CN109742320A - 一种三维多孔铝负极及其铝电池应用 - Google Patents
一种三维多孔铝负极及其铝电池应用 Download PDFInfo
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- CN109742320A CN109742320A CN201811644587.4A CN201811644587A CN109742320A CN 109742320 A CN109742320 A CN 109742320A CN 201811644587 A CN201811644587 A CN 201811644587A CN 109742320 A CN109742320 A CN 109742320A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 112
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000005275 alloying Methods 0.000 claims abstract description 10
- 239000011241 protective layer Substances 0.000 claims abstract description 4
- 239000004411 aluminium Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
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- 238000004062 sedimentation Methods 0.000 claims description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- JAVAMPMGHYGCHA-UHFFFAOYSA-M N1C=NC=C1.[I-].C(C)[N+]1=CC(=CC=C1)C Chemical class N1C=NC=C1.[I-].C(C)[N+]1=CC(=CC=C1)C JAVAMPMGHYGCHA-UHFFFAOYSA-M 0.000 claims description 2
- 229910003322 NiCu Inorganic materials 0.000 claims description 2
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940080818 propionamide Drugs 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 230000001413 cellular effect Effects 0.000 claims 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 229940050176 methyl chloride Drugs 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
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- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
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- 101100247620 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) RCK2 gene Proteins 0.000 description 1
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Classifications
-
- 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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- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明属于新能源电池技术领域，提供一种三维多孔铝负极的制备及其铝电池构筑。三维多孔铝负极包括：沉积于非金属三维基体上的多孔铝、沉积于金属三维基体上的多孔铝、表面具有保护层包覆的三维多孔铝、合金化三维多孔铝材料。通过对三维多孔铝的空间结构、孔道结构及比表面积调控、界面保护及合金化改性，优化电池电化学反应效率及动力学，提高铝负极的电化学稳定性，从而提升典型铝电池的比容量、倍率性能及循环寿命等关键性能。
Description
技术领域
本发明涉及一种三维多孔铝负极的制备及其铝电池应用，属于新能源技术领域。
背景技术
金属铝具有高理论比容量(2978mAh/g,或8034mAh/cm3)、高地壳含量、低成本、安全易操作等优势。因此，近年来铝电池引起了研究者的广泛关注。然而，现有铝电池的负极主要为铝箔，存在界面电化学反应效率低、易于被腐蚀破坏、倍率及循环性能较差、氧化层作用复杂难控等问题与挑战。因此，针对铝电池的界面电化学特性，设计制备高性能铝负极，是提升铝电池综合性能的关键策略之一。
三维多孔铝具有轻质、比表面积大、孔道结构丰富等特征，可作为优良的电极材料。本发明所提供的三维多孔铝结构，具有较高的孔隙率和优良的空间结构，为电池电化学反应提供了高效界面，增强了电解液的储存与传输能力，加速了电化学反应的动力学过程，提高了金属铝的利用效率，增强了电池在高倍率下的性能和库伦效率，并能够有效克服或延缓铝负极在电化学沉积/溶出中的结构破坏和枝晶生长，从而提高铝电池的使用寿命。
