JP2021530847A - 金属発泡体のアノードおよびカソードを有するリチウムイオン蓄電池 - Google Patents
金属発泡体のアノードおよびカソードを有するリチウムイオン蓄電池 Download PDFInfo
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- JP2021530847A JP2021530847A JP2021502848A JP2021502848A JP2021530847A JP 2021530847 A JP2021530847 A JP 2021530847A JP 2021502848 A JP2021502848 A JP 2021502848A JP 2021502848 A JP2021502848 A JP 2021502848A JP 2021530847 A JP2021530847 A JP 2021530847A
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- Prior art keywords
- metal foam
- anode
- cathode
- active material
- electrode
- Prior art date
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- 239000006262 metallic foam Substances 0.000 title claims abstract description 159
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 87
- 239000011149 active material Substances 0.000 claims abstract description 79
- 239000002002 slurry Substances 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005266 casting Methods 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 61
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 60
- 239000011148 porous material Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 49
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- 239000002184 metal Substances 0.000 claims description 25
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- 239000000956 alloy Substances 0.000 claims description 20
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- 229910052718 tin Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011888 foil Substances 0.000 claims description 14
- -1 vacuum Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000006183 anode active material Substances 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 12
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011244 liquid electrolyte Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910005177 Ga—Li Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910017859 Sb—Li Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
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- 239000010935 stainless steel Substances 0.000 claims description 3
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- 239000010936 titanium Substances 0.000 claims description 3
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910015118 LiMO Inorganic materials 0.000 claims description 2
- 229910006025 NiCoMn Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
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- 239000007769 metal material Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract description 14
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract description 14
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 description 29
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- 229910052708 sodium Inorganic materials 0.000 description 7
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
