TW201523968A - 積層電池 - Google Patents
積層電池 Download PDFInfo
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- TW201523968A TW201523968A TW103126954A TW103126954A TW201523968A TW 201523968 A TW201523968 A TW 201523968A TW 103126954 A TW103126954 A TW 103126954A TW 103126954 A TW103126954 A TW 103126954A TW 201523968 A TW201523968 A TW 201523968A
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- Prior art keywords
- lithium
- cathode
- laminate
- anode
- layer
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 100
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000011888 foil Substances 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 30
- 239000011593 sulfur Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical class [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 229910000733 Li alloy Inorganic materials 0.000 claims description 16
- 239000001989 lithium alloy Substances 0.000 claims description 16
- 125000006850 spacer group Chemical group 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims 2
- IBXOPEGTOZQGQO-UHFFFAOYSA-N [Li].[Nb] Chemical compound [Li].[Nb] IBXOPEGTOZQGQO-UHFFFAOYSA-N 0.000 claims 1
- -1 polypropylene Polymers 0.000 description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011800 void material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- VQSLYBNAHOGNCE-UHFFFAOYSA-N pentan-3-yl propanoate Chemical compound CCC(CC)OC(=O)CC VQSLYBNAHOGNCE-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/045—Cells or batteries with folded plate-like electrodes
