· * 用微孔片板作爲陽極和分離器,該微孔片板包含8〇_99.9重 量%無機’視需要之導電粒子,具有高分子量之〇· 1一2〇重 量〇/❶聚烯烴化合物及〇_20.0重量%聚合物,於接觸電解質 時,此聚合物膨脹;如果使用微孔片板作爲陰極(其中含 有0.1-1.9重量%的定量之具有高分子量之聚烯烴化合物), 則該微孔片板包含80至99·9重量%無機,視需要之導電粒 子及0-20重量%聚合物,於接觸電解質時此聚合物膨脹, 而如果使用微孔片板作爲陰極其中含有19-2〇重量%的定. 量之具有高分子量之聚烯烴化合物,則該微孔片板包含 80-98重量%無機,視需要之導電粒子及〇1_2〇重量。/❶聚合 物,於接觸電解質時,此聚合物膨脹。 顯然可見··如本文中所使用之術語陰極係述及正電極而 術語陽極係述及負電極。 關於具有高分子之聚烯烴化合物.,較佳使用具有自丨_ i 〇 百萬範圍内之重量平均分子量之超高分子量聚乙缔 (UHMWP)或超高分子量聚丙稀·(UHMWPP)。 使用於本發明中之此聚晞烴化合物可另外由具有高分子 量之聚乙烯和具有低分子之聚乙烯混合物所組成。然而, 交替式可能使用具有高分子量之聚乙烯和具有高分子量之 聚丙烯混合物。此種混合物顯示對於高溫之高抗性和低收 縮。 爲了獲得具有高溫穩定性之撓性,導電電極,需要將聚 ,晞烴化合物連接。連接可經由使用游離輻射,電子輻射或 K-輻射而發生。聚合物的數量(在與電解質接觸後此聚合 ------------- ^ · I------^------ I I · ^ (請先閱讀背面之注咅?事項再填寫本頁) -5- 480767 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 B7 五、發明說明(3 ) 物顯示膨脹)範圍較佳自〇 · 1至5重量%而較佳係選自經由聚 苯乙烯、聚氧化乙烯、聚氧化丙烯、聚丙晞酸酯、聚碳酸 酯及其共聚物所形成之該團中。 可將依照本發明之元件適當使周作爲陰極。如果使用該 元件作爲陰極’較佳使用無機粒子例如由下列各氧化物中 選出之粒子·· 3 d -過渡金屬氧化物例如LiMn204,LiCo02, LiNi〇2,視需要可將導電粒子例如碳及/或金屬加至其中。 亦可適‘使用相關之元件作爲陽極。如果使用相關元件 作爲陽極,較佳使用碳及/或石墨作爲無機,導電粒子。 亦可適當使用相關之元件作爲分離器。如果使用相關元 件作爲分離器,較佳使用無機,非電粒子,此等粒子宜選 自陶瓷物料及/或氧化物。關於陶瓷物料,較佳使用
Ll(V+x)A1>cTl(2-x)(p〇4)3及 / 或 Li3xLa(2/3-x)Ti03。關於氧化物, 可適當使用A1203及/或Si02。 本發明另外係關於由一或數層的電流收集器、陽極,、八 離器、陰極和電流收集器所組成之電池,依照本發明之;^ 池其特徵爲:至少一種的下列組件:陰極、陽極和分離器 是上述之陰極、氣極和分離器。 °° 本發明另外係關於製造如上文中所述之元件的方法,梦 方法之特徵爲:將各種出發原料,即:無機,視需要之= 電粒子、聚晞烴化合物和聚合物與一種溶劑混合物,其後 將所產生之混合物供應至擠壓機以便形成箔,其後將、容L 自箔中移出而獲得微孔片板。 ' 依照本發明之方法,可將陽極、陰極和分離器以此種、 -6 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -----------· ^--------訂---------Μ (請先閱讀背面之注意事項再填寫本頁) 480767
五、發明說明(4 經濟部智慧財產局員工消費合作社印製 式製造。如上文中所述,如果製造分離器可使用陶资粒 子0 可隨後使用經如此獲得之元件來製造鋰離子電池。製造 程序可以許多不同方法而進行。可將陽極和陰極經由在壓 力下加熱與電流收集器層合。此操作可以乾態或有溶劑存 在下進,隨後將溶劑自該系統中移出。以此種方式,製造 成連續電流收集器/陽極/分離器/陰極/電流收集器的複合 片板。 另種可能是使陽極、陰極以及分離器連合歷經共擠壓處 理。可將所產生(複合元件隨後提供以電流收集器並配置 而製成電池。 π可能使陽極或陰極連同分離器歷經共擠壓處理。隨後 可將所產生之複合片板材料提供以電流收集器並配置而製 成電池。 依照更另外之方法,在其製造期間,將陽極和陰極兩者 均提供以電流收集器。隨後可將此等自撑式片板材料與習 用,之分離器聯合而製成電池。 可將上文中所述之系統最後提供以有機離子導電之液體 而獲得成品.電池。本發明將藉許多實例予以解釋,不應^ 此等實例解釋爲限制本^明之範圍。 之製诰 製備具有分子量高於1百萬之5 ·3克,内消旋碳微粒,5 克,十氫化萘和〇·〇5克,UHMWPE的混合物。將混合物溶 入一種惰性溶劑中並製成薄膜。在移除過量溶劑後,使薄 本紙張尺度適用1^國國家標準(CNS)A4規格(210 X 297公楚) 1IIIIIIIIII ^ --- ---I I ^ ·1111111! ^ (請先閱讀背面之注意事項再填寫本頁) 480767 經濟部智慧財產局員工消費合作社印製 A7 _ B7___ 五、發明說明(5 ) 膜歷經輥壓操作而獲得微孔片板。 陰極之製造 除去首先製備包含5克LiC 〇02、5克,十氫化萘、0.05克 具有分子量高於1百萬之UHMWPE和〇 · 3克,烟炱之混合 物以外,陰極以與陽極相同之方式而製成。隨後將該混合 物溶入一種惰性溶劑中並以與陽極相似之方式處理。在移 除溶劑後’獲得乾微孔片板。實驗顯示··片板的模數係隨 著聚合物含量增加而增加。 分離器之製造 分離器係使用具有分子量高於1百萬之1克,UHMWPE和 具有大概1 Tm之粒子大小之9克,Li0 55L〜 35Ti03粒子而製 成。將兩種出發原料溶入十氫化萘中其後形成一種多孔聚 合物膜。發現:包含丙烯碳酸鹽溶液中之丨莫耳%]LipF6之 此種薄膜在室溫下的傳導度是1.2 mS/cm。 電池之製造
使用適合陽極之銅電流收集器及適合陰極之鋁電流收集 器,製成由交替陽極,陰極和分離器各層所組成之電池。 隨後將該電池浸沒入1 : 1 EC ·· DEC溶液中之1莫耳LipF 中。蚯後,將電池提供在鋁層合之合成樹脂容器中。可將 電池充電而不須任何外壓(力)。 -8- 本紙張尺度適用中國國家標準(CNS)A4規格(21(^297公髮) (請先閱讀背面之注意事項再填寫本頁) -裝 訂--------

