TWI698536B - 具有優異接著性之銅箔 - Google Patents
具有優異接著性之銅箔 Download PDFInfo
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- TWI698536B TWI698536B TW109101364A TW109101364A TWI698536B TW I698536 B TWI698536 B TW I698536B TW 109101364 A TW109101364 A TW 109101364A TW 109101364 A TW109101364 A TW 109101364A TW I698536 B TWI698536 B TW I698536B
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- Prior art keywords
- copper foil
- electrolytic copper
- item
- patent application
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- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011889 copper foil Substances 0.000 title claims abstract description 111
- 239000011800 void material Substances 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 230000008021 deposition Effects 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 21
- 239000011149 active material Substances 0.000 description 18
- 238000000151 deposition Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical group [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/04—Electroplating: Baths therefor from solutions of chromium
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
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- H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K1/181—Printed circuits structurally associated with non-printed electric components associated with surface mounted components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
本揭露係關於具有適合用於鋰離子二次電池之集電體之特性的電解銅箔。該電解銅箔係包括輥筒面及沉積面。該沉積面或該輥筒面之至少一者係具有約0.17至約1.17μm3/μm2之空隙體積(Vv)值。
Description
本揭露係關於具有高耐久性及可加工性之電解銅箔。本揭露亦關於包括該電解銅箔作為組件之鋰離子二次電池。
鋰離子二次電池係具有高能量及高功率密度之組合,使其作為可攜式電子裝置、電動工具、電動車(EVs)、能量儲存系統(ESS)、行動電話、平板電腦、航太應用、軍事應用、及鐵路之技術選擇。電動車(EVs)係包括混合動力電動車(HEVs)、插電式混合動力電動車(PHEVs)、及純電池電動車(BEVs)。若電動車(EVs)取代大部分以化石燃料(例如,汽油、柴油等)作為動力之運輸工具,則鋰離子二次電池將顯著減低溫室氣體排放。鋰離子二次電池之高能量效率亦可允許其用於各種電網應用中,包括改善從風力、太陽能、地熱及其他可再生能源收集之能量的品質,因此有助於其更廣泛地用於建立永續能源的經濟。