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- YYCNOHYMCOXPPJ-UHFFFAOYSA-N alumane;nickel Chemical compound [AlH3].[Ni] YYCNOHYMCOXPPJ-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
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- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LBKMJZAKWQTTHC-UHFFFAOYSA-N 4-methyldioxolane Chemical compound CC1COOC1 LBKMJZAKWQTTHC-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 description 1
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- 239000011812 mixed powder Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1146—After-treatment maintaining the porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
本特許出願は、2018年7月19日付で提出された米国特許出願第62/700,793号の利益を主張し、この特許出願を、本願中で引用される他のすべての先行技術文献とともに、引用により本明細書に援用する。
リチウムイオン蓄電池は、金属発泡体を用いて製造され、アノード電極およびカソード電極に金属発泡体を用いている。金属発泡体のアノード電極およびカソード電極を有するリチウムイオン二次電池は、エネルギー密度の増大、出力の増大、安全性の向上、およびサイクル寿命の延長を目的として、高容量活物質またはこれと標準的なアノード(黒鉛)およびカソード(酸化リチウムコバルトまたはLCO)活物質との混合物が充填された孔を有し得る。アルミニウムまたはニッケル金属発泡体カソードおよび銅アノード金属発泡体を空間保持材法および凍結鋳造法を用いて製造し、続いて、それぞれに、黒鉛、スズ、またはケイ素、または組み合わせ(アノード)、および酸化リチウムコバルト(カソード)のスラリーを被覆および/または充填する。次いで、これら2つの金属発泡体電極を容易に付着させて慣習的なセパレータで分離することによって、孔中に含有される高容量材料とこれに対応して生じる体積膨張への効果的対応性とに起因してサイクル寿命が長くなった高容量リチウムイオン二次電池を形成できる。この新しい電池設計は、リチウムイオン電池製造プロセスのコストを著しく削減でき、慣習的なシート積層電池プロセスに代わってより大きな成功を収め得る。
本特許に係る電池技術は、以下の利点を提供する。慣習的な二次元「シート」積層製造プロセスよりも製造工程が単純で、安全性が向上し、容量が増大し、サイクル寿命が長い革新的な新しい電池設計を提供するために;(「薄い」慣習的な箔電極ではなく)調節された開孔を有する三次元の「厚い」金属発泡体をリチウムイオン二次電池のアノードおよびカソードに使用する。ここで、粉末スラリー状の高容量活物質が表面に被覆されている、または内孔に充填されている、またはその両方である。;一般的なスラリー粒子径および孔の中での拡散距離を考慮して孔サイズの範囲が数十ミクロン〜二、三百ミクロンである多孔質金属発泡体を製造するための任意の加工法が許容され得る。;一方、空間保持材(たとえば、図5)および氷晶テンプレート法(ice−templating)(たとえば、図6)という技術は、大量生産特性に優れ孔サイズを微小スケールで制御できるため、非常に魅力的である。
金属発泡体の内孔に充填された状態で高容量活物質を含有できる多孔質構造を含む革新的かつ単純なリチウムイオン二次電池設計のアノード電極およびカソード電極として使用するための金属発泡体が提供される。孔サイズが十分に小さい(数十ミクロンの桁)三次元構造金属発泡体は、集電体と活物質との接触面積が、従来から集電体として使用されている活物質が二次元被覆された金属箔と比較して大幅に大きい。さらに、この三次元の金属発泡体集電体設計は、リチウムイオン電池の充電プロセスまたは放電プロセスまたはその両方において生じる大きな体積膨張に耐え得て、ゆえに、エネルギー密度の増大、優れたサイクル特徴、および充電効率または放電効率またはその両方の大幅な改善が導びかれる。
このように金属発泡体をアノード電極およびカソード電極の両方として有するリチウムイオン二次電池を作製する一例として、以下の空間保持材プロセスを使用できる(たとえば、図6)。
図5Aおよび図5Bはアルミニウム発泡体集電体(カソード)の顕微鏡写真を示し、図5Cはニッケル発泡体集電体(カソード)の顕微鏡写真を示し、これらはすべて、空間保持材技術を用いて作製したものである。図6中に示すように、市販の塩粉末をアルミナ型の中で約20分間手粉砕して均一に小さな塩化ナトリウム粉末(数十〜数百ミクロンの桁)を得て、これを続いて篩にかけ、塩化ナトリウム粉末のサイズを厳密に制御された範囲(好ましくは30〜100ミクロン)とした。次いで、市販のアルミニウムと篩にかけた塩化ナトリウム粉末とをspex mill機で約30分間、混合またはボールミルまたはその両方に供する。アルミニウムと塩化ナトリウム粉末の混合物を、室温加圧機を用いて約10分間加圧する。加圧したアルミニウムと塩化ナトリウムの混合粉末を、次いで、窒素雰囲気下においてセ氏約650度で数時間焼結させる。最後に、超音波装置を用いて塩化ナトリウム粉末を水に溶解して除去することによって、制御された孔サイズの孔がアルミニウム発泡体中で三次元的に繋がっている調節された孔を得る。
図6は、凍結鋳造技術を用いて二、三〜数十ミクロンの桁の調節された孔をつくることにより作製した銅発泡体集電体(アノード)の光学顕微鏡写真を示す。注目すべきは、この凍結鋳造技術によれば、より小さなサイズの縦長の孔(二、三〜数十ミクロン)を作ることができ、これにより電解質との接触面積が大きくなって電気化学反応が向上し得る点である。孔へのスラリー活物質の充填は、重力送り法(たとえば、図8)を用いて容易に行なうことができる。一方、孔サイズがより小さい場合には、孔充填プロセスをより良好とするために真空引きデバイスが必要とされる場合がある。米国特許出願第13/930,887号は凍結鋳造技術を記載しており、これを引用により本明細書に援用する。このプロセスは単純かつ低コストの加工法であり、大規模多孔質構造の作製に好適である。しかしながら、多孔質金属発泡体の製造プロセスは凍結鋳造法に限定されない。