发明内容
本发明是为了克服铝箔作为铝电池负极时，存在的电化学效率低、比容量和倍率性能差、易腐蚀破坏、循环性能差等问题，旨在提高铝二次电池的倍率性能和循环寿命等关键性能。
本发明提供一种三维多孔铝负极材料。包括：沉积于非金属三维基体上的三维多孔铝、沉积于金属三维基体上的三维多孔铝、表面具有保护层包覆的三维多孔铝、合金化三维多孔铝材料。三维多孔铝的孔隙率为10％-95％，骨架(即空隙与空隙之间的材料，类似于金属网中网丝的直径)直径为0.005mm-1mm，孔道形貌为开放孔道及部分闭合孔道，孔道尺寸分布为大孔、介孔或微孔的单一或多元分布，孔道取向性包括各向同性及各向异性。孔道形貌参数由三维多孔基体控制，孔道各向异性通过施加机械外力如压缩或拉伸实现。
本发明提供了沉积于非金属三维基体上的三维多孔铝。所述非金属三维基体包含但不限于聚氯酯、聚苯乙烯、聚乙烯、聚氨酯、聚氯乙烯、聚丙烯、酚醛树脂等三维多孔泡沫塑料，及石墨烯、石墨烯组装体、碳纳米管组装体、碳纤维组装体等三维多孔碳材料。所获得多孔铝电极包括非金属三维基体-多孔铝复合电极和去除非金属三维基体的纯多孔铝电极。
本发明还提供了沉积于金属三维基体上的三维多孔铝。所述金属三维基体包含但不限于泡沫镍、泡沫铜、泡沫ZnCu、NiCu、NiCrW、NiFe、NiCrFe合金、纳米孔镍、纳米孔铜、纳米孔金、纳米孔银、纳米孔铂、纳米孔钯等三维多孔金属。所获得多孔铝电极包括金属三维基体-多孔铝复合电极和进一步合金化的多孔铝合金电极。
上述沉积于非金属或金属三维基体上的三维多孔铝负极，通过电化学沉积法或真空蒸镀法沉积制备。电化学沉积法：将非金属或金属三维基体作为阴极，高纯铝作为阳极，铝盐水溶液、铝盐有机溶液或铝基离子液体作为电解液，通过电化学沉积将铝沉积于基体之上，沉积之后进行洗涤和干燥获得。优选阳极为铝箔(纯度：99.99％)，优选电解液为EMICl/AlCl3(1/1.3)型离子液体，优选温度为室温，优选洗涤剂为无水乙醇。真空蒸镀法：将非金属或金属三维基体固定于真空蒸镀仪中，以高纯铝作为靶材，加热蒸发金属铝，沉积于非金属或金属三维基体。优选靶材为铝块(纯度：99.99％)，优选加热法为电加热法。
本发明还提供具有表面包覆层的三维多孔铝，以改善负极的电化学稳定性。所述表面沉积层包括但不限于碳、硅、钛、钨、镍、金、银、铂、钯、锌、碳纳米管、石墨烯、石墨炔、碳纤维、聚乙炔、聚噻吩、聚吡咯、聚苯胺、聚苯撑、聚苯撑乙烯、聚双炔等的一种或几种，通过在三维多孔铝表面高温或气相沉积法技术实现，或前驱体分散液在三维多孔铝表面的反应、吸附、组装等方法实现。
本发明还提供了一种合金化三维多孔铝材料。合金化材料包括但不限于金属镓、铜、铬、铁、镍、铅、铋、锡或银。合金化方式包括但不限于：制备铝基合金再进行真空蒸镀沉积、电沉积等；在制备三维多孔材料的过程中同时进行多元金属的真空蒸镀沉积、电沉积等；将沉积于金属三维基体上的多孔铝进行高温合金化所获得的合金化三维多孔铝。不同金属的比例可以通过前驱体比例控制、热蒸发等方式进行调控。
本发明进一步提供以三维多孔铝负极制备的铝电池，正极为碳材料、硫副族单质及其化合物、过渡金属氧化物或卤化物材料、硫-碳复合材料、三维多孔铝-硫复合材料等，包括但不限于：导电碳纸、石墨粉、乙炔黑、升华硫、沉降硫、单质硒、硫化钼、硫化锡、五氧化二钒等材料；电解液为卤化铝和碱金属卤化物、碱土金属卤化物、咪唑鎓有机盐、吡啶类、酰胺等物质形成的共晶盐，包括但不限于：卤化铝和NaCl、KCl、LiCl、CsCl、MgCl2、BaCl2、NaBr、1-乙基-3-甲基溴化咪唑鎓、1-乙基-3-甲基氯化咪唑鎓、1-乙基-3-甲基碘化咪唑鎓、尿素、甲酰胺、乙酰胺、丙酰胺等形成的共晶盐。所组装的电池结构包括：密封玻璃电解池、Swagelok电池、耐高温软包电池、扣式电池等电池装置。
附图说明
图1是实施例5所述电池循环性能示意图；
图2是实施例7所述电沉积铝-泡沫镍微观形貌图。
具体实施方式
下面结合实施例对本发明做进一步说明，但本发明并不限于以下实施例。
实施例1
将聚氨酯泡沫用丙酮、稀盐酸和水分别超声清洗5分钟，并在80℃下真空干燥12小时，用作电沉积铝基体。以EMICl/AlCl3(1/1.3)为沉积电解液。将该聚氨酯裁成长2cm、宽2cm、厚1mm大小的工作电极，相同尺寸的高纯铝片作为对电极和参比电极，固定于含电解液的密封电解池中，施加恒电压-0.6V沉积2小时。将沉积后的铝-聚氨酯用无水乙醇和去离子水清洗干净，并在80℃下真空干燥12小时。上述所得样品可作为电池负极。
以厚度为0.05mm的石墨纸为正极，将石墨纸裁剪为长2cm、宽1cm的片状；采用whatman GF/A玻璃纤维隔膜，裁剪为与正极面积相同的片状，并将其与石墨纸一同固定于集流体钼箔(厚度0.1mm)上，将正极及集流体一同固定于铂片电极夹上；以质量分数分别为8.75％、12.5％、78.75％的KCl、LiCl、AlCl3混合物为电解液；按比例称量所需电解质原料，搅拌混合均匀，将正负极固定于电解池内，加热至100℃并保温，待电解质熔化至液体后，其液面高度应足以浸润正负极，浸润正负极至八小时以完成活化，进行电池性能测试。该电池较普通铝箔相比，其容量虽无明显提升但其循环性能在500圈后库伦效率维持在98％。
实施例2
负极：在泡沫镍金属基体上沉积铝金属，泡沫镍清洗及干燥同实施例1。将该泡沫镍裁剪为长2cm、宽2cm、厚1mm片状，利用离子溅射仪沉积3分钟铝，该铝-泡沫镍作为电池负极。
正极、电解液及电池组装测试同实施例1。该电池较实施例1相比，其容量提升了5％，且循环性能良好。
实施例3.
