TW201212360A - Porous conductive active composite electrode for lithium ion batteries - Google Patents
Porous conductive active composite electrode for lithium ion batteries Download PDFInfo
- Publication number
- TW201212360A TW201212360A TW100134913A TW100134913A TW201212360A TW 201212360 A TW201212360 A TW 201212360A TW 100134913 A TW100134913 A TW 100134913A TW 100134913 A TW100134913 A TW 100134913A TW 201212360 A TW201212360 A TW 201212360A
- Authority
- TW
- Taiwan
- Prior art keywords
- conductive
- composite
- lithium ion
- active
- active material
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000011149 active material Substances 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 6
- 239000004917 carbon fiber Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000007769 metal material Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000004020 conductor Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011834 metal-based active material Substances 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920005598 conductive polymer binder Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- -1 salt salt Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- 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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
-
- 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
- H01M4/624—Electric conductive 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
201212360 六、發明說明： 【發明所屬之技術領域】 本發明係關於鋰離子電池之電極，且更特定言之，係關 於包括活性複合材料之電極，該活性複合材料分散在多孔 導電基質中，該多孔導電基質具有用於鋰離子擴散之通 道0 【先前技術】 鋰離子電池用於諸如行動電話及膝上型電腦之眾多攜帶 型電子器件中。儘管鋰離子電池具有適當特性以用於攜帶 型電子器件，但用於電子車輛之電池通常比當前可用之電 池需要更高容量。已使用不同方法來增大鋰離子電池材料 之容量，包括形成美國專利公開案第201 1/01 14254號、第 2008/0237536 號、第 2010/0021819 號、第 2〇1〇/〇119942 號、第 2010/0143798 號、第 2010/0285365 號及第 2010/0062338號、WO 2008/021961 及 EP 1 207 572 中揭示 之多孔陽極及複合陽極。雖然此等陽極可改良電池效能， 但此項技術中仍需要改良之鋰離子電池電極並同時兼顧到 電極製做便利性，可容易且低廉地大量生產以供大規模地 用於電動車輛及攜帶型電子器件中。 【發明内容】 本發明係關於複合鋰離子電池電極，其係由分散在一導 電性夕孔基質中之活性複合材料形成，該導電性多孔基質 形成於一電流收集器上。該活性複合材料包括分散在一導 電骨系結構上之活性材料的奈米叢集。