CN113698183B - 一种碳包覆氧化铝陶瓷材料及其制备方法和应用 - Google Patents
一种碳包覆氧化铝陶瓷材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920005546 furfural resin Polymers 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007789 gas Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000005539 carbonized material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- -1 Polyethylene Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
本发明公开了一种碳包覆氧化铝陶瓷材料及其制备方法和应用。所述碳包覆氧化铝陶瓷材料为表面包裹有碳层的氧化铝颗粒;所述碳包覆氧化铝陶瓷材料的颗粒大小为11nm‑124μm,其中,被包裹的氧化铝颗粒大小为10nm‑120μm,碳层的平均厚度为1nm‑2μm,所述碳层为连续薄膜、不连续薄膜或紧密排列的碳微粒中的一种或多种组成;所述碳层对氧化铝颗粒表面的覆盖率为50%‑100%;所述碳包覆氧化铝陶瓷材料中碳与氧化铝质量比为(0.002‑0.6):1。本发明的碳包覆氧化铝陶瓷材料可用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料,能够提高锂离子电池的安全性能。
Description
技术领域
本发明涉及材料技术领域,尤其涉及一种碳包覆氧化铝陶瓷材料及其制备方法和应用。
背景技术
我国具有较丰富的铝土矿资源,迄今已探明保守储量23亿吨,位居世界第4,具备发展氧化铝工业的资源条件。据统计,2010年全国氧化铝产量2896万吨,是世界第一大氧化铝生产国。氧化铝具有多种晶型,且具有众多优异性能,如耐高温、耐磨损、电绝缘、抗氧化、耐腐蚀和机械强度高等特点,上述出色的理化性能使其在国防、建筑、化工和冶炼等众多领域有着广泛的应用需求。
众所周知,在微观上,氧化铝陶瓷材料是一种共价键和离子键结合而成的材料,使其具有较高的机械强度,因此在锂离子电池领域,使用氧化铝作为隔膜的涂层材料,极片的涂边材料等被广泛应用,以此来提高电池的安全性能。但是同时由于氧化铝的较高的绝缘性能,会导致电池内阻的增大,从而对电池性能造成影响。
发明内容
本发明实施例提供了一种碳包覆氧化铝陶瓷材料及其制备方法和应用,旨在解决氧化铝材料的应用导致电池内阻增大的问题。
第一方面,本发明实施例提供了一种碳包覆氧化铝陶瓷材料,具体为表面包裹有碳层的氧化铝颗粒;
所述碳包覆氧化铝陶瓷材料的颗粒大小为10nm-120μm,其中,被包裹的氧化铝颗粒大小为11nm-124μm,碳层的平均厚度为1nm-2μm,所述碳层为连续薄膜、不连续薄膜或紧密排列的碳微粒中的一种或多种组成;所述碳层对氧化铝颗粒表面的覆盖率为50%-100%;所述碳包覆氧化铝陶瓷材料中碳与氧化铝质量比为(0.002-0.6):1。
优选的,所述氧化铝为α-Al2O3、β-Al2O3、γ-Al2O3中的一种或多种晶型的混合。
优选的,所述碳层为无定形碳或晶态碳中的一种或多种共存。
优选的,所述碳包氧化铝陶瓷材料为球型、椭球型、鹅卵石形、片状或无规则形状中的一种或多种。
第二方面,本发明实施例提供了一种第一方面所述的碳包覆氧化铝陶瓷材料的制备方法,所述制备方法包括:将氧化铝粉末与碳源粉末混合均匀,置于300℃-1300℃的惰性气氛中热处理。
优选的,所述材料制备方法为干法制备方法或湿法制备方法;
所述干法制备方法包括:将氧化铝粉末与碳源粉末按照质量比1:(0.002-0.6)在混合设备中均匀混合后放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料;
所述湿法制备方法包括:将氧化铝粉末与碳源粉末按照质量比1:(0.002-0.6)加入混合设备中,并加入溶剂、助剂均匀混合成浆料,将浆料烘干得到的固体前驱体,放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料。
优选的,所述惰性气体为氮气、氦气、氖气、氩气中的一种或多种。
优选的,所述碳源包括石墨、活性炭、乙炔黑、介孔碳、石墨烯、酚醛树脂、糠醛树脂、环氧树脂、脲醛树脂、沥青、柠檬酸、葡萄糖、蔗糖、聚氯乙烯、聚乙烯醇缩丁醛中的一种或多种。
优选的,所述碳包覆氧化铝陶瓷材料用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料。
第三方面,本发明实施例提供了一种锂电池,包括上述第一方面所述的碳包覆氧化铝陶瓷材料。
本发明本发明的碳包覆氧化铝陶瓷材料可用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料,能够提高锂离子电池的安全性能。
附图说明
下面通过附图和实施例,对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例1提供的碳包覆氧化铝陶瓷材料的X射线衍射(XRD);
图2为本发明实施例1提供的碳包覆氧化铝陶瓷材料的扫描电镜(SEM)图。
具体实施方式
下面通过附图和具体的实施例,对本发明进行进一步的说明,但应当理解为这些实施例仅仅是用于更详细说明之用,而不应理解为用以任何形式限制本发明,即并不意于限制本发明的保护范围。