因此,鋰離子二次電池引起商業資本以及政府和學術實驗室之基礎研究的強烈興趣。儘管近年來此領域之研究及發展已經大量存在,且鋰離子二次電池當前已在應用中,但對於關於更高容量、更高電流生成以及可進行更多次充電/放電循環從而延長其使用壽命的電池仍存在改善
的需求。此外,需要改善電池之重量以改善其在例如車輛、可攜式電子裝置及航太應用等多種環境中之應用。
鋰離子二次電池通常包括塗佈有活性材料之金屬箔之集電體。銅箔經常用作集電體,蓋因銅係良好之電流導體。由於對較低重量之電池的需求變得越來越迫切,需要更薄之集電體以降低鋰離子二次電池之尺寸及重量。此外,為了增加鋰離子二次電池之電容量,係將諸如矽(Si)、鍺(Ge)及錫(Sn)之材料與高電容量活性材料混合或填充於電池中,會加劇該活性材料之膨脹及收縮以及其所接觸之銅箔上的應力。再者,於一些近期之進展中,為了增加電池之電容量,係將用作電極之銅箔折疊或彎曲並捲繞。如果銅箔在電池使用期間不能承受該活性材料之膨脹及收縮,或不能承受電池製造過程中之折疊及捲繞,則該電池之循環特性受到負面影響。
因此,仍需要改進用於鋰離子二次電池之銅箔。對於具有提升之可加工性及耐久性之更薄銅箔亦存在需求,並且當該銅箔與活性材料組合以提供鋰離子二次電池時,不會因該銅箔與該活性材料之間的分離或者銅箔的斷裂而在高度充放電循環下失效。為了滿足降低鋰離子二次電池之重量並增加其電容量之目標,需要更薄之銅箔,且不會於電池之製造過程中或在電池之使用過程中失效。
總的來說,本文中所述之發明係關於一種銅箔,例如可用作鋰離子二次電池中之集電體之電解銅箔。舉例而言,電解銅箔業經製備為具有如空隙體積(void volume,Vv)之受控特性。
於第一態樣中,本發明係包含一種電解銅箔,係包含輥筒面以及相對該輥筒面之沉積面,其中,該輥筒面及沉積面之至少一者係具有0.17至1.17μm3/μm2之空隙體積(Vv)值。視需要,該輥筒面及沉積面係各自具有0.17至1.17μm3/μm2之空隙體積(Vv)值。視需要,該輥筒面及沉積面之至少一者進一步具有0.16至1.07μm3/μm2之核心部空隙體積(core void volume,Vvc)值。視需要,該輥筒面及沉積面係各自進一步具有0.16至1.07μm3/μm2之核心部空隙體積(Vvc)值。視需要,該輥筒面及沉積面之至少一者進一步具有0.01至0.10μm3/μm2之波谷部空隙體積(dale void volume,Vvv)值。視需要,該輥筒面及該沉積面係各自進一步具有0.01至0.10μm3/μm2之波谷部空隙體積(Vvv)值。視需要,銅箔之表面係包含選自由鋅-鉻塗層、鉻塗層及有機塗層所組成群組之至少一種塗層。視需要,銅箔之表面係包含鉻鍍層。
根據本發明之第一態樣係包括下列一些額外特性。視需要,電解銅箔進一步包括大於5次/μm之疲勞壽命/厚度。視需要,該疲勞壽命/厚度係8至40次/μm。視需要,該電解銅箔係具有2μm至25μm之厚度。
於第二態樣中,本發明係包含用於鋰離子二次電池之集電體,係包含電解銅箔,舉例而言,如本發明之第一態樣所述的電解銅箔。視需要,該集電體復包含與該電解銅箔之沉積面接觸的負極活性材料。視需要,該集電體復包含與該電解銅箔之輥筒面接觸的負極活性材料。
於第三態樣,本發明係包含鋰離子二次電池,係包含集電體,舉例而言,如本發明之第二態樣所述之集電體。
本文中所描述之電解銅箔用於例如鋰離子二次電池時,展現優異特性。除了可製造具有高電容量之輕型二次電池外,使用此等電解銅箔製備之電池亦具有優異之充電-放電循環特性。舉例而言,於鋰離子二次電池之大量充電-放電循環期間,該銅箔與活性材料不會分離或破碎。未受限於特定機制,其意味此等改善之至少一部分係由於該銅箔與活性材料之間的優異接著力,以及該銅箔中斷裂點或失效點的數量減少。
上述發明內容並非試圖代表本發明之所有實施例或所有態樣。反之,前述發明內容僅提供本文闡述的新穎態樣及特徵之示例。當結合所附圖式及申請專利範圍時,由下述用以實施本發明的代表性具體實施例和模式的詳細說明,上述特徵及優點與本揭露的其他特徵及優點將是顯而易見的。
110‧‧‧峰
112‧‧‧孔