該活性材料係選自 158655.doc 201212360 ，其粒徑在約1奈米至 一導電聚合物或一導 法或化學接枝法而分 包括Sn、A卜Si、Ti及C之精細顆粒 約10微米之間。該導電骨架包括至少 電細絲。該活性材料係藉由原位聚合 散在該導電骨架上。 導電f夕孔基質包括一導電性聚合黏合劑及鋰離子擴散 通道’該等通道係在將活性複合材料混合在導電性多孔基 質内期間由造孔材料建立。導電顆粒進一步包括於該導電 性多孔基質中。 【實施方式】 詳細地轉至圖式，圖旧繪根據本發明之複合鐘離子電 池電極10 °在圖1之實施例中’電極包括電流收集器20, 其通常為諸如銅之導電金屬板。分散在—導電性多孔基質 40中之活性複合材料3〇安置於電流收集器⑼上。該活性複 合材料包括如圖2最佳所見分散在導電骨架，结構34上之活 性材料32的精細顆粒q性材料32具有精細微粒結構，其 粒徑範圍在約1奈米至約職米。當該電極用做陽極時， 顆粒包括金屬基材料，諸如Sn、Si' Ti或碳基材料（如 石墨、碳纖維、奈米碳管（CNT))，或其組合。在陽極中， 此等材料在充電階段為鋰離子提供極佳之嵌入媒質 (intercalation media)。在放電期間，鋰離子自陽極轉移至 陰極。由於在鋰離子之插入及移除期間引起之體積變化， 在重複之充電及放電循環後，固體金屬活性材料會經受部 分分離（裂成較小顆粒）。使用奈米級顆粒活性材料有利地 避免了此問’且亦提供更大之表面積用於鐘嵌入。 158655.doc 201212360 導電骨架34包括至少一導電聚合物或導電細絲，其中活 性材料32藉由原位聚合法或化學接枝法（將在下文論述）而 分散在該導電骨架上。藉由以此方式將活性材料分凝在導 電骨架上，活性材料在多孔導電基質4〇中之聚結得以避 免，因此增大了本發明進行大規模生產之可製造性。 導電骨架34之例示性導電聚合物包括吡咯（pyrr〇ie)、苯 胺（aniline)或噻吩（thiofuran);或者，諸如奈米碳管或碳奈 米纖維之導電細絲可用作骨架34。如圖2中所見’骨架34 與分散之活性材料32組合而成之開放結構建立鋰離子之微 擴散通道，從而增強活性材料32之嵌入。所得電池之容量 藉由活性複合材料30之結構而增大。當鋰離子在充電及放 電期間插入及移除時，微通道亦有助於適應活性材料顆粒 之膨脹及收縮。 如圖1中所見，活性複合材料30分散在導電性多孔基質 40内。導電性多孔基質40包括導電性聚合黏合劑及鋰離子 擴散通道42，該等通道42係在將活性複合材料混合在導電 性多孔基質内期間由造孔材料建立（下文將論述）。導電性 聚合黏合劑選自經改質之吡咯 '苯胺及噻吩中之一或多 者，或其他合適之導電聚合物（尤其導電率高於約l〇 s/cm 之聚合物）。鋰離子通道42有利地提供鋰於電極層移動至 活性材料32之轉移通路。另外，當在充電及放電期間分別 添加及移除鋰離子時，通道42有助於適應整個活性電極之 膨脹及收縮。在一實施例中，通道經選擇以具有小於電極 之5%之體積百分比。 g 158655.doc 201212360 為了增強多孔基質狀導電性，諸如難5()或6()之至少 —種導電顆粒包括於導電性多孔基質中。在圖以實施例 中’顆粒50為石墨，且顆粒6G為碳黑n亦可選擇其 他導電顆粒用在多孔基質40中。 描述用於製造電極1G之例示性方法。活性複合材料⑽ 形成包括自合適之前驅體溶液（諸如^㈣时驅體 鹽（石肖酸鹽、碳酸鹽等））沈澱出活性材㈣（諸如I &或叫。將前驅體溶液與添加劑（諸如續酸鹽、亞胺及氛 化物）混合，隨後脫水以獲得沈澱物前驅體粉末，其粒徑 約為1，〇微米。在低於攝氏1000度之溫度下於空氣或惰 性環境中對該沈澱物進行熱處理，產生活性材料之還原/ 煅燒粉末；研磨並銑磨以將粒徑減小至小於100微米之範 圍内，較佳約1奈米至10微米。此技術易複製生産電極活 性材料，且具成本效益可大量生產。 為了將分散之活性材料32形成於骨架結構34上，可選擇 若干技術。在一技術中，對碳纖維、奈米碳管及或碳棒進 仃表面處理，以產生鍵結至碳基骨架之_c〇〇H基團。將活 性材料之精細顆粒與添加劑（諸如APTES(胺基丙基三乙氧 基矽烷）、APTMS(3-胺基丙基三甲氧基矽烷）或八？1>八(2_胺 基-5-偶磷基-3戊烯酸））混合，且經沖洗及乾燥以形成經活 化之活性材料粉末。為了在碳骨架結構上形成WOOH基 團’將碳骨架結構與試劑（諸如EDC(N-(3-二曱胺基丙基）_ Ν'-乙基碳化二亞胺）或NHS(N_羥基硫代丁二醯亞胺d混 合。將具有-COOH基團之碳基骨架與該經活化之活性材料 I58655.doc 201212360 粉末之溶液混合 骨架。 以化學方切騎㈣_結至該碳基 在形成分散在骨架上之活性材料之一替代實施例中使 用原位聚合。