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Inorganic Chemistry (AREA)
- Primary Cells (AREA)
Abstract
本發明係有關於一含積層之鋰-硫電化學電池,該積層含:一含鋰金屬箔或鋰金屬合金箔之層的鋰陽極;一含一活性硫材料的陰極;一配置於該鋰陰極與該陰極之間的多孔隔離件;及一電解質;其中:該積層係以鋸齒狀構形摺疊;且該陰極係相對於該積層內之鋰陽極而偏移,因此該陰極可自該積層之一側接近,而該鋰陽極可自該積層之反向側接近。
Description
本發明係有關於含一以鋸齒狀構形摺疊之積層的鋰-硫電池。
典型的鋰-硫電池包含一自鋰金屬或鋰金屬合金形成的陽極(負極)、及一自元素硫或其它電活性硫材料形成的陰極(正極)。該硫或含其它電活性硫之材料可以與一導電性材料(諸如碳)混合以改善其導電性。典型上,係粉碎該碳及硫,然後經一溶劑與黏合劑混合以形成一漿體。施加該漿體至一電流收集器,然後乾燥以移除該熔劑。所形成該結構係經壓延以形成一沉積在一電流收集器上之陰極材料的複合片材,其係經切成該所欲形狀以形成一陰極。施加電解質至該陰極,然後將一隔離件放在該陰極上並將一鋰陽極放在該隔離件上。
迄今,鋰-硫電池業經一含數個耗時的步驟之分批方法而製成。例如在進行電池組裝前,必需將陰極材料之複合片材及鋰金屬或鋰金屬合金之片材切割成所欲形狀。詳細地,該等片材之切割方式必需可提供接觸鉛可經焊接
之突出部份或垂片。其可添加該總方法的複雜性。而且,在電池組裝之已知方法內,係以分批方法將陰極、隔離件及陽極之個別、預經切割的個別片材放在彼此之上。此等方法難以自動化。
本發明者已設計可以以有效率且有效的方式組裝之鋰-硫電池。本發明者亦已研發一用於製造一鋰-硫電池的有效率且有效之方法。
在描述本發明之特定實例前,應瞭解本揭示內容並不限於文中所揭示的特定電池、方法或材料。亦應瞭解文中使用之術語係僅用於說明特定實例,且無意具限制性,就如同保護的範圍可藉申請專利範圍及其等之同義字而界定一樣。
在說明並主張本發明的電池及方法之權利時,可使用以下術語:除非內文另有明確表示,單數形式“一”、及“該”包括複數形式。因此,例如凡提及“一陽極”係包括論及此等元素中之一或多者。
根據本發明之一方面,係提供含一積層之鋰-硫電化學電池,該積層包含:一含鋰金屬箔或鋰金屬合金箔之層的鋰陽極;一含一活性硫材料的陰極;一配置於該鋰陰極與該陰極之間的多孔隔離件;及電解質;
其中:該積層係以鋸齒狀構形摺疊;且該陰極係相對於該積層內之鋰陽極而偏移,因此該陰極可自該積層之一側接近,而該鋰陽極可自該積層之反向側接近。
根據本發明另一方面,係提供一製造鋰-硫電池的方法,該方法包含:形成一含以下部份之積層:i)一含鋰金屬或鋰金屬合金箔之層的鋰陽極、ii)多孔隔離件、iii)電解質及iv)一含活性硫材料之陰極,其中該隔離件係配置在該鋰陽極與該陰極之間,且該陰極係相對於積層內之鋰陽極而偏移,因此該陰極可自該積層之一側接近,而該鋰陽極可自該積層之一反向側接近;並以鋸齒狀構形摺疊該積層。
可藉提供呈材料之薄片或網狀物形式(其等可一起經疊層以形成一積層)之該陰極、隔離件及陽極而組裝本發明該電池。因此,有利的是,該積層可以呈材料之流動(例如連續流)網狀物形成。藉相對於該積層內之陽極而偏移該陰極,可自該積層之一側接近該陰極,且可自另一側接近該陽性。因此,有利的是,可自該積層接近該陰極及陽極,且不需在疊層前以任何特定方式切割該陽極或陰極。在一實施例中,該陰極、隔離件及陽極係自網狀物材料之個別軋輥饋入。例如該陰極及陽極材料之軋輥係相對於彼此偏移以確保這些部份在所形成之積層內係呈偏移狀態。因此,