负极：首先配制涂碳浆料，其质量比为4：3：92：1的炭黑、丙烯酸(成膜剂)、N-甲基吡咯烷酮(溶剂)和亚甲基二奈磺酸钠(分散剂)混合搅拌调配成浆料过筛，利用逆转辊凹版印刷装置在实施例2所得的多孔铝表面进行碳层涂覆。将所得涂碳铝烘干后，再用去离子水超声清洗，并二次烘干。该涂碳铝作为电池负极。
正极、电解液及电池组装测试同实施例1。
实施例4.
负极：在泡沫铜表面沉积多孔铝，泡沫铜前后处理及沉积过程同实施例1。将该铝-泡沫铜在1100℃氩气氛围下热处理12小时，自然降温冷却。所得合金作为电池负极。
正极、电解液及电池组装测试同实施例1。
实施例5
负极：厚度为3mm、孔隙率为70％、骨架尺寸约为1mm，经过6Mpa，持续5s的机械施压的三维多孔纯铝，将其铳成直径12mm的圆片，并夹持于铂片电极夹上。
正极、电解液及电池组装测试同实施例1。
图1为本实例的电池长循环性能示意图。由图1可见，在1A的大电流密度下，该电池可以循环2500圈而无明显衰减，充放电容量稳定在80mAh/g，库伦效率接近100％，足以证明其循环稳定性能。(注：该电池工作温度为100℃)
实施例6
负极：将泡沫镍置于离子液体(AlCl3:EMIC＝1.3,mole ratio)中并作为阴极，阳极为纯铝箔，在-0.6V电压下，恒压电解铝，可在泡沫镍上镀得一层铝膜，电镀完成后将镀铝泡沫镍用无水乙醇清洗干净并烘干作为电池负极。
正极、电解液及电池组装测试同实施例1。该电池充放电容量较普通铝箔提升10％，库伦效率为90％-98％，电池性能稳定。
实施例7
负极：长2cm，宽2cm、厚度为1mm、孔隙率为60％、骨架尺寸为0.1mm-2mm的泡沫镍。清洗及干燥过程同实施例1，在2A/g电流密度下恒流沉积10h，将铝层镀于泡沫镍上，之后该电极直接作为电池负极。其微观形貌SEM图如图2所示。
正极、电解液及电池组装测试同实施例1。
实施例8
负极：将3mm厚、孔隙率为70％、骨架尺寸范围为1mm-3mm三维多孔铝进行6Mpa、持续5s机械施压，并将其浸入AlCl3:EMIC(摩尔比)＝1.5的离子液体中浸泡24h，取出并擦拭干净表面残余电解液，用无水乙醇清洗并烘干，该电极微观形貌为多级腐蚀孔。
正极、电解液及电池组装测试同实施例1。
实施例9
负极：利用微波等离子体化学气相沉积装置对三维多孔铝进行石墨烯包覆。将系统抽真空至0.1Pa的基础压力，用氩气吹扫数次后，用100标准立方厘米每分钟(sccm)氢气在20分钟内将系统加热至600℃。然后，在15Pa的压力下引入7sccm甲烷，用150W的功率打开等离子体发生器，产生甲烷等离子体。沉积时间为5-10分钟，然后快速冷却到室温。至此获得石墨烯包覆的三维多孔铝。将其铳成直径为12mm的薄片，夹持于铂片电极夹上。正极、电解液及电池组装测试同实施例1。
实施例10
负极：如实施例1。
正极：将负载于有序介孔碳CMK3上的硫-碳复合材料(载硫量50％)与导电炭黑和PTFE粘结剂制成直径6mm的圆形极片，并压制到集流体钼网上。电解液：AlCl3-acetamide类离子液体(摩尔比1.3：1)；隔膜：如实施例1；电池组装：该电池利用Swagelok模型组装。
实施例11
负极：利用三聚氰胺泡沫，在氮气保护下于管式炉中以5℃/min的升温速率升到800℃，保温30min碳化，冷却至室温后取出作为电沉积基体，沉积三维多孔铝过程如实施例1。将该三维多孔铝浸入AlCl3:EMIC(摩尔比)＝1.5的离子液体中浸泡24h，取出并擦拭干净将表面残余电解液擦拭干净，用无水乙醇清洗并烘干。该极片作为电池负极。
正极、电解液及电池组装测试同实施例1。该电池性能同普通铝箔相比，循环及倍率性能有一定提升，循环50圈后容量可稳定在600mAh/g。
Claims (10)