Claims (1)

  1. 480767 A B c D
    第8 9 1 1 7 0 2 1號專利申請案 中文申請專利範圍修正本(90年12月) 六、申請專利範圍 • 一種供用於非水電池中之元件,特別是電極,此元件勹 括由無機,視需要之導電粒子,具有高分子量之聚人= 及含有烴類之化合物所組成之至少一微孔片板,其ς徵 為:如果使用微孔片板作為陽極和分離器,該微孔片 包含80-99.9重量%無機,可能之導電粒子,具有高分子 量〇_1】重量%聚#烴化合物及心2〇重量%聚合物= 觸電解質時此聚合物膨脹;如果使用微孔片板作為陰極 (其中含有0.1-1.9重量%的定量之具有高分子量之聚缔庐 化合物),則該微孔片板包含80至99 9重量%無機,視= 要之導電粒子及0-20重量%聚合物,於接觸電解質時此 聚合物膨脹,而如果使用微孔片板作為陰極其中含有 1.9-20重量%的定量之具有高分子量之聚晞烴化合物, 則該微孔片板包含80-98重量%無機,視需要之導電粒子 及0.1-20重量%聚合物,於接觸電解質時此聚合物膨 脹。 2·如申請專利範圍第1項之元件,其特徵為:使用具有範 圍自1至10百萬之重量平均分子之UHMW-聚乙埽作為具 有高分子量之聚缔烴化合物。 3·如申請專利範圍第1項之元件,其特徵為:使用具有範 圍自1至10百萬之重量平均分子之UHMW-聚丙埽作為具 有高分子量之聚婦烴化合物。 4.如申凊專利範圍第1 _ 3項中任一項之元件,其特徵為: 將具有高分子量之聚缔烴化合物連接。 5·如申凊專利範圍第1 - 3項中任一項之元件,其特徵為: 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 六、申請專利範圍 聚合物的數量範圍自〇·1至5重量%。6·如申請專利範圍第3項中任一一在與電解質接觸後顯示膨脹之聚人:兀件’其特徵為·· 缔、聚氧化乙缔、聚氧化丙埽、;:枝經由聚苯乙 及其共聚物所形成之該團卜,料酿、聚碳酸7· 請專利範圍第Μ项中任一项之元件,其係作為8.:種依:請專利範圍第7項元件所獲得之陰極,其特 τ播機,導電之粒子係選自經由UMn2〇4,Lic〇〇 金1屬該囷中,視需要將導電粒子例如碳及/2 9·=申請專利範圍第山項中任一項之元件,其係作為 酯 陰 徵 ’或 陽 1〇· —種依申請專利範圍第9項元件所獲得之陽極,其特徵 為:無機粒子係選自碳及/或石墨。 11. 如申請專利範圍第"項中任一項之元件,其係作為分 離器。 12. —種依申請專利範圍第i i項元件所獲得之分離器,其特 徵為:無機粒子係選自陶瓷物料及/或氧化物。 13·如申請專利範圍第^ 2項之分離器,其特徵為··使用 Li(1+X)A1xT.1(2-x)(P〇4)3 及/或1^3乂1^(2/3-}〇1^〇3作為陶瓷物 料。 14·如申請專利範圍第1 2項之分離器,其特徵為··使用 ai2o3及/或Si02作為氧化物。 -2- 本紙張尺度適用中國國家標準(CMS) A4規格(210X297公釐) 480767 A8 B8 C8 _______D8 六、申請專利範圍 15. —種由一或數層的電流收集器、陽極、分離器、陰極和 電流收集器及電解質所組成之電池,其特徵為··至少一 種的下列組件·陰極、陽極和分離器是申請專利範圍第 8項之陰極、申請專利範圍第丨〇項之陽極及申請專利範 圍第12項之分離器。 16. —種製造申請專利範圍第^項中任一項之元件的方 法,其特徵為·起始原料是無機,視需要之導電粒子、 一種聚烯烴化合物和一種聚合物、將彼等與一種溶劑混 合,其後將如此獲得之混合物供應至擠壓機而形成羯, 其後將溶劑自箔中移出而獲得微孔片板。 -3- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
TW089117021A 1999-03-31 2000-08-24 Element, in particular an electrode, for use in a non-aqueous battery, a method of manufacturing such an element, the application of such an element as a cathode, an anode and a separator as well as a battery TW480767B (en)

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