TW507392B - Separator for a high energy rechargeable lithium battery - Google Patents
Separator for a high energy rechargeable lithium battery Download PDFInfo
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- TW507392B TW507392B TW090106202A TW90106202A TW507392B TW 507392 B TW507392 B TW 507392B TW 090106202 A TW090106202 A TW 090106202A TW 90106202 A TW90106202 A TW 90106202A TW 507392 B TW507392 B TW 507392B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- 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
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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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Description
507392 A7 B7 五、發明説明(彳) 發明範圍 本文係揭示一種高能再充電鋰電池之分離器和高能再充 電鋰電池。 發明背景 一個高能再充電鋰電池具有能量容積至少為372毫安培-小 時/克(mAh/g)之陽極。此類的陽極包括例如,鐘金屬、經合 金(如·鋰鋁)、及鋰金屬或鋰合金和例如碳、鎳、和銅材料 之混合物。此類的陽極,不包括僅有鋰之陽極。 基於持續不斷的安全問題,商業上成功的鋰金屬或鋰合 金電池,已經避開除了一次電池之外的所有電池。 關於使用前述陽極的困難點,主要係源自於,反覆充電 放電循環後所產生之鋰樹枝體。(然而,如此技術中所熟知 者,樹枝體的生長係任何鋰電池的潛在問題,此問題的嚴 重性對上述高能電池而言,係更甚於其他的鋰陽極(例如·純 碳嵌入的陽極)。當鋰樹枝體成長並穿過分離器時,則會發 生電池内部的短路(任何陰極與陽極的直接接觸均稱為"電 子"短路(electronic shorting),而藉由樹枝體的接觸所造成者 係一種電氣短路之一種)。一些由非常小的樹枝體造成之 短路(亦即,輕微短路(soft short),或許只會降低電池循環效 率。但是,.其他的短路可能會導致鋰電池熱逸散,此係一 個再充電鋰電池嚴重的安全問題。 此陽極樹枝體成長之無法控制,仍為一個問題,而此問 題會限制具有此等陽極之電池(特別是具有液態有機電解質 之電池)的商業化。 O:\70\70012-910606.DOQ 4 - 4 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 2 五、發明説明( 有必要改進咼能再充電鋰電池。 概要 本發明係說明高能再充電鋰 分離器包括至少,組二二也:離"及對應電池。此 層包括Α機 曰 〆一聚合微孔層。陶瓷 ,二Γ二 的混合物和—基質材科。此陶资層,至少 =且:樹枝體的成長並防止電氣短路。聚合物層,至少 U、,..、逸散的情況下,阻播陰極與陽極間離子的流動。 凰·^的詳細銳曰t 為了說月本發明,因此以圖式顯示較佳的形式;然而, 怎知本發明並不受限於所示準確的排列與配置β 圖ι·鍾金屬電池的截面圖 圖2·分離器的橫截面圖 的詳細說明 、圖式中,相同的數字表示相同的元件,此在圖這金屬電 池(battery或cell)1(3中顯示。鐘金屬電池1〇含有一錢金屬陽 極12,一陰極14,和配置在陽極12及陰極14間之分離器μ ,其全部被包裝在罐20内。用以說明的電池1〇為圓柱狀的 電池或”膠凍捲”電池,但本發明並無此限制。其他的構形 ,例如棱形、鈕釦狀電池、或聚合電池亦包括在内。除此 之外,電解‘質並未示出。此電解質可能係液狀(有機或無機 的)或膠狀(或聚合物)。本發明為了方便,將敘述關於具有 液.¾有機電解液圓柱狀電池,但本發明不會因此而受限, 且可以發現可使用於其他電池型態(e.g·能量儲存系統,組 合電池和電容器)和構形。 -5- O:\70\70012*910606.DOC\ 4 本紙張尺度適用中國國家標準(CNS) A4規格(21〇X 297公愛) 507392 A7 B7五、發明説明(3 ) 陽極12之能量容量應大於或等於372毫安培小時/克,較佳 係2 700毫安培小時/克,且最佳係-1000毫安培小時/克。 陽極12可由鐘金屬箔或鐘合金箔(例如.11銘合金),或鐘金 屬及/或鐘合金和例如碳(如焦炭、石墨)、鎳、銅的材料之 混合物構成。