114、210、212、214、216‧‧‧區域
由以下例示性實施例的說明結合參考附圖將更佳地理解本發明。
第1圖係顯示3D表面圖以及負載率(material ratio)圖。
第2圖係顯示負載率圖之細節。
本揭露可接受進行各種修改及替代形式。藉由圖式中的示例顯示一些代表性具體實施例,並將於本文中對其詳細描述。惟,應理解的
是,本揭露並不受所揭露之特定形式所限。反之,本揭露涵蓋所有落入本發明之申請專利範圍所定義之精神及範圍內的修飾、等效物及替代物。
應明確理解,所有圖表及圖式之呈遞係僅為示意之用。於圖式之各個圖中,相同之數字係用以表示相似元件,以便理解所揭露之具體實施例。
本文所製造的物品係關於電解銅箔,係具有可量化之特徵且其用作集電體時提供良好之效能。舉例而言,此等電解銅箔可與活性材料組合以提供鋰離子二次電池之負極。於一些具體實施例中,該電解銅箔的特徵在於調整銅箔之空隙體積至特定量。
如本文中所用,銅箔之“輥筒面”係與電沉積過程中使用之輥筒接觸之銅箔表面,而“沉積面”係該輥筒面之相對側,或在形成銅箔之電沉積過程中與電解液接觸之電解銅箔表面。此等術語係關於生產電解銅箔之製造方法,係包括將轉動之輥筒組件部分地浸沒於含有銅離子以及視需要之其他添加劑(如稀土金屬及界面活性劑)之電解液中。因此,於電流之作用下,銅離子被吸引至該輥筒並被還原,導致銅金屬鍍覆於該輥筒之表面上,並於該輥筒之表面上形成電解銅箔。藉由旋轉該輥筒,並於所形成之銅箔隨著該輥筒一起轉出該電解液時移除該銅箔,從而於連續製程形成並從輥筒上移除電解銅箔。舉例而言,該電解銅箔可隨著其形成而被拉離輥筒,並於連續製程中橫越或通過輥。
該電解銅箔係具有影響其特性及用於電池時之最終效能的表面紋理或特徵,其中一個上述特徵係如第1圖所示之空隙體積參數。第1圖係顯示例如電解銅箔之輥筒面或沉積面的3D表面以及用於獲得空隙體積參數之負載率圖的推導。第1圖之左側係代表表面之表面幾何形狀的三維圖示。第1圖之右側係顯示藉由ISO標準方法ISO 25178-2:2012以得到負載率曲線之推導,其係從位於最高的峰110之頂部的0%負載率(material ratio,mr)跨越至mr為100%之最低的谷或孔112之底部。空隙體積(Vv)係藉由將設定在對應於介於0%(峰110之頂部)與100%(孔112之底部)之間的特定負載率(mr)的高度下之表面上方及水平切割平面下方所圍住的空隙之體積積分而計算。舉例而言,mr為70%之Vv係顯示為第1圖之右側曲線圖中之陰影區域114。如本文中所用,除非另有說明,否則所列出之Vv係負載率為10%之Vv。
第2圖係顯示負載率圖與關於各種空隙體積參數所定義的一些關係之更多細節。核心部空隙體積(Vvc)係兩個負載率之間的空隙體積差,例如區域210所示之mr1及mr2之間的空隙體積差。舉例而言,如本文所用,除非另有指明,否則Vvc之計算係選擇mr1為10%且mr2為80%。波谷部空隙體積(Vvv),也稱為谷空隙體積(valley void volume),為特定mr值的空隙體積,如區域212所示之mr為80%的空隙體積。如本文中所用,除非另有指明,否則Vvv以負載率80%計算。在mr1之空隙體積(Vv)係mr1與mr2之間的核心部空隙體積(Vvc)(區域210)與在mr2的波谷部空隙體積(Vvv)(區域212)的總和。其他區域包括波峰部實體體積(peak material
volume,Vmp)(區域214),以及核心部實體體積(core material ratio,Vmc)(區域216)。
於一些具體實施例中,電解銅箔具有介於低值與高值之間的受控範圍內的空隙體積,例如,介於約0.17(μm3/μm2)的低值與約1.17(μm3/μm2)的高值之間。當Vv過低時,例如低於約0.17(μm3/μm2),由於錨固效應(anchor effect)薄弱,銅箔對活性材料之接著力差。換言之,由於材料無法順利錨固至表面,因此其接著性差。相反地,如果Vv過高,例如高於約1.17(μm3/μm2),則該活性材料不能均勻地塗覆在銅箔的表面上。換言之,大的Vv對應於銅箔表面上之大空隙,而活性材料不能有效地填充所有空隙,使銅箔與活性材料層之間留下一些未覆蓋及被覆蓋之空隙。是以,在過低及過高的兩個區域內,活性材料對電解銅箔之接著力皆不佳,且使用不具有該受控範圍內之Vv之銅箔製備的電池可能會顯現出較差的電池特性。