本发明的碳包覆氧化铝陶瓷材料为表面包裹有碳层的氧化铝颗粒;碳包覆氧化铝陶瓷材料的颗粒大小为11nm-124μm,其形貌为球型、椭球型、鹅卵石形、片状或无规则形状中的一种或多种。
被包裹的氧化铝颗粒大小为11nm-124μm,氧化铝具体为α-Al2O3、β-Al2O3、γ-Al2O3中的一种或多种晶型的混合。
碳层的平均厚度为1nm-2μm,碳层为连续薄膜、不连续薄膜或紧密排列的碳微粒中的一种或多种组成,结构为无定形碳或晶态碳中的一种或多种共存。
碳层对氧化铝颗粒表面的覆盖率为50%-100%;碳包覆氧化铝陶瓷材料中碳与氧化铝质量比为(0.002-0.6):1。
本发明以上材料可以通过将氧化铝粉末与碳源粉末混合均匀,置于300℃-1300℃的惰性气氛中热处理来制备获得。
具体所采用的方法可以为干法制备方法或湿法制备方法。
干法制备方法包括:将氧化铝粉末与碳源粉末按照质量比1:(0.002-0.6)在混合设备中均匀混合后放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料。
湿法制备方法包括:将氧化铝粉末与碳源粉末按照质量比1:(0.002-0.6)加入混合设备中,并加入溶剂、助剂均匀混合成浆料,将浆料烘干得到的固体前驱体,放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料。
以上制备方法中,惰性气体为氮气、氦气、氖气、氩气中的一种或多种。碳源包括:石墨、活性炭、乙炔黑、介孔碳、石墨烯、酚醛树脂、糠醛树脂、环氧树脂、脲醛树脂、沥青、柠檬酸、葡萄糖、蔗糖、聚氯乙烯、聚乙烯醇缩丁醛中的一种或多种。碳包覆氧化铝陶瓷材料用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料。
本发明的碳包覆氧化铝陶瓷材料用于锂离子电池,尤其是用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料,能够提高锂离子电池的安全性能。
为更好的理解本发明提供的技术方案,下述以多个具体实例分别说明应用本发明上述实施例提供的方法制备碳包覆氧化铝陶瓷材料的具体过程,及其特性。
对比例
将锰酸锂、炭黑、聚偏氟乙烯按质量比95:3:2混合均匀,涂布于铝箔上制成电池正极,石墨作电池负极,1M LiPF6的(碳酸乙烯酯)EC/(碳酸二甲酯)DMC/(碳酸甲乙基酯)EMC(体积比1:1:1)溶液作电解液,涂覆了Li0.5La0.5TiO3(LLTO)的聚乙烯(PE)膜作隔膜,在手套箱中组装成扣式电池。
实施例1
将粒度大小为1μm的α-Al2O3氧化铝与乙炔黑按照质量比7:1在研钵中手动研磨混合,然后将充分混合后的粉体转移至管式炉中并以0.5L/min的流量通入氩气,排除空气后以5℃/min升温至900℃,并恒温1小时,然后自然冷却至室温,关闭氩气源,将碳化后的材料破碎、细粉粉碎即可得到碳包覆氧化铝陶瓷材料。材料的XRD图如图1所示,图2为材料的SEM图形。
从XRD图形分析显示材料在经过包碳改性后内核的基本结构晶型未发生变化,从SEM图形显示材料为无规则多边形。
实施例2
将锰酸锂、炭黑、聚偏氟乙烯、上述实施例1得到的碳包覆氧化铝陶瓷材料按质量比95:3:1:1混合均匀,涂布于铝箔上制成电池正极,石墨作负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,涂覆了LLTO的PE膜作隔膜作隔膜,在手套箱中组装成扣式电池。
实施例3
将锰酸锂、炭黑、聚偏氟乙烯按质量比95:3:2混合均匀,涂布于铝箔上制成电池正极,石墨作负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,将实施例1中的碳包覆氧化铝陶瓷材料涂覆于单层PE膜上作为电池隔膜,在手套箱中组装成扣式电池。
实施例4
将粒度大小为1μm的α-Al2O3氧化铝粉末与粒度大小为1μm酚醛树脂按照质量比10:1在三维混合机中混合均匀,然后将充分混合后的粉体转移至管式炉中并以0.5L/min的流量通入氮气,排除空气后以5℃/min升温至820℃,并恒温6小时,然后自然冷却至室温,关闭氮气源,将碳化后的材料破碎、细粉粉碎即可得到碳包覆氧化铝陶瓷材料。
实施例5
将锰酸锂、炭黑、聚偏氟乙烯、上述实施例4得到的碳包覆氧化铝陶瓷材料按质量比95:3:1:1混合均匀,涂布于铝箔上制成电池正极,石墨作负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,涂覆了LLTO的PE膜作隔膜,在手套箱中组装成扣式电池。
实施例6
将锰酸锂、炭黑、聚偏氟乙烯按质量比95:3:2混合均匀,涂布于铝箔上制成电池正极,石墨作负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,将LLTO与实施例4中的碳包覆氧化铝陶瓷材料按质量比9:1混合均匀,涂覆于PE膜上作为电池隔膜,在手套箱中组装成扣式电池。
实施例7
将粒度大小为3μm的γ-Al2O3氧化铝与葡萄糖按照质量比18:1置于行星搅拌机中,并加入适量去离子水混合均匀得到浆料,然后将浆料在烘箱中干燥成固体前驱体,再将前驱体粉末转移至管式炉中并以0.5L/min的流量通入氮气,排除空气后以5℃/min升温至650℃,并恒温3小时,然后自然冷却至室温,关闭氮气源,将碳化后的材料破碎、细粉粉碎即可得到碳包覆氧化铝陶瓷材料。
实施例8
将锰酸锂、炭黑、聚