TW200423449A - Secondary cell with polymer coated anode - Google Patents
Secondary cell with polymer coated anode Download PDFInfo
- Publication number
- TW200423449A TW200423449A TW093102488A TW93102488A TW200423449A TW 200423449 A TW200423449 A TW 200423449A TW 093102488 A TW093102488 A TW 093102488A TW 93102488 A TW93102488 A TW 93102488A TW 200423449 A TW200423449 A TW 200423449A
- Authority
- TW
- Taiwan
- Prior art keywords
- anode
- battery
- tin
- lithium ions
- cell
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 37
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000002033 PVDF binder Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011713 Li4.4S Inorganic materials 0.000 description 1
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- -1 LixCo02 Chemical compound 0.000 description 1
- 229910001091 LixCoO2 Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
-
- 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
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
200423449 玖、發明說明: 【發明所屬之技術領域】 本發明係關於一種二次電池,其中該陽極包含一當第 一次充電及放電時會歷經結構改變的材料,諸如砂或錫; 及關於一種製造此電池之方法。 【先前技術】 數年來已熟知製ia —種具有鋰金屬陽極且可夾入或插 入鋰離子的陰極材料之電池。廣泛多種的夾入或插入材料 已熟知可作爲可再充電式鋰電池之陰極材料,諸如TiS2或 V6〇13。爲了避免在循環期間於鋰金屬陽極處引發樹模石生 長的問題,已建議使用一夾入材料(諸如碳)作爲陽極材 料。在此實例中,該陰極材料通常爲一初始包含鋰離子(諸 如LixCo02,其中X少於1)的夾入材料。此型式之可再充電 電池(其中陽極及陰極二者皆包含夾入的鋰離子)現在可商 業購得,且指爲鋰離子電池或指爲鞦韆或搖椅電池。已建 議將一些不同的含碳材料(諸如煤焦、石墨或碳纖維)使用 在陽極上。商業上通常使用石墨,但是此材料在商業電池 上的容量已接近理論上LiC6的極限(372毫安培小時/克)。 因此,已建議另一種陽極材料來增加電極容量;且在此方 面,錫及矽電極具有理論上顯著較高容量的優勢:Li4.4S η 爲994毫安培小時/克及Li4.4Si爲4198毫安培小時/克。但 是其在鋰離子插入期間將發生非常大的體積改變,此會導 致電極材料斷裂,因而具有差的循環性能。 【發明內容】 本發明提供一種製造二次鋰電池的陽極之方法,其包 200423449 括:將鋰離子電化學插入陽極,該陽極包含一當第一次充 電及放電時會歷經結構改變的材料;然後電化學移除鋰離 子;隨後將一包含聚合材料的層塗佈至該會歷經結構改變 之材料。 根據本發明,可利用下列方法來製造二次鋰電池之陽 極,該方法包括:製造一陽極,其包含一當第一次充電及 放電時會歷經結構改變的材料;組合一電池,其包含該陽 極、一含鋰離子的陰極及一含鋰離子的電解質;讓電流通 過該電池,以便讓鋰離子插入該會歷經結構改變的材料, 因此充電該電池,然後放電該電池;從該電池移出該陽極, 且淨化該會歷經結構改變的材料表面;及以一包含聚合材 料的層被覆該會歷經結構改變的材料。 然後,可藉由組合此被覆陽極與一合適的陰極及一電 解質來製造二次鋰電池。 該當第一次充電及放電時會歷經結構改變之材料,較 佳爲第IV族元素,更佳爲矽或錫,最佳爲錫。該材料在該 陽極中典型爲層的形式。 在較佳的具體實施例中,用來製造二次鋰電池用之陽 極的方法包括:將鋰離子電化學插入一包含錫層的陽極; 然後電化學移除鋰離子;隨後以一包含聚合材料的層被覆 該錫層。 