電解銅箔之沉積面或輥筒面之至少一者的Vv值係揭示為在0.17至1.17(μm3/μm2)範圍內,且該值係獨立選自沉積面與輥筒面之間。應明確理解的是,此等範圍係連續範圍且可表示為:0.17、0.18、0.19、0.20、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、
0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、及1.17(μm3/μm2),且每一個值都代表範圍數值之端點。於一些具體實施例中,電解銅箔之沉積面或輥筒面之至少一者的核心部空隙體積(Vvc)值係位於0.16至1.07(μm3/μm2)範圍內,且如針對Vv所述,此等範圍係連續範圍且可由介於0.16與1.07(μm3/μm2)之間的任何範圍或值表示。於一些具體實施例中,電解銅箔之沉積面或輥筒面之至少一者具有波谷部空隙體積(Vvv)值,其係在0.01至0.10(μm3/μm2)範圍內,且如針對Vv及Vvc所述,此等範圍係連續範圍且可由介於0.01與0.10(μm3/μm2)之間的任何範圍或值表示。
如本文中所用,“疲勞壽命”是與電解銅箔之彎曲特徵有關的量化測量,本文中係以疲勞壽命相對於厚度(疲勞壽命/厚度)的值表示銅箔之疲勞壽命,且疲勞壽命測試係詳述如下。銅箔之彎曲特性可能影響如導電碳材料之活性材料對銅箔之接著性,並因此可能影響電池之效能。於一些具體實施例中,銅箔係具有高疲勞壽命,例如疲勞壽命/厚度係大於5次/μm(例如,大於8、10、20或30次/μm)。低疲勞壽命可能產生在充放電循環測試中更容易受影響而失效(例如斷裂)之電解銅箔。
於一些具體實施例中,電解銅箔可用來形成電池。舉例而言,疊片型鋰離子電池或鈕扣型鋰離子電池。因此,於一些具體實施例中,使用該銅箔製成之電極可形成正極,且塗佈於其上之活性材料係正極活性材料。於一些其他具體實施例中,使用該銅箔製成之電極可形成負極,且塗佈於其上之活性材料係負極活性材料。
於一些具體實施例中,該電解銅箔係包括形成於其表面上之防鏽層,且該防鏽層可保護該電解銅箔免於如由於腐蝕造成之劣化。防鏽層可藉由任何已知方法製備,係包括令所形成之電解銅箔浸沒於或通過含有形成防鏽層之添加劑的溶液,或將金屬或合金膜鍍覆(例如,電鍍)於所形成之電沉積片材上。舉例而言,包括鋅、鉻、鎳、鈷、鉬、釩及其組合之任一者或多者之電鍍浴;或形成防鏽層之有機化合物。該過程可為連續製程且係製備該電解銅箔之整體製程的一部分。
如本文中所用,充放電測試係指下述測試:施加橫跨電池之正極及負極之電勢以對該電池充電;隨後將該正極和負極與負載連結,並令電流通過該負載以將該電池放電。這一充放電係表示一次充放電循環。可進行該測試以模擬電池於重複使用方面的表現。“循環壽命”或“充放電循環壽命”係定義為電池在其標稱電容量低於其初始額定電容量之80%之前可執行的充放電循環次數。
於一些具體實施例中,該電解銅箔可作為集電體用於電池(例如,鋰離子二次電池)以及用於裝置中。如本文中所用,裝置係包含其運作需要電能之任何物品或器件。舉例而言,獨立的、隔離的和移動式器件及裝置,其係需要小且輕的電池。可包括但不限於載運工具(汽車、有軌電車、公車、卡車、輪船、潛艇、飛機)、電腦(例如,微控制器、筆記型電腦、平板電腦)、電話(例如,智慧型手機、無線電話)、個人健康監控及維持設備(例如,血糖監測器、心律調整器)、工具(例如,電鑽、電鋸)、照明器(例如,手電筒、緊急照明、標誌)、手持型量測裝置(例
如,酸鹼度測定計、空氣監測裝置)以及居住單位(例如,太空艙中、拖車中、房屋中、飛機內、潛艇內)。
應理解,於本揭露之範疇內,上述及下述提及的技術特徵(諸如實施例)可自由且相互組合以形成新的或較佳的技術方案,為簡要起見省略之。
[實施例]
電解銅箔的製備
使用可旋轉之金屬陰極輥筒及不溶性金屬陽極製備電解銅箔。將該不溶性金屬陽極放置於該金屬陰極輥筒之大約下半部並環繞該金屬陰極輥筒。使用連續電沉積以製造電解銅箔,藉由令硫酸銅電解液流動於該金屬陰極輥筒與不溶性金屬陽極之間,並在陰極與陽極之間施加電流而使銅電沉積在該金屬陰極輥筒上,從而形成電解銅箔。