陽極12不是單獨只由嵌入含鋰化合物或插入 含鋰化合物而製成。 陰極.14可以是任何能與陽極相容之陰極,且其可包括有 後入化合物、插入化合物、或電化學活性聚合物。合適的 後入材料,包括例如·· MoS2、FeS2、Mn02、TiS2、NbSe3 、LiCo〇2、LiNi〇2、LiMn2〇4、V6〇i3、V2O5、和 C11CI2 0 合 適的聚合物包括例如聚乙炔、聚 咯、聚苯胺、聚吩。 電解質可以為液狀或膠態(或聚合物)。電解質一般主要係 由鹽類和介質組成(例如·液體電解質之介質可以被視為溶劑 :在膠態電解質之介質可為一聚合物基質)。此鹽類可為 鋰鹽。鋰鹽可包括,例如LiPF6、LiAsF6、LiCF3S〇3、 LiN(CF3S03) 3、LiBF6、和 LiC104,BETTE 電解質(可購自明 尼蘇達州明尼亞玻理斯(Minneapolis)之3M公司之商品),和 其結合物。溶劑可包括例如,乙二醇碳酸酯(EC)、丙二醇 碳酸酯(PC)、EC/PC、2-MeTHF(2-甲基四氫 喃)/EC/PC、 EC/DMC(碳酸二甲酯)、EC/DME(二甲基乙烷)、EC/DEC(碳 酸二乙酯)、EC/EMC(碳酸乙基甲酯)、EC/EMC/DMC/DEC 、EC/EMC/DMC/DEC/PE、PC/DME、及 DME/PC。聚合物 基質可以包括例如PVDF(聚偏二氟乙婦)、PVDF : THF(PVDF :四氫喃)、PVDF : CTFE(PVDF :氯三氟乙婦 O:\7O\70012-910606.000 4 -6-
裝 訂
緣 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) A7 B7 4 五、發明説明( )、PAN(聚丙缔)、和pE〇(聚氧化乙缔)。 見圖 其中示出分離器16。分離器16含有一陶资組 :m和氷合微孔層24。此陶資:組合層係至少適於防止 私氣L路(例如·陰極和陽極之直接或物理接觸)和阻擋樹 枝體的成長。聚合微孔層係至少適於在熱逸散期間能阻 擋(或停止)陰極與陽極間離子之傳導(或流動)。分離器16之 Π瓷、、且口層22 ’必須有足夠的傳導性,以使離子能在陰極 與陽極足間流動,而能由電池產生所需量的電流。層22和 24應彼此黏附好,亦即,應該不會發生分離。層22和24可 藉由層壓法、共擠出法、或塗佈法所形成。陶資;組合層22 可以為塗佈層或分離層,此二者之厚度可為0.001微米到50 微米的範圍,較佳係在〇〇1微米到25微米的範圍。聚合微 孔層24較佳為一分離膜,其厚度為5微米到5〇微米的範圍, 較佳係在12微米到25微米的範圍。分離器16整體的厚度係 k 5微米到1〇〇微米的範圍,較佳係在12微米到5〇微米的範 圍。 陶资組合層22含有一基質材料26,其中無機粒子28散佈 於其中不同處。陶瓷組合層22係無孔洞的(當然,一旦與電 解質接觸則可能產生一些孔洞,但層22之離子導電性主要 是決定於所選擇的基質材料26與粒子28)。層22之基質材料 26與前述的聚合物基質(亦即·以上討論有關之電解質介質) 至少在作用上不同。亦即,基質材料26係分離器的一部份 ’其在某種程度上,可藉由防止樹枝體的成長,來防止電 氣短路;而聚合物基質會受限於帶有被解離鹽類之介質(電 O:\70\70012-910606.DOCN 4 本紙張尺度適财目國家標準(CNS) A4规格(2獻297公董) 507392 A7 B7 五、發明説明(5 ) 流藉此在電池中傳導)。除此之外,此基質材料26也可如前 述的聚合物基質(例如.帶著電解質的鹽類)進行相同之作用 。基質材料26約包含陶瓷組成物層22的5-80重量%,無機粒 子28約包含層22的20-95重量%。較佳係組合層22,包含30 重量%-75重量%的無機粒子。最佳係組合層22包含40重量 %-60重量%之無機粒子。 基質.材料26可以為離子導電性或不導電性,所以任何被 建議用於鋰聚合電池或固態電解電池之形成膠體的聚合物 均可使用。基質材料26,可以選自於例如聚氧化乙稀(PEO) 、聚偏二氟乙晞(PVDF)、聚四氟乙晞(PTFE)、聚胺基甲酸 乙酯、聚丙婦 (PAN)、聚甲基甲基丙烯酸酯(PMMA)、聚 四甘醇二丙婦酸g旨、其共聚物、和其混合物。較佳之基質 材料係PVDF和/或PEO及其共聚物。PVDF共聚物包括 PVDF:HFP(聚偏二氟乙婦:六氟丙晞),和PVDF:CTFE(聚偏 二氟乙婦:氯三氟乙婦)。最佳之基質材料包括 PVDF:CTFE(其中 CTFE 少於23重量 %)、PVDFrHFP(其中 HFP 少於28重量%)、任何形式的PEO、與其混合物。 無機粒子28在正常情況下被認為係非導電性的,然而, 當這些粒子與電解質接觸時會顯現出(但是,本發明並不希 望因此而被限制)發展超導的表面,此種表面會改善分離器 16之導電性(降低電阻)。無機粒子28可以選自於例如二氧化 矽(Si02)、氧化鋁(Al2〇3)、碳酸鈣(CaC03)、二氧化鈦 (Ti02)、SiS2、SiP04、和其類似物、或其混合物。