1.一种三维多孔铝负极，其特征在于，该铝负极具有三维多孔形貌结构；包括：沉积于非金属三维基体上的三维多孔铝、沉积于金属三维基体上的三维多孔铝、表面具有保护层包覆的三维多孔铝、合金化三维多孔铝；该三维多孔铝负极的孔隙率为10％-98％，骨架直径为0.005mm-1mm，孔道形貌为开放孔道及部分闭合孔道，孔道尺寸分布为大孔、介孔或微孔的单一或多元分布，孔道取向性为各向同性或各向异性。
2.根据权利要求1所述的一种三维多孔铝负极，其特征在于，沉积于非金属三维基体上的三维多孔铝包括：沉积于多孔状聚氯酯、聚苯乙烯、聚乙烯、聚氨酯、聚氯乙烯、聚丙烯、酚醛树脂等泡沫塑料上的三维多孔铝；沉积于多孔石墨烯、石墨烯多孔组装体、碳纳米管多孔组装体、碳纤维多孔组装体等多孔碳材料上的三维多孔铝。
3.根据权利要求1所述的一种三维多孔铝负极，其特征在于，沉积于金属三维基体上的三维多孔铝包括：沉积于泡沫镍、泡沫铜、泡沫NiCrFe、ZnCu、NiCu、NiCrW、NiFe合金、纳米孔镍、纳米孔铜、纳米孔金、纳米孔银、纳米孔铂、纳米孔钯等具有三维多孔结构的金属或合金上的三维多孔铝。
4.根据权利要求1所述的一种三维多孔铝负极，其特征在于，表面具有保护层包覆的三维多孔铝包括：表面沉积有碳、硅、钛、钨、镍、金、银、铂、钯、锌等一种或几种原子的三维多孔铝；表面涂覆有碳纳米管、石墨烯、石墨炔、碳纤维、聚乙炔、聚噻吩、聚吡咯、聚苯胺、聚苯撑、聚苯撑乙烯、聚双炔等材料的三维多孔铝。
5.根据权利要求1所述的一种三维多孔铝负极，其特征在于，合金化三维多孔铝材料包括：铝与金属镓、铜、铬、铁、镍、铅、铋、锡或银形成的二元或多元多孔合金。
6.根据权利要求2所述的沉积于非金属三维基体上的三维多孔铝，其特征在于，铝沉积方法包括电化学沉积法及真空蒸镀法；所获得多孔铝电极包括非金属三维基体-多孔铝复合电极和去除非金属三维基体的纯多孔铝电极。
7.根据权利要求3所述的沉积于金属三维基体上的三维多孔铝，其特征在于，铝沉积方法包括电化学沉积法及真空蒸镀法；所获得多孔铝电极包括金属三维基体-多孔铝复合电极和进一步合金化的多孔铝合金电极。
8.权利要求1所述的三维多孔铝的应用，三维多孔铝应用于铝离子电池、铝硫电池、铝空气电池、含铝的双(多)离子电池等铝电池。
9.根据权利要求8所述的铝电池，其特征在于，铝电池由正极、电解液、隔膜和负极构成，其中负极为上述三维多孔铝。
10.根据权利要求8所述的铝电池，其特征在于，正极材料包括：导电碳纸、石墨粉、乙炔黑、升华硫、沉降硫、单质硒、硫化钼、硫化锡、五氧化二钒等材料；电解液包括：卤化铝和NaCl、KCl、LiCl、CsCl、MgCl2、BaCl2、NaBr、1-乙基-3-甲基溴化咪唑鎓、1-乙基-3-甲基氯化咪唑鎓、1-乙基-3-甲基碘化咪唑鎓、尿素、甲酰胺、乙酰胺、丙酰胺等形成的共晶盐；电池结构包括：密封玻璃电解池、Swagelok电池、扣式电池、耐高温软包电池等电池装置。
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| US12040162B2 (en) | 2022-06-09 | 2024-07-16 | 6K Inc. | Plasma apparatus and methods for processing feed material utilizing an upstream swirl module and composite gas flows |
| US12094688B2 (en) | 2022-08-25 | 2024-09-17 | 6K Inc. | Plasma apparatus and methods for processing feed material utilizing a powder ingress preventor (PIP) |
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