該陰極及陽極可相對於彼此以一和該積層的縱軸呈垂直的方向偏移。以和該積層之縱軸呈垂直的方向偏移之步驟可促進該積層的連續製造,因為陰極及陽極材料之軋輥可方便地以和該陰極及陽極材料之流動呈垂直的方向偏移(見下文)。本發明該電池之一優點在其可以使用連續方法製成。另一優點在該電池適合使用一可方便地經自動化的方法製成。
在一實施例中,係提供呈一材料網狀物、較佳呈一網狀物材料之連續流的形式之該含一活性硫材料的陰極。可施加電解質至該陰極,例如藉使該電解質與該活性硫材料接觸。可以以任何合適方式進行本接觸步驟,例如藉將該電解質噴塗、擠壓、傾倒及/或塗抹在該活性硫材料上。在某些實施例中,可施加該電解質(例如藉噴塗)至該陰極之一移動網狀物,例如以連續或間歇噴塗方式。
在施加該電解質至該陰極前或後(較佳在施加後),可施加一多孔隔離件至該陰極,例如呈網狀物材料之流(例如連續流)的形式之陰極。一旦施加電解質至該陰極時,其較佳浸泡在該隔離件之細孔內。因此,該電解質可濕化該陰極及該隔離件。然後該鋰陽極可以呈網狀物材料之連續流形式疊層至該隔離件上以形成該積層。該積層較佳呈網狀物材料之流(例如連續流)的形式形成,因此,該鋰陽極材料之網狀物及陰極材料之網狀物係相對於彼此以一和該流的方向呈垂直的方向偏移。因此,在一較佳實施例中,該陰極係相對於該陽極以一和該積層的縱軸呈垂直之方向
偏移。在將該積層材料切割成一預定長度之前或後,該積層可以沿著其長度(亦即沿著該積層的縱軸)以鋸齒狀構形摺疊。藉相對於該陰極以一和該積層之縱軸呈垂直的方向偏移,該陰極可自該積層之一側接近,而該陽極可自該積層之反向側接近。該積層較佳在切割前經摺疊。
該積層較佳進一步包含另一鋰陽極及另一含電解質的多孔隔離件。該陰極較佳配置在該等鋰陽極之間,而一多孔隔離件係配置在該陰極與各鋰陽極之間。在一較佳實施例中,該等鋰陰極係經配置致使兩鋰陽極可自該積層之反向側接近。例如該等鋰陽極可彼此對齊。該等陽極可以於該積層之相關側彼此接觸。其可允許單一接觸鉛被用以自該電池內之該等陽極供應並取出電流。該接觸鉛可經焊接至該陽極(群)上。
若該積層包含兩鋰陽極及兩多孔隔離件時,可施加一鋰陽極及多孔狀隔離件至該陰極的各側。在一實施例中,該陰極包含一含沉積在電流收集器之任一側上之活性硫材料及一導電性材料的混合物之層。可有利地施加電解質至該電流收集器之任一側上的該層。在該電解質施加之前及後,可施加一多孔隔離件至該電流收集器之任一側。其後,可施加鋰陽極至各隔離件以形成該積層。如上述,該陰極、隔離件及陽極可呈材料之連續網狀物形式提供。因此,有利的是,可形成呈一連續網狀物形式之該積層。
如上述,該鋰陽極包含一鋰金屬箔或鋰金屬合金箔之層。該鋰金屬箔或鋰金屬合金箔之層可具有20至120微
米、較佳30至50微米之厚度。該鋰金屬箔或鋰金屬合金箔之層的位置最先係與一承載基片接觸。換言之,該陽極原先可呈承載在一基片上之一含鋰金屬箔或合金箔之層的陽極前驅物形式提供。合適的基片包括一聚合物材料(諸如聚丙烯)所形成的基片。在該電池之製造期間且尤其在該疊層步驟期間,該基片可用以承載該箔層。較佳使該箔簡單地與該基片接觸且不需要黏合。在一實施例中,係提供基片材料之軋輥及鋰金屬箔或鋰金屬合金箔之軋輥。可自各該等軋輥分配材料以產生該如網狀物材料流之陽極前驅物。例如可以以連續方式將本網狀物饋入該疊層方法內。較佳在,例如進行該摺疊步驟前,自該積層移除該基片。一旦製成該電池之積層時,可藉簡單地收集在一軋輥上之該基片材料而進行上述移除步驟。