較佳之 無機粒子係Si02、Al2〇3、及CaC03。這些粒子的平均粒子 0:V70\70(H2-910606.DOC\ 4 - 8 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 507392 A7 B7 五、發明説明(6 ) 大小範圍係從0.001微米到25微米,最好係在0.01微米到2微 米。 聚合微孔層24包括任何商業上可得到的微孔膜(例如.單層 或多層),例如由北卡羅莱納州之查羅特(Charlotte)西爾 格得公司(Celgard Inc·)、日本東京旭化成(Asahi Chemical) 、和曰本東京多南(Tonen)公司製造。層24孔率的範圍係在 20-80%,較佳係在28-60%。層24的平均孔徑大小範圍係從 0.02微米到2微米,較佳係在0.08微米到0.5微米。層24之葛 利數(Gurley Number)在15到150秒的範圍,較佳係在30到 80秒的範圍。(葛利數係指10 cc的空氣在12.2英吋的水中 ,通過1平方英吋膜的時間)。層24較佳係聚晞烴。較佳之 聚婦烴包括聚乙婦與聚丙烯。聚乙晞係最佳的。 前述之分離器雖然主要被設計使用於高能再充電鋰電池 ,但其亦可用在其他有樹枝體成長問題的電池系統。 前面之敘述將更進一步用下列非限定的例子來說明。 實例 於35 °C,高剪混合下,將60份之細碳酸鈣粒子,40份 PVDF : HFP(Kynar 2801), 溶解在100份的丙酮中3小時。 將此溶液倒在15微米的薄膜上。丙酮在室溫下蒸發後,組 合膜在與2層(8微米)Celgard 2801膜加熱層壓。所得組合關 閉分離器之結構係PE/組合物/PE,其厚度為30微米。 於35eC,高剪混合下,將30份二氧化矽,30份碳酸鈣, 40份PVDF : HFP(Kynar 2801),溶解在100份丙酮中3小時。 將此溶液倒入或塗佈在23微米之聚乙婦微孔層(其由Celgard O:\70\70012-910606.DOQ 4 - 9 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 507392 A7 B7 五、發明説明(7 )
Inc.所製造)上。丙酮在室溫下蒸發後,此聚乙烯/組合物之 薄膜厚度為38微米。 本發明可以其他特定形式具體實施而不會偏離其精神或 主要特質,因此,當表示本發明範圍時,應參考附加之申 請專利範圍而非前述之說明書。 O:\70\70012-910606.DOQ 4 - 1〇 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
Claims (1)
- A B c D 、申請專利範圍 • 一種高能再充電鋰電池之分離器,其包括: 至少一陶瓷組合層,該層包括在基質材料中之無機粒 子混合物;該層至少適於阻擋樹枝體成長並防止電 氣短路;及 至少一聚合微孔層,該層適於阻擋陰極與陽極間離子 的流動。 2·如申請專利範圍第i項之分離器,其中該混合物包括20重 量%到95重量%之無機粒子,和5重量%到8〇重量%之基 質材料。 & 如申4專利範圍第1項之分離器,其中該無機粒子係選自 由下列各物組成之群:Si02、 Al2〇3、 CaC03 、Ti〇2 、SiS2、 SiPCU及其類似物、與其混合物。 4·如申請專利範圍第1項之分離器,其中該基質材料係選自 由下列各物組成之群··聚氧化乙烯、聚偏二氟乙婦、聚四 氟乙烯、聚胺基甲酸乙酯、聚丙晞、聚甲基甲基丙烯 酸、聚四甘醇二丙缔酸酯、其共聚物、和其混合物。 5·如申請專利範圍第1項之分離器,其中該聚合微孔層係聚 缔烴膜。 6·如申請專利範圍第5項之分離器,其中該聚烯烴膜係聚乙 缔膜。 1 · 一種高能再充電鋰電池之分離器,其包括: 至少一陶瓷組合層或塗佈層,該層包括2〇到95重量% 之無機粒子(其係選自由下列各物組成之群:Si〇2、 Al2〇3、CaC〇3、Ti〇2、SiS2、SiP04及其類似物、 O:\70\70012-9106O6.DOO 5 - 1 1 - 本纸張尺度適用中國國家標準(CNS) A4規格(2i〇x297公爱) -m ----—.C8 D8 申請專利範圍 與其混合物)’和5到80重量❶/。之基質材料(其係選自 由下列各物組成之群··聚氧化乙烯、聚偏二氟乙缔 、聚四氟乙缔、前述的共聚物、和其中混合物)之 混合物; 至少一聚埽烴微孔層,其孔率為2〇-8〇%,平均孔徑大 小為0.02到2微米,及葛利數(Gudey Number)為15 到150秒。 8·如申請專利範圍第7項之分離器,其中該無機粒子的平均 t子大小範圍在0.001到24微米。 如申凊專利範圍第7項之分離器,其中該無機粒子係選自 由下列各物組成之群:Si〇2、Ai2〇3、CaC〇3、和其混合 物。 〇·如申4專利範圍第7項之分離器,其中該基質材料係選自 由下列各物組成之群:聚偏二氟乙缔和/或聚氧化乙婦、 其共永物、和其混合物。 