將Sn、A1、以或Ti之精細顆粒與諸如續酸、 納鹽或續酸鹽之添加劑混合。將此混合物添加至包括„比 咯、苯胺或噻吩之聚合.玄达.％^ 卞口冷液，添加選自諸如三氣化鐵或硫 酸銨之材料之添加劑。聚合較佳在脫氣之溶液中在低於約 攝氏10度以下之溫度發生^所得活性材料複合材料包括分 散在一多孔骨架中之活性材料。 以製備活性材料複合物’活性材料之精細顆粒分散於骨 架上。可接著將該活性材料複合物併入於導電性多孔基質 中而活性材料顆粒不會聚結，因此確保活性材料之大2積 用於鋰嵌入。為了建立導電性多孔基質，將諸如吡咯、苯 胺或噻吩中之一或多者的導電聚合物表面改質以建立黏合 劑，該黏合劑將與活性材料複合物鍵結。將該活性材料複 合物、導電聚合物黏合劑及造孔劑（其可為造孔材料及/或 發泡材料，諸如碳酸鹽（NH4)2C〇3或（：2Η4Ν4〇2)連同另外之 導電顆粒（諸如顆粒50及/或60(石墨、碳黑））混合在一起。 將該混合物塗覆至諸如銅板之電流收集器2〇，且抽空氣體 並蒸發溶劑’從而留下其中分散有活性材料複合物之多孔 導電基質。造孔材料導致原位孔形成，從而建立連續之互 連多孔通道以增強鋰離子轉移。 雖然已於各實施例描述前述發明，但此等實施例並非限 制性的。一般熟習此項技術者將理解眾多變化及修改。應 J58655.doc 201212360 為此等變化及修改包括於所附中請專利範圍之範嘴内。 【圖式簡單說明】 圖1為根據本發明之一實施例之複合鋰離子電池電極的 示意圖。 圖2為用於圖丨之電極中的活性複合材料之示意圖。 【主要元件符號說明】 20 電流收集器 30 活性複合材料 32 活性材料 34 導電骨架結構 40 導電性多孔基質 42 锂離子擴散通道 50 導電顆粒 60 導電顆粒 158655.doc
Claims (1)
- 201212360 七、申請專利範圍： ι· 一種複合鋰離子電池電極，其包含·· 分散在一導電性多孔基質中之一活性複合材料，該導 電性多孔基質形成在―電流收集器上，該活性複合材料 包含分散在-導電骨架結構上或分散在該結構中之活性 材料’該活性材料選自精細難，料精細顆粒具有小 於約10微米之—粒徑，且包括選自以下各者之至少一材 料：金屬基材料，包括Sn、八卜Si、Ti中之—或多者，· 或碳基材料’包括石墨、碳纖維、碳奈米管乃中之 一或多者；或該金屬基材料與該碳基㈣之組合；且該 導電骨架包括至少一導電聚合物或一導電細絲；該活性 材料係藉由-原位聚合法或—化學接枝法而分散在該導 電骨架上； 该導電性多孔基質包括—導電性聚合黏合劑及鐘離子 擴放通道，该等鋰離子擴散通道係在將該活性複合材料 混合在該導電性多孔基質内期間由造孔劑建立，該導電 性多孔基質進一步包括微粒狀導電顆粒。 2. 如請求項1之複合鋰離子電池電極，其中該電流收集器 為一個銅片。 3. 如請求項1之複合鋰離子電池電極，其中該等導電顆粒 為碳黑及/或石墨。 4·如明求項1之複合鋰離子電池電極，其中該導電骨架為 碳纖維及或碳奈米管。 5.如凊求項1之複合鋰離子電池電極，其中該導電骨架為 158655.doc 201212360 導電聚合物。 6. 如請求項丨之複合鋰離子電池電極，其中該電極為一陽 極。 7. 如請求項丨之複合鋰離子電池電極，其中該導電性聚合 黏合劑包括吡咯、苯胺或噻吩中之一或多者。 士凊求項1之複合鋰離子電池電極，其中該造孔劑包括 一造孔材料或發泡材料中之至少一者。 9· 種製造如請求項1之複合鋰離子電池電極之方法，其 中：藉由自Sn、八卜Si或Ti前驅體鹽或其混合物之前驅 體溶液沈澱出Sn、A卜SuiTi中之一或多者而形成該金 屬基活性材料；將該等前驅體溶液與選自磺酸鹽、亞胺 或氮化物中之一或多者的添加劑混合；對該等沈澱物脫 水以獲得粒徑為約丨微米至丨〇〇微米之沈澱物前驅體粉 末；隨後在大致低於攝氏1〇〇〇度以下之溫度於空氣或一 隋f生環境中對该等沈澱物進行熱處理，以產生該活性材 料之一經還原/煅燒之粉末；且進一步研磨或銑磨或者研 磨且銑磨該粉末以將該活性材料之一粒徑減小至小於約 100微米。 10’ 一種製造如請求項1之複合鋰離子電池電極之方法其 中該活性材料之該粒徑在約1奈米至10微米之一範圍 内。 11 ·種製造如请求項1之複合鋰離子電池電極之活性複合 材料之方法’其包含：藉由試劑來活化包括碳纖維、碳 奈米管或碳棒之一骨架材料以形成鍵結至該骨架材料 158655.doc 201212360 之-COOH基團；及將活性材料之精細顆粒與―或多種添 加劑：合，以形成一經活化之活性材料粉末，隨後藉由 將於/合液中之具有鍵結之.⑶如基團的該骨架材料與該 、’·呈活化之活f生材料粉末混合而以化學方式將該活性材料 鍵結至該骨架材料。 12. -種製造如請求項！