在另一個較佳的具體實施例中,用來製造二次鋰電池 用之陽極的方法包括:製造一包含錫層的陽極;組合一電 池,其包含該陽極、一包含鋰離子的陰極及一包含鋰離子 的電解質;讓電流通過該電池,以便讓鋰離子插入錫中, 200423449 因此充電該電池,然後放電該電池;從該電池移出陽極且… 淨化該錫表面;及以一包含聚合材料的層被覆該錫層。 · 而了解的是,使用於該被覆的聚合材料必需與欲使用 在一次電池中的電解質相容,且必需不會阻礙鋰離子傳遞 至該會歷經結構改變的材料及從其傳遞出鋰離子。因此, 聚口材料可爲在聚合物電解質中所使用的型式。例如, 其可包含PVdF(聚偏二氟乙烯)同聚物、或聚偏二氟乙烯共 聚物、或聚環氧乙烷聚合物。該聚合材料可爲一種多微孔 性聚合物、一種經塑化的聚合物、一種凝膠聚合物或一種肇 聚合物電解質。其可藉由從一在合適的鑄塑溶劑中之溶液 來被覆或藉由積層來塗佈。此被覆已驚人地發現可抑制當 電池連續循環時電池性能之降低。 較佳的是’該塗佈步驟包括真空浸漬該會歷經結構改 變的材料,以保証該聚合物可滲入在該層中的全部裂痕 內。 現在,將僅藉由實例且參考至伴隨的圖形來進一步及 更特別地描述本發明。 φ 【實施方式】 錫陽極可藉由將錫電鍍到一已經酸處理之銅箔上而製 得。在電鍍後,退火該經電沉積的錫陽極。第1圖顯示出 該錫的表面。然後,將該陽極與Li Co02陰極及包含1M的 LiPF6之碳酸次乙酯與碳酸丙二酯(2 : 1,以體積計)的電解 質組合在一電池中。以0.125毫安培/平方公尺來充電該電 池3.8小時,然後完全放電。拆開該電池,以碳酸二甲酯 沖洗該錫電極,讓其乾燥。第2圖顯示出在此階段的錫表 200423449 面。需了解的是,已發生明顯的結構改變。特別是錫已發 展出裂痕。至於刻度尺標誌’該彳奉代表15微米的距離° 實例1 然後,藉由將1克的PVdF溶解在3克的EC及32克 的DMC中,以製備一在碳酸二甲酯/碳酸次乙酯中的同聚 物PVdF溶液’且升溫此混合物以保証溶解。然後’將該經 循環的錫電極浸入該聚合物溶液中’且將該溶液曝露至真 空1 0秒的時間,以保証讓任何存在於錫表面的裂痕中之氣 體逸出,以便讓該聚合物滲入任何此裂痕中。然後移出電 極,風乾,然後在室溫下真空乾燥1 6小時。因此,形成一 聚合物被覆電極。 然後製造一測試電池,其每個電池皆爲一 3電極的測 試電池,其含有一如上述所製造之被覆錫陽極、一鋰金屬 參考電極及一包含LiCo02的陰極。該電解質由包含1M的 LiPF6之碳酸次乙酯及碳酸丙二酯(2: 1,以體積計)所組成, 該些電極由多孔的PVdF聚合物分離器所分隔,且將該電池 真空封裝在鋁積層封裝材料中。 然後,在0.01伏特至2.00伏特之電壓限制(此爲該陽 極相對於該鋰參考電極的電壓)間,以0.125毫安培/平方公 分的恆定電流重覆循環那些測試電池。現在參照至第3 圖’以標記A顯示出多個以此方法製造的電池其連續循環 的循環效率。爲了比較,亦顯示出一比較電池的結果,其 中以精確相同的方法來被覆該陽極,但是該陽極未經先前 的預循環,此標記爲C。在超過50個充電及放電循環下, 本發明之電池的電池效率會從約 98.5%向下降低至約 200423449 9 4 · 0 %,而比較電池則會向下至約9 3.2 %。 需了解的是,該聚合物被覆可與在此實例中所描述的 ^ 不同,在隨後的實例中將描述某些其它聚合物被覆。 實例2 藉由將1克的共聚物溶解在3克的EC及30克的DMC 中,來製備一含有6%六氟丙烯的偏二氟乙烯六氟丙烯共聚 物溶液,加熱此混合物以保証溶解;在該混合物中亦溶解 0.4克的LiPF6。如在實例1中般,然後將一經循環的錫電 極浸入該聚合物溶液中,且將該溶液曝露至真空10秒的時 φ 間,以保証任何存在於錫表面的裂痕中之氣體逸出,以便 讓該聚合物滲入任何此裂痕中。然後移出此電極,風乾, 然後在室溫下真空乾燥1 6小時。因此可形成一聚合物被覆 電極,該聚合物被覆包含PVdF/HFP共聚物、EC增塑劑及 鋰鹽。 如實例1般精確地製造出測試電池,且以相同方法循 環。 實例3 · 藉由將5克的聚合物及0.36克的Li BF4溶解在15克的 碳酸次乙酯與30克的碳酸二甲酯之混合物中,來製備一包 含PVdF同聚物的溶液。加熱該溶液以保証溶解。如在實例 1中般,將一經循環的錫電極浸入該聚合物溶液,移出且 排掉過量的溶液。真空乾燥該電極過夜。因此形成一聚合 物被覆電極,該聚合物被覆包括PVdF聚合物、EC增塑劑 及鋰鹽。 以類似於實例1的那些方法來製造一測試電池,但是, 200423449 於此實例中該電解質爲包含1M的LiBF4的碳酸次乙酯/二 碳酸乙酯。 · 使用此相同聚合物溶液來塗佈一未經循環的錫電極, 但是此聚合物薄膜的黏附性不好。 實例4 藉由將2.7克的PEO及0.8克的Li BF4溶解在47克的 碳酸二甲酯及14克的碳酸次乙酯中,來製造一包含聚(環 氧乙烷)的溶液。如在先前實例中般,將一經循環的錫電極 浸入該溶液、移出且排掉過量溶液。真空乾燥該電極過夜。 φ 於此實例中,該聚合物被覆包含PEO聚合物、EC增塑劑及 鋰鹽。 如在實例3中般製造出測試電池。 【圖式簡單說明】 第1及2圖各別爲在第一循環前及後之錫電極的掃描 式電子顯微圖;及 第3圖顯示出不同電池在連續循環時的電池效率變化 圖0 掴 -10-