在一較佳實施例中,該鋰鍚極包含一非連續層之鋰金屬箔或鋰合金箔。例如該鋰金屬箔或鋰合金箔層可以每隔一段距離(較佳為沿著該陽極之長度的恆定距離)不存在。在一實例中,該鋰陽極包含一系列沿著該陽極之長度之實質上均勻寬度的區域或細長條,其中該鋰金屬箔或鋰合金箔之層可摺疊。這些“空隙”區域可有利地藉一實質上均勻數量而分隔。較佳,該等空隙區域與該積層經切割以供使用之點相符。有利的是,該等空隙可減少或去除該經組裝電池內之短路風險。因為在切割期間,該陽極經壓擠而接觸該陰極的風險減少或被去除。
可使用任何合適方法以製備該鋰陽極之空隙區
域。例如若該鋰陽極原先包含一位於一基片上之鋰金屬箔或鋰合金箔之層,則可藉切割或削去法而移除該層之區段。在一實施例中,係藉使該鋰陽極通過一對輥之間(其中之一係配備切斷器,其被建構為自該非導電陽極基片切割或剝去該鋰金屬或鋰合金層之區段。其允許當陽極材料之一連續網狀物係饋入該輥之間時,可自該鋰陽極移除該等區段。因此,當該材料以連續方法饋入該疊層方法內時,可形成該等空隙區域。一旦該積層形成時,可藉例如剝離法而移除該基片。
一旦該積層形成時,可以使接觸鉛連接至該積層之易接近的陽極及陰極。然後在一防水之不漏氣容器內密封該積層。
如上述,該陰極包含一電活性硫材料。該電活性硫材料較佳係與一導電性材料摻合。本混合物可形成一電活性層,可以使其與一電流收集器接觸。
該含電活性硫材料及導電性材料之混合物可以在一溶劑(例如水或有機溶劑)內呈漿體形式施加至該電流收集器。然後可移除該溶劑且壓延所形成結構以形成一複合結構。在一較佳實施例中,該電活性硫材料及,可擇地,該導電性材料並未覆蓋該電流收集器之整個區域。例如該電流收集器之邊緣可維持呈暴露狀,因此該陰極之電流收集器可自該積層之一側接近。有利的是,其允許接觸鉛以一方便的方式焊接或黏合至該陰極。
該電活性硫材料可包含元素硫、以硫為基礎的有
機化合物、以硫為基礎的無機化合物及含硫之聚合物。較佳使用元素硫。
該固體導電性材料可以是任何合適的導電材料。本固體導電性材料較佳可以由碳形成。實例包括碳黑、碳纖維及碳奈米管。其它合適材料包括金屬(例如薄片、鐵銼屑及粉末)及導電聚合物,較佳使用碳黑。
該電活性硫材料(例如元素硫)與導電性材料(例如碳)的重量比可以是1至30:1、較佳2至8:1、更佳5至7:1。
該電活性硫材料及導電性材料之混合物可以是一微粒混合物。該混合物可具有50奈米至20微米、較佳100奈米至5微米的平均粒度。
該電活性硫材料及導電性材料(亦即該電活性層)可選擇性包括一黏合劑。合適的黏合劑可自以下中之至少一者形成:例如聚氧化乙烯、聚四氟乙烯、聚雙氬亞乙烯、乙烯-丙烯-二烯橡膠、甲基丙烯酸酯(例如UV可固化甲基丙烯酸酯)、及二乙烯酯(例如熱可固化的二乙烯酯)。
合適的電流收集器包括金屬基片,諸如由一金屬或金屬合金形成之箔、薄片或網狀物。在一較佳實施例中,該電流收集器為鋁箔。
該隔離件可以是允許離子在該電池之該等電極之間移動的任何合適的多孔基片。該基片之孔隙率應該是至少30%、較佳至少50%,例如大於60%。合適的隔離件包括一由聚合物材料形成的網狀物。合適的聚合物包括聚丙烯、尼龍及聚乙烯。非織造聚丙烯更特佳。可使用多層狀
隔離件。
該隔離件應該位於該等電極之間以防止該等電極直接接觸。該隔離件之各該側未必與該陽極或陰極對齊。例如該隔離件可相對於該陰極及/或陽離而偏移。在一實施例中,若該電池包含第一及第二陽極位於一陰極之各側上,則一隔離件可位於該陰極與各陽極之間,因此,在可接近該等陽極之該積層的區域內,該等隔離件可延伸越過該陰極通至一介於該陰極與該等陽極之間的位置。其允許該等陽極沿著該積層之相關側一起壓擠,且該等陽極及陰極並不會直接接觸。有利的是,其可減少或去除該電池短路之風險。