之複合輯子電池電極之活性複合 材料之方法，其包含：將該活性材料之精細顆粒混合至 包括-導電聚合物之一聚合溶液中，以藉由一多孔導電 骨架分散該活性材料。 13. 如請求項12之方法，其中該導電聚合物包括吡咯、苯胺 或噻吩中之一或多者。 14. 一種製造如請求項丨之複合鋰離子電池電極之方法，其 包含：藉由將該活性材料分散在一導電骨架上或該導電 骨架中而形成該活性複合材料；及將該活性複合材料添 加至包括一導電聚合物之一混合物中，該導電聚合物已 經表面改質以建立黏合劑，該黏合劑將與該活性材料複 合物鍵結以形成一導電聚和黏合劑，且該混合物進一步 包括選自一造孔材料或發泡材料或其組合之造孔劑且進 步包括導電顆粒；及將該混合物塗覆至該電流收集器 以建立一多孔導電基質，其中該活性複合材料及導電顆 粒分散在該多孔導電基質中。 15. 如請求項14之方法，其中該導電聚合物包括吡咯、苯胺 或售吩中之一或多者。 158655.doc -3-
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| DE102016202459A1 (de) | 2016-02-17 | 2017-08-17 | Wacker Chemie Ag | Kern-Schale-Kompositpartikel |
| DE102016202458A1 (de) | 2016-02-17 | 2017-08-17 | Wacker Chemie Ag | Verfahren zur Herstellung von Si/C-Kompositpartikeln |
| US10125274B2 (en) | 2016-05-03 | 2018-11-13 | Baker Hughes, A Ge Company, Llc | Coatings containing carbon composite fillers and methods of manufacture |
| US20190131660A1 (en) * | 2017-10-30 | 2019-05-02 | Ford Global Technologies, Llc | Solid-state battery design using a mixed ionic electronic conductor |
| KR102883984B1 (ko) | 2020-03-09 | 2025-11-07 | 삼성전자주식회사 | 전고체 이차 전지 및 그 제조방법 |
| US12573618B2 (en) | 2020-03-09 | 2026-03-10 | Samsung Electronics Co., Ltd. | All-solid secondary battery and method of preparing the same |
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| CA2506104A1 (en) * | 2005-05-06 | 2006-11-06 | Michel Gauthier | Surface modified redox compounds and composite electrode obtain from them |
| CN101499522B (zh) * | 2008-01-28 | 2011-12-28 | 财团法人工业技术研究院 | 锂电池正极材料、其制造方法及应用此材料的锂二次电池 |
| US8936874B2 (en) * | 2008-06-04 | 2015-01-20 | Nanotek Instruments, Inc. | Conductive nanocomposite-based electrodes for lithium batteries |
| CN101894940B (zh) * | 2010-08-03 | 2012-12-19 | 哈尔滨工业大学 | 用于锂离子电池的多孔硅基负极的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115312777A (zh) * | 2022-09-07 | 2022-11-08 | 湖北亿纬动力有限公司 | 一种低曲折度厚电极及其制备方法和应用 |
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| TWI442618B (zh) | 2014-06-21 |
| US20130045423A1 (en) | 2013-02-21 |
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