於一些實驗中,如下表2中所示,於電沉積的形成過程中,以陽極袋(BEIP308W10L20,由台灣恩慈股份有限公司製造)覆蓋陽極,以製備電解銅箔。陽極袋包住陽極但在其位於電解液外的頂部為敞開的,使得氧氣氣泡流出該電解液並遠離該陽極。
於製備未處理之電解銅箔之後,將銅箔從輥筒拉出,並以連續方式藉由導輥使該電解銅箔通過電鍍浴,而用防鏽材料處理電解銅箔之表面。
電解液之組成及鍍覆條件係提供如下。
[電解液]
硫酸(50重量%):75g/L
硫酸銅(CuSO4.5H2O):280g/L
氯離子濃度:15mg/L(來自鹽酸,購自RCI Labscan公司)
硫酸鈰(Ce(SO4)2):0至55mg/L(購自Sigma-Aldrich)
液體溫度:40℃電流密度:33至65A/dm2
[防鏽處理]
三氧化鉻(CrO3):1500mg/L(購自Sigma-Aldrich)
液體溫度:25℃
電流密度:0.5A/dm2
鍍覆時間:1秒
疊片式鋰離子二次電池
如下述般製備疊片式鋰離子二次電池,並進行高C倍率(c-rate)充放電測試。
使用N-甲基-2-吡咯烷酮(NMP)作為溶劑以製備正極漿料及負極漿料。以固液比195重量%(195g之NMP:100g之正極活性材料)配製正極漿料。以固液比60重量%(60g之NMP:100g之負極活性材料)調配負極漿料。正極活性材料及負極活性材料之配方係顯示於表1中。
將正極漿料塗佈於鋁箔上,並將負極漿料塗佈於電解銅箔上。溶劑蒸發之後,壓合負極及正極並切割為所需之尺寸。將正極與負極交替堆疊,並將隔離膜(Celgard Company)夾置於其間,再置於由層疊膜塑造之容器中。該容器係填充有電解液,並將其密封以形成電池。疊片式電池的尺寸為41mm×34mm×53mm。
就高C倍率充電及放電測試(例如,充電-放電測試)而言,充電模式係恆定電流-恆定電壓(CCCV)模式,其中充電電壓係4.2V,且充電電流係5C。放電模式係恆定電流(CC)模式,放電電壓為2.8V,且放電電流係5C。電池之充放電測試係於高溫下(於55℃)執行。
電解銅箔實施例
表2係顯示設計為例示性說明電解銅箔之具體實施例的實驗。於陽極袋一欄中,X係表示不存在陽極袋,而O係表示存在陽極袋。表3係顯示該電解銅箔之所得特性或特徵。於Vv一欄中,△係表示沉積面與輥筒面之間之Vv的差(絕對值)。濕式接著力是指如下文“濕式接著力測試”中所述而製備之負極的濕式接著力。各列係列出7個實施例(E.1至E.7)及5個比較例(C.1至C.5)。
數據尤其顯示,當電解銅箔之至少一側的空隙體積(Vv)為介於約0.17至約1.17μm3/μm2的範圍內時,該銅箔具有高疲勞壽命,具有很強的濕式接著力,且使用此等銅箔製備之電池的循環壽命高。當銅箔之空隙體積(Vv)不在此等範圍內時,疲勞壽命、接著力及循環壽命特性較差。舉例而言,疲勞壽命/厚度小於約8次/μm,濕式接著力測試失敗且循環壽命小於約800。
1 O表示使用陽極袋;X表示不使用陽極袋
測試方法
體積參數
表3中之空隙體積(Vv)係藉由根據ISO 25178-2(2012)之步驟,從實施例及比較例中獲得。以雷射顯微鏡的圖像進行表面紋理分析。雷射顯微鏡為Olympus製造之LEXT OLS5000-SAF,且圖像係於24±3℃之空氣溫度以及63±3%之相對濕度下製成。濾波器設定為未濾波。光源係405nm波長之光源。物鏡係100x倍率(MPLAPON-100xLEXT)。光學變焦設定為1.0x。圖像面積設定為129μm x 129μm。解析度設定為1024像素x 1024像素。條件設定為自動傾斜移除。
以p為10%而q為80%的負載率來計算Vvc,使用80%之負載率計算Vvv,並使用10%之負載率計算Vv。空隙體積之單位為μm3/μm2。
單位面積重量及厚度
單位面積重量係每單位面積之重量。使用具有100mm×100mm之測試試樣以測定面積。重量係藉由微量天平(AG-204型,Mettler Toledo International Inc.)測定,且單位面積重量係透過重量除以面積而計算並轉換單位為公克/平方公尺(g/m2)。
電解銅箔之厚度係使用IPC-TM-650之測試方法2.4.18量測。使用下述公式:
厚度=M/(A ρ):厚度係以微米(μm)計,M係以公克(g)計之樣本重量,A係以平方公尺(m2)計之樣本面積,且ρ係樣本密度。所使用之電解銅箔的密度為8.909g/cm3。