如上述,該電池包含一電解質。該電解質係存在或配置在該等電極之間,其允許電荷在該陽極與陰極之間經轉移。該電解質較佳可濕化該陰極之細孔以及該隔離件之細孔。該電解質較佳包含至少一鋰鹽及至少一有機溶劑。合適的鋰鹽包括以下中之至少一者:六氟磷酸鋰(LiPF6)、六氟砷酸鋰(LiAsF6)、過氯酸鋰(LiClO4)、三氟甲磺醯亞胺(LiN(CF3SO2)2)、硼氟化鋰及三氟甲磺酸鋰(CF3SO3Li)。該鋰鹽較佳為三氟甲磺酸鋰。
合適的有機溶劑為四氫呋喃、2-甲基四氫呋喃、碳酸二甲酯、碳酸二乙酯、碳酸乙基甲酯、碳酸甲基丙酯、丙酸甲基丙酯、丙酸乙基丙酯、乙酸甲酯、二甲氧基乙烷、1,3-二氧伍圜、二乙二酸二甲醚(2-甲氧基乙醚)、四乙二酸二甲醚、碳酸乙二酯、碳酸丙二酯、γ-丁內酯、二氧伍圜、
六甲基磷醯胺、吡啶、二甲基亞碸、磷酸三丁酯、磷酸三甲酯、N,N,N,N-四乙基磺醯胺、與碸及其等之混合物。該有機溶劑較佳為碸、或碸類之混合物。碸之實例為二甲碸及環丁碸。可使用環丁碸作為唯一的溶劑、或可併用,例如其它碸。
用於該電解質內之該有機溶劑應該可溶解,例如含式Sn2-(其中n=2至12)之聚硫化物物種,其等係在該電池放電期間減少該電活性硫材料時所形成。
在該電解質內之鋰鹽的濃度較佳為0.1至5M、更佳為0.5至3M,例如1M。該鋰鹽較佳係以一以下的濃度存在:飽和之至少70%、較佳至少80%、更佳至少90%,例如95至99%。
10‧‧‧積層
12‧‧‧陰極
14‧‧‧隔離件
16‧‧‧鋰陽極
18‧‧‧接觸垂片
100‧‧‧裝置
112、116、120‧‧‧軋輥
114‧‧‧陰極網狀物
118‧‧‧隔離件網狀物
122‧‧‧陽極網狀物
124、124a、124b‧‧‧切割輥
126‧‧‧噴塗裝置
128‧‧‧摺疊元件
130‧‧‧切斷器
132‧‧‧鋰金屬或鋰合金層
134‧‧‧基片
本發明之實施例現在參考以下附圖而經由實例加以說明,其中:圖1為可用於根據本發明之一實施例之電池內的積層之橫截面簡圖;圖2為可用於根據本發明之一實施例之電池內的經摺疊積層之平面簡圖;圖3為可用於根據本發明之一實施例之電池內的經摺疊積層之側視簡圖;圖4為可用以產生一用於根據本發明之一實施例之電池內的積層之裝置的簡圖;圖5a及5b為可用以切割一用於根據本發明之一
實施例之電池內的陰極之輥的簡圖;及圖6a及6b為可用以摺疊一用於根據本發明之一實施例之電池內的積層之摺疊裝置的簡圖。
首先參考圖1,其係描述一用於根據本發明之一實施例之電池內的積層之橫截面圖。該積層10包含一陰極12。隔離件14及鋰陽極16。該陰極12包含一含一活性硫材料及一導電性材料之電活性層(圖中未顯示)。該鋰陽極16係自鋰金屬箔或鋰合金箔形成,且可擇地藉一非導電性基片(圖中未顯示)而承載。如自該圖可知,該陰極12及陽極16係以一和該積層之縱軸呈垂直的方向偏移(其中該縱軸可被視為自該頁伸出或進入該頁內),因此該陰極12可自該積層10之一側接近,而該等陽極可自該積層10之反向側接近。在本實施例內,該等陽極16係經對齊。該等隔離件14經定位或相對於陽極16及陰極12而調整大小,因此,在可接近該等鋰陽極16之該積層10的區域內,該等隔離件14係延伸越過該陰極12通至一介於該陰極12與該等陽極16間之位置。因此,該等鋰陽極16可一起沿著該積層10之該側壓擠,且該等陽極16及陰極12並不會直接接觸。其優點為可減少或去除該電池短路的風險。
現在參考圖2及3,其等係描述一用於根據本發明之一實施例之電池內的呈摺疊構形之積層10。如自圖3可更清楚地瞭解,該積層係以鋸齒狀構形沿著其長度或縱軸摺疊。如自圖2可知,該等陽極16可自該積層10之一側接近,
而該陰極12可自該積層10之另一側接近。可施加接觸垂片18至該等陽極16及陰極12以促進,例如藉焊接而連接至接觸鉛。