Claims (1)
- 200423449 拾、申請專利範圍: 1·—種製造一次鋰電池用陽極之方法’其包括··將鋰離子 以電化學插入一陽極,該陽極包含一當第一次充電及放 電時會歷經結構改變的材料;然後電化學移除鋰離子; 隨後將一包含聚合材料的層塗佈至該會歷經結構改變的 材料。 2.如申請專利範圍第丨項之方法,其包括··製造一陽極, 該陽極包含一當第一次充電及放電時會歷經結構改變的 .材料;組合一電池,其包含該陽極、一包含鋰離子的陰 極及一包含鋰離子的電解質;讓電流通過該電池,以便 讓鋰離子插入該會歷經結構改變的材料,因此充電該電 池,然後放電該電池;從該電池移出該陽極,且淨化該 會歷經結構改變的材料表面;及以一包含聚合材料的層 被覆該會歷經結構改變的材料。 3 ·如申g靑專利範圍第2項之方法,其包括將該會歷經結構 改變的材料表面與一包含聚合材料的溶液接觸。 4·如申請專利範圍第3項之方法,其包括將該會歷經結構 改變且覆蓋一包含聚合材料的溶液之材料曝露至減壓 下’以輔助從表面裂痕移除氣體。 5 ·如申請專利範圍第2至4項之任何一項的方法,其中該 聚合材料層亦包括鋰鹽。 6·如申請專利範圍第2至5項之任何一項的方法,其中該 聚合材料爲偏二氟乙烯的同聚物或共聚物。 7·如申請專利範圍第丨至6項之任何〜項的方法,其中該 會歷經結構改變的材料爲矽或錫。 200423449 8. 如申請專利範圍第7項之方法,其中該會歷經結構改變 的材料爲錫。 9. 一種二次鋰電池,其倂入一利用如前述申請專利範圍之 任何一項的方法所製造之被覆陽極。 10. —種用具,其倂入一如申請專利範圍第9項之二次鋰電 池。-12-
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| GBGB0302834.7A GB0302834D0 (en) | 2003-02-07 | 2003-02-07 | Secondary cell with tin anode |
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| WO (1) | WO2004070861A2 (zh) |
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| JP5470696B2 (ja) * | 2007-10-31 | 2014-04-16 | ソニー株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
| JP5343516B2 (ja) * | 2008-11-06 | 2013-11-13 | 株式会社豊田中央研究所 | リチウム2次電池用負極、リチウム2次電池及びリチウム2次電池用負極の製造方法 |
| EP2246923A1 (en) | 2009-02-13 | 2010-11-03 | Panasonic Corporation | Anode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| KR101177995B1 (ko) * | 2009-02-27 | 2012-08-29 | 파나소닉 주식회사 | 비수 전해질 이차전지용 음극 및 비수 전해질 이차전지 |
| US8658313B2 (en) * | 2009-09-30 | 2014-02-25 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing electrode, and method for manufacturing power storage device and power generation and storage device having the electrode |
| JP5655494B2 (ja) * | 2010-10-19 | 2015-01-21 | 日産自動車株式会社 | 電極製造方法及び電極の補修剤 |
| JP2014160540A (ja) * | 2011-06-16 | 2014-09-04 | Panasonic Corp | リチウムイオン二次電池用負極とその製造法、およびその負極を用いたリチウムイオン二次電池 |
| TWI494350B (zh) | 2013-09-26 | 2015-08-01 | Univ Nat Taiwan Science Tech | 寡聚物高分子的製備方法及鋰電池 |