図8は、酸化リチウムコバルト(LCO)粉末スラリーが首尾よく充填されたアルミニウム発泡体カソードを示す。まず、LCO活物質スラリーを水およびバインダ(必要であればいくらかのカーボンブラックと共に)と混合して、適切な粘度のスラリー状にした。次いで、これをアルミニウム発泡体の上に置き、2、3分間かけてアルミニウム発泡体の孔の中に重力送りし、続いて、必要であればこのプロセスを繰り返すことができる。
Claims (20)
- 円筒型、パウチ型、またはディスク型の「厚い」一体型連続気泡金属発泡体のアノード電極およびカソード電極の少なくとも1つを備え、その内孔の少なくとも一部または全体には、リチウムと反応する1種以上の活物質が充填されている、リチウムイオン二次電池デバイス。
- コインセルは、慣習的なセパレータで分離されていて慣習的な液体電解質で濡れている一体型金属発泡体アノードおよび一体型金属発泡体カソードを備える、請求項1に記載のデバイス。
- 前記コインセルは、一体型金属発泡体アノード(またはカソード)および慣習的な箔カソード(またはアノード)をそれぞれ備える、請求項2に記載のデバイス。
- 前記円筒またはディスクセルは、慣習的なセパレータで分離されていて慣習的な液体電解質で濡れている一体型金属発泡体アノードおよび一体型金属発泡体カソードを備える、請求項1に記載のデバイス。
- 前記円筒またはディスクセルは、一体型金属発泡体アノード(またはカソード)および慣習的な箔カソード(またはアノード)をそれぞれ備える、請求項1に記載のデバイス。
- 前記パウチセルは、慣習的なセパレータで分離されていて慣習的な液体電解質で濡れている一体型金属発泡体アノードおよび一体型金属発泡体カソードを備える、請求項1に記載のデバイス。
- アノードの活物質のキャパシタが比較的大きい前記パウチセルは、一体型金属発泡体アノードと、前記一体型金属発泡体アノードに両側で付着している二体型金属発泡体カソードとを備える、請求項6に記載のデバイス。
- 前記パウチセルは、一体型金属発泡体アノード(またはカソード)および慣習的な箔カソード(またはアノード)をそれぞれ備える、請求項6に記載のデバイス。
- 前記金属発泡体アノードは銅、チタン、鉄、マグネシウム、スズ、またはニッケルの発泡体のうちの少なくとも1種であり、前記金属発泡体カソードはアルミニウム、ステンレス鋼、またはニッケルの発泡体のうちの少なくとも1種である、請求項1に記載のデバイス。
- 前記活物質は、ケイ素、スズ、または黒鉛とケイ素の混合物のうちの少なくとも1種の高容量材料を備えるアノード活物質であってよい、請求項1に記載のデバイス。
- 前記カソードの活物質は、LCO(LiCoO2)、LMO(LiMn2O4)、LMO(LiMn2O4)、LFP(LiFePO4)、NCM(Li(NiCoMn)O2)、NCA(Li(NiCoAl)O2)、およびOLO(Li2MnO.LiMO2)からなる群より選択される、請求項1に記載のデバイス。
- 前記アノードの活物質は、黒鉛に基づく材料、金属に基づく材料、または酸化物に基づく材料、または組み合わせを備え、人工黒鉛、天然黒鉛、ソフトカーボン、ハードカーボン、Sn、Si、ならびにSi−Liに基づく合金、In−Liに基づく合金、Sb−Liに基づく合金、Ge−Liに基づく合金、Bi−Liに基づく合金、Ga−Liに基づく合金、ならびに、SnO2、Co3O4、CuO、NiO、およびFe3O4を含む酸化物に基づく材料からなる群より選択される、請求項10に記載のデバイス。
- 前記多孔質金属発泡体電極を形成する製造プロセスは、約10ミクロン〜約150ミクロンの制御された孔サイズを有する凍結鋳造法を備える、請求項1に記載のデバイス。
- 蓄電池の多孔質金属発泡体電極を形成する製造プロセス方法であって、前記方法は、
セラミック型の中で約5分間〜約60分間にわたり塩化ナトリウム粉末を均一に小さくなるまで(数百ミクロンの桁まで)粉砕またはボールミルに供することのうち少なくとも一方を実施する工程と、
粉砕された前記塩化ナトリウム粉末を篩にかけて、粉末のサイズを40ミクロン〜100ミクロンの範囲とする工程と、
金属と篩にかけた前記塩化ナトリウム粉末とを約5分間〜約60分間にわたって混合またはボールミルに供することのうち少なくとも一方を実施する工程と、
前記金属と塩化ナトリウム粉末の混合物を、室温加圧機を用いて約1分間〜約30分間にわたり約10〜100メガパスカルの圧力下において加圧する工程と、
加圧された前記金属と塩化ナトリウムの粉末の混合物を、セ氏約400〜650度にて約30分間〜数時間、窒素、真空、またはアルゴン雰囲気のうちの少なくとも1つにおいて焼結させる工程と、
超音波装置を用いて約10分間〜数時間かけて前記塩化ナトリウム粉末を水またはその他の任意の塩溶解液中に溶解して除去することによって、金属発泡体中において厳密に制御された孔を得る工程と、
を備える空間保持材法である、方法。 - 前記活物質は、水、バインダ、ならびにスズおよびケイ素などの高容量活物質粉末と混合された黒鉛粉末のスラリー(前記高容量材料の重量パーセントは約0パーセント〜約100パーセントの範囲である)を備える、請求項10に記載のデバイス。
- 前記スラリーの組成および粘度は、重力送りまたは真空引きプロセスがスラリーにとって最良となるように調整される、請求項15に記載のデバイス。
- 前記活物質のスラリーが、前記金属発泡体電極の上に置かれ、金属発泡体の孔の中にゆっくりと重力送りされる、請求項15に記載のデバイス。
- この重力送りにより充填する方法は、前記金属発泡体電極の底から真空引きデバイスで補助される、請求項17に記載のデバイス。
- 充填が完了するまでこのプロセスが乾燥プロセスと共に繰り返される、請求項17に記載のデバイス。
- アノード電極およびカソード電極の両方として金属発泡体を用いて組み立てられるリチウムイオン二次電池デバイスであって、前記金属発泡体は凍結鋳造または空間保持材使用の少なくとも一方によって作製され、作製された前記金属発泡体のアノード電極およびカソード電極は、電解質で濡らされ、組み合わせて円筒型、ディスク型、またはコイン型とされ、セパレータで分離される、リチウムイオン二次電池デバイス。
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