11 · 一種高能再充電鋰電池,其包括: 1%極,其含有鍾金屬或鐘合金,或經金屬和/或鐘合 金和其他材料之混合物; 一陰極; 一如申請專利範圍第丨-10項之分離器,其係配置在該 陰極與該陽極之間;和 私解貝’其係藉由該分離器使該陰極與該陽極間進 行離子傳遞。 12· —種用在能量儲存系統之分離器,其包括: O:\70\70012-910606.DOD 5 - 12 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 507392 A8 B8 C8至少一陶瓷組合層或塗佈層,該層包含2〇到95重量% 之無機粒子(其係選自由下列各物組成之群:Si〇2 、Al2〇3、 CaC〇3 、Ti〇2、 SiS2、 SiP〇4及其類 似物、與其混合物),和5到8〇重量。/❶之基質材料(其 係選自由下列各物組成之群:聚氧化乙婦、聚偏二 氟乙烯、聚四氟乙晞、前述共聚物、和其混合物)之 混合物,該層至少適於阻斷樹枝體的成長並防止電 氣知1路;和 至少一聚婦烴微孔層,其孔率為20-80%,平均孔徑大 小為0.02到2微米,及葛利數為15到150秒,該層適 於阻斷陰極與陽極之間的離子流動。 -13- O:\7O\70012-910606.DOC 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)
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2000
- 2000-04-10 US US09/546,266 patent/US6432586B1/en not_active Ceased
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2001
- 2001-03-15 EP EP01106513A patent/EP1146576A1/en not_active Withdrawn
- 2001-03-15 CA CA002340876A patent/CA2340876A1/en not_active Abandoned
- 2001-03-16 TW TW090106202A patent/TW507392B/zh not_active IP Right Cessation
- 2001-03-21 SG SG200101769A patent/SG99897A1/en unknown
- 2001-04-04 KR KR1020010017994A patent/KR20010091048A/ko not_active Application Discontinuation
- 2001-04-10 CN CNB011163534A patent/CN1210821C/zh not_active Expired - Lifetime
- 2001-04-10 JP JP2001110899A patent/JP4570271B2/ja not_active Expired - Lifetime
-
2008
- 2008-11-28 KR KR1020080119658A patent/KR20090005268A/ko not_active Application Discontinuation
-
2010
- 2010-03-22 KR KR1020100025257A patent/KR100990003B1/ko active IP Right Grant
-
2015
- 2015-10-05 US US14/875,434 patent/USRE47520E1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CN1325145A (zh) | 2001-12-05 |
CN1210821C (zh) | 2005-07-13 |
JP2001319634A (ja) | 2001-11-16 |
USRE47520E1 (en) | 2019-07-16 |
US6432586B1 (en) | 2002-08-13 |
CA2340876A1 (en) | 2001-10-10 |
KR100990003B1 (ko) | 2010-10-26 |
SG99897A1 (en) | 2003-11-27 |
KR20010091048A (ko) | 2001-10-22 |
KR20100038350A (ko) | 2010-04-14 |
JP4570271B2 (ja) | 2010-10-27 |
EP1146576A1 (en) | 2001-10-17 |
KR20090005268A (ko) | 2009-01-13 |
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