| EP3278383A4 (en) * | 2015-03-30 | 2018-09-05 | Solidenergy Systems | Composite coating systems and methods for lithium metal anodes in battery applications |
| WO2016205653A1 (en) | 2015-06-19 | 2016-12-22 | SolidEnergy Systems | Multi-layer polymer coated li anode for high density li metal battery |
| KR102160708B1 (ko) | 2016-09-30 | 2020-09-28 | 주식회사 엘지화학 | 이중 보호층이 형성된 리튬 이차전지용 음극 및 이를 포함하는 리튬 이차전지 |
| US11302917B2 (en) * | 2017-07-28 | 2022-04-12 | Research Foundation Of City University Of New York | Process for making manganese dioxide and its polymorphs reversible |
| EP3840086A1 (en) * | 2019-12-20 | 2021-06-23 | Arkema France | Alkali metal electrodes and methods for preparing the same |
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2003
- 2003-02-07 GB GBGB0302834.7A patent/GB0302834D0/en not_active Ceased
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2004
- 2004-01-16 WO PCT/GB2004/000208 patent/WO2004070861A2/en not_active Ceased
- 2004-01-16 EP EP04702754A patent/EP1590852B1/en not_active Expired - Lifetime
- 2004-01-16 AT AT04702754T patent/ATE339015T1/de not_active IP Right Cessation
- 2004-01-16 US US10/543,418 patent/US20060191794A1/en not_active Abandoned
- 2004-01-16 JP JP2006502192A patent/JP4673289B2/ja not_active Expired - Fee Related
- 2004-01-16 DE DE602004002276T patent/DE602004002276T2/de not_active Expired - Lifetime
- 2004-01-16 KR KR1020057014437A patent/KR101118482B1/ko not_active Expired - Fee Related
- 2004-02-04 TW TW093102488A patent/TWI360248B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE339015T1 (de) | 2006-09-15 |
| TWI360248B (en) | 2012-03-11 |
| EP1590852A2 (en) | 2005-11-02 |
| GB0302834D0 (en) | 2003-03-12 |
| US20060191794A1 (en) | 2006-08-31 |
| WO2004070861A2 (en) | 2004-08-19 |
| DE602004002276T2 (de) | 2007-10-04 |
| JP4673289B2 (ja) | 2011-04-20 |
| WO2004070861A3 (en) | 2005-03-31 |
| DE602004002276D1 (de) | 2006-10-19 |
| KR20050100658A (ko) | 2005-10-19 |
| EP1590852B1 (en) | 2006-09-06 |
| KR101118482B1 (ko) | 2012-03-12 |
| JP2006517719A (ja) | 2006-07-27 |
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