濕式接著力測試
藉由將負極漿料以5m/min之速度塗覆於銅箔之表面上至200μm之厚度,並透過160℃烘箱使其乾燥,以製備負極。隨後,使用壓製機以1m/min之壓速及3000psi之壓力壓製該負極。該壓製機之壓輥的尺寸為φ 250mm×寬250mm,壓輥之硬度為62至65HRC,且壓輥之材料係高碳鉻軸承鋼(SUJ2)。之後將該負極切割成10cm×10cm的片材作為試片,並將其浸沒在60℃的電解液(LBC322-01H,由深圳新宙邦科技股份有限公司(Shenzhen Capchem Technology Co.,Ltd.)製造)中4小時。如果負極漿料從該銅箔上剝離或於與該銅箔之間膨脹,則視為失敗。相反的,如果沒有剝離或膨脹,則視為通過。
疲勞壽命
疲勞壽命係使用標準方法IPC-TM-650 2.4.2.1測試。簡而言之,該方法係包括將薄帶形式之測試試樣(例如,電解銅箔)附接至懸掛有配重之支架,隨後使用具有設定直徑之心軸(mandrel)快速上下振動該測試試樣之中心。測試係使用3FDF型號之疲勞延展性測試儀(Jovil Universal Manufacturing Company)進行。測試試樣係12.7mm×200mm的電解銅箔條。測試條件如下:心軸直徑=0.8mm,振動速度=100次振動/分鐘,用於提供張力之配重=84.6g。為了測試,用膠帶將試樣附接至樣品架上,使得其不能從該樣品架上滑動。此外,對於取樣方向,係切割每一試樣,使得其長邊(200mm)係平行於機器方向。
如本文中所用,術語“包含”或“包括”係關於所要求保護的發明必要的組成物、方法及其各自組分,但該術語可包括未具化之元件,無論其是否為必要。
如本文中所用,術語“主要由...組成”係指代給定具體實施例所需之彼等元件。該術語係允許不實質上影響本發明所主張之具體實施例的基本及新穎或功能特徵的元件之存在。
術語“由...組成”係指代本文中揭示之組成物、方法及其各自組分,其係不包含任何於該具體實施例之描述中未述及之元件。
如本說明書及所附申請專利範圍中所用,除非上下文中明確指出,否則單數形式“一”及“該”係包括複數形式。因此,舉例而言,關於“該方法”之描述係包括一種或多種方法,及/或本文所述類型的步驟
及/或在閱讀本揭露等之後,對於所屬領域具有通常知識者而言是顯而易見的。同樣,除非上下文明確指出,否則詞語“或”係旨在包括“及”。
除了操作的實施例或另外說明以外,在所有情況下,本文中用以表示成分數量及反應條件的數字應理解為皆以術語“約”修飾。術語“約”可意指所指代之值的±5%(例如,±4%、±3%、±2%、±1%)。
若提供一數值範圍,則介於該範圍之上限與下限之間的每一數值且包括該範圍之上限及下限,係視為揭露於本文中。
除非本文另外定義,否則本申請案中使用之科技術語應具有與發明所屬領域中具通常知識者所一般理解之含義。再者,除非文中另有要求,否則單數之術語應包括複數,且複數之術語應包括單數。
應理解,本發明並不限於本文所述之特定方法、方案及試劑等,且此等可變。本文所用之術語的目的僅在於描述特定具體實施例,並非意圖限制本發明之範圍,本發明之範圍僅為申請專利範圍所界定。
本文中揭露之任何包括ASTM、JIS方法的專利、專利申請案及出版物係藉由引用而明確併入本文以作描述及揭露目的之用,例如,此等出版物中描述之方法可與本發明結合使用。此等出版物僅因為其在本申請案之申請日之前公開而提供。這方面之任何內容皆不應理解為承認本發明人無權憑藉先前之發明或出於任何其它原因而先於此等揭露。所有關於日期之敘述或對此等文件內容之陳述係基於申請人可獲得之訊息,而不構成對該等日期或此等文件內容之正確性的承認。
Claims (16)
- 一種電解銅箔,係包含:輥筒面以及相對該輥筒面之沉積面,其中,該輥筒面及沉積面之至少一者係具有0.17至1.17μm3/μm2之空隙體積(Vv)值。
- 如申請專利範圍第1項所述之電解銅箔,其中,該輥筒面及沉積面係各自具有0.17至1.17μm3/μm2之空隙體積(Vv)值。
- 如申請專利範圍第1項所述之電解銅箔,其中,該輥筒面及沉積面之至少一者係進一步具有0.16至1.07μm3/μm2之核心部空隙體積(Vvc)值。
- 如申請專利範圍第1項所述之電解銅箔,其中,該輥筒面及該沉積面係各自進一步具有0.16至1.07μm3/μm2之核心部空隙體積(Vvc)值。