圖4為可用以產生一用於根據本發明之一實施例之電池內的積層之裝置的簡圖。該裝置包含一陰極網狀物114之軋輥112、隔離件網狀物118之軋輥116、及陽極網狀物122之軋輥120。該裝置100亦包含用於使該等網狀物通過該裝置之引導軋輥、以及一對用於製備用於疊層(見下文)之該陽極網狀物122的切割軋輥124。該裝置100亦配備用於施加電解質至該陰極網狀物114之兩側的噴塗元件126、以及一以鋸齒狀構形摺疊所製成該積層之摺疊元件128。
該陰極網狀物114包含一含以下材料之電活性層:一活性硫材料(例如硫)及一導電性材料(例如碳)。該層係沉積在一含,例如鋁箔之電流收集器的兩側上。有利的是,該網狀物114之邊緣係維持未受該電活性層覆蓋,因此該電流控制器維持可自所形成該積層接近。
在操作時,該陰極網狀物114係自軋輥112連續饋送。使用噴塗裝置126將電解質噴塗在該移動的網狀物114之兩側上。隔離件網狀物118係連續自軋輥116饋送且疊層至該陰極網狀物114上。其後,陽極網狀物122係自軋輥120連續饋送並疊層至該隔離件網狀物118上。以網狀物形式將所形成積層連續饋至該摺疊元件128,其可以以鋸齒狀構形摺疊該積層。圖6a及6b為該摺疊元件128之放大圖。然後可將該經摺疊積層切割成所欲強度(圖中未顯示)。
該陽極網狀物122原先包含一承載於,例如聚丙烯之基片134上的鋰金屬或鋰合金箔之層132(見圖5a)。在該陽極網狀物122疊層至該隔離件網狀物118上之前,沿著該網狀物122之長度於恆定間隔將其切割以移除該鋰金屬或鋰合金之層的區段。如自圖5a及5b可知,可使用該等切割輥124a及124b以進行切割。輥124b係配備切斷器130,其等係在該輥124b上經分隔。當該陽極網狀物122係經由該等輥124而饋入時,該等切斷器130可自該基片134移除該鋰金屬或鋰合金層132之一部份以得到一空隙區域或細長條,其中該陽極網狀物無鋰金屬箔或鋰合金箔。經由確認該陽極網狀物122係以恆定速率通過該等切割輥124a及124b,可確認該等空隙區域具有實質上均勻大小且實質上係彼此均勻地分隔。這些空隙可將該積層應該被切割的點作記號。有利的是,該等空隙可減少或去除該經組裝電池內之短路的風險,因為在切割期間該陽極被壓擠而與該陰極接觸的風險減少或去除。
一旦該積層形成時,該基片134係自該基片移除。可藉例如焊接而使接觸鉛連接至該積層。然後可將該積層密封在一防水不漏氣的容器(圖中未顯示)內。
10‧‧‧積層
12‧‧‧陰極
14‧‧‧隔離件
16‧‧‧鋰陽極
Claims (15)
- 一種含一積層之鋰-硫電化學電池,該積層包含:一含鋰金屬箔或鋰金屬合金箔之層的鋰陽極;一含一活性硫材料的陰極;一配置於該鋰陰極與該陰極之間的多孔隔離件;及一電解質;其中:該積層係以鋸齒狀構形摺疊;且該陰極係相對於該積層內之鋰陽極而偏移,因此該陰極可自該積層之一側接近,而該鋰陽極可自該積層之一反向側接近。
- 如請求項1之電池,其中該陰極係相對於該鋰陽極以一和該積層之縱軸呈垂直的方向偏移。
- 如請求項1或2之電池,其中於該經摺疊積層之末端處並不存在該鋰金屬箔或鋰合金箔之層。
- 如上述請求項中任一項之電池,其中該陰極包含一含沉積在一電流收集器上之活性硫材料及導電性材料之混合物的層。
- 如請求項4之電池,其中該電流收集器係由金屬箔形成。
- 如上述請求項中任一項之電池,其進一步包含另一鋰陽極及另一多孔隔離件,其中該陰極係配置在該等鋰陽極之間,且一多孔隔離件 係配置在該陰極與各鋰陽極之間,且該等鋰陽極之配置致使兩鋰陽極可自該經摺疊積層之反向側或末端接近。
- 一種製造鋰-硫電池的方法,該方法包含:形成一含以下部份的積層;i)一含鋰金屬或鋰金屬合金箔之層的鋰陽極、ii)一多孔隔離件、iii)電解質;及iv)一含一活性硫材料之陰極,其中該隔離件係配置在該鋰陽極與該陰極之間,且該陰極係相對於該積層內之該鋰陽極而偏移,因此該陰極可自該積層之一側接近,而該鋰陽極可自該積層之一反向側接近;且以鋸齒狀構形摺疊該積層。
- 如請求項7之方法,其中該積層進一步包含另一鋰鍚極及另一含電解質之多孔隔離件,其中該陰極係配置在該等鋰陽極之間,且一多孔隔離件係配置在該陰極與各鋰陽極之間,且該等鋰陽極之配置致使兩鋰陽極可自該積層之反向側接近。
- 如請求項7或8之方法,其包含:提供該呈網狀物材料之流的含一活性硫材料之陰極;施加電解質至該陰極;將該多孔隔離件疊層至該呈網狀物材料之流的陰極上;並將該鋰陽極疊層至該呈網狀物材料之流的隔離件 上以形成該呈網狀物材料之流的積層,其中該鋰陽極材料之網狀物與陰極材料之網狀物係相對於彼此以一和該流之方向呈垂直的方向偏移;其中該電解質係在該多孔隔離件經疊層至該陰極上之前或後,施加至該陰極。
- 如請求項9之方法,其進一步包含以鋸齒狀構形摺疊該積層材料之網狀物並將該積層材料切割成一預定長度。
- 如請求項9至10中任一項之方法,其中該陽極之網狀物材料包含一非連續之鋰金屬箔或鋰合金箔層,且其中該積層係沿著該層之該等非連續處切割。
- 如請求項11之方法,其中該鋰陽極原先係呈一含承載於一基片上之鋰金屬箔或鋰合金箔之層的陽極前驅物提供,且其中,該前驅物係呈一材料之網狀物提供,且沿著該網狀物材料之長度以恆定間隔自該基片移除該鋰金屬箔或鋰合金箔之層的區段。
- 如請求項13之方法,其中該等區段係在該鋰陽極疊層至該隔離件上之前被移除。
- 如請求項12或13之方法,其中該等區段係藉使該前驅物通過一對軋輥而移除,該等軋輥之一係配備被建構為自該基片切割或削去該鋰金屬或鋰合金層之區段的切割器。
- 如請求項12至14中任一項之方法,其進一步包含自該積層移除含該陽極前驅物之基片。
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| CA2920681C (en) | 2024-01-23 |
| WO2015022529A1 (en) | 2015-02-19 |
| US20160204473A1 (en) | 2016-07-14 |
| CN105493331A (zh) | 2016-04-13 |
| GB201405957D0 (en) | 2014-05-14 |
| US10020533B2 (en) | 2018-07-10 |
| JP6351127B2 (ja) | 2018-07-04 |
| CN105493331B (zh) | 2018-11-06 |
| CA2920681A1 (en) | 2015-02-19 |
| GB2517228A (en) | 2015-02-18 |
| JP2016530682A (ja) | 2016-09-29 |
| TWI630744B (zh) | 2018-07-21 |
| EP3033793A1 (en) | 2016-06-22 |
| HK1202710A1 (zh) | 2015-10-02 |
| KR20160044006A (ko) | 2016-04-22 |
| GB2517228B (en) | 2016-03-02 |
| EP3033793B1 (en) | 2019-01-30 |
| ES2711113T3 (es) | 2019-04-30 |
| KR102296847B1 (ko) | 2021-09-01 |
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