- 如申請專利範圍第1項所述之電解銅箔,其中,該輥筒面及該沉積面之至少一者係進一步具有0.01至0.10μm3/μm2之波谷部空隙體積(Vvv)值。
- 如申請專利範圍第1項所述之電解銅箔,其中,該輥筒面及該沉積面係各自進一步具有0.01至0.10μm3/μm2之波谷部空隙體積(Vvv)值。
- 如申請專利範圍第1項所述之電解銅箔,其復具有大於5次/μm之疲勞壽命/厚度。
- 如申請專利範圍第7項所述之電解銅箔,其中,該疲勞壽命/厚度係8至40次/μm。
- 如申請專利範圍第1項所述之電解銅箔,係具有2μm至25μm的厚度。
- 如申請專利範圍第1項所述之電解銅箔,其表面係包含選自由鋅-鉻塗層、鉻塗層及有機塗層所組成群組之至少一種塗層。
- 如申請專利範圍第1項所述之電解銅箔,其表面係包含鉻鍍層。
- 一種用於鋰離子二次電池之集電體,係包含如申請專利範圍第1項所述之電解銅箔。
- 如申請專利範圍第12項所述之集電體,復包含與該電解銅箔之沉積面接觸的負極活性材料。
- 如申請專利範圍第12項所述之集電體,復包含與該電解銅箔之輥筒面接觸的負極活性材料。
- 一種鋰離子二次電池,係包含如申請專利範圍第12項所述之集電體。
- 一種裝置,係包含如申請專利範圍第15項所述之鋰離子二次電池。
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US16/584,157 | 2019-09-26 | ||
US16/584,157 US10622637B1 (en) | 2019-02-01 | 2019-09-26 | Copper foil with excellent adhesion |
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TW109101372A TWI720784B (zh) | 2019-02-01 | 2020-01-15 | 電解銅箔、電極及包含其之鋰離子二次電池 |
TW109101363A TWI720783B (zh) | 2019-02-01 | 2020-01-15 | 表面處理銅箔、層壓體及用於處理電子訊號的裝置 |
TW109101350A TWI745835B (zh) | 2019-02-01 | 2020-01-15 | 表面處理銅箔及銅箔基板 |
TW109101285A TWI718843B (zh) | 2019-02-01 | 2020-01-15 | 附載體銅箔及銅箔基板 |
TW109101355A TWI722763B (zh) | 2019-02-01 | 2020-01-15 | 表面處理銅箔及銅箔基板 |
TW109101362A TWI705607B (zh) | 2019-02-01 | 2020-01-15 | 用於鋰離子二次電池之負極集電體的銅箔 |
TW109101373A TWI700394B (zh) | 2019-02-01 | 2020-01-15 | 電解銅箔、集電體、電極及包含其之鋰離子二次電池 |
TW109101365A TWI719805B (zh) | 2019-02-01 | 2020-01-15 | 具低傳輸損耗之銅箔 |
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- 2019-09-26 US US16/584,157 patent/US10622637B1/en active Active
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- 2019-11-25 US US16/694,412 patent/US10787751B2/en active Active
- 2019-11-25 US US16/694,434 patent/US10765010B2/en active Active
- 2019-12-16 US US16/715,284 patent/US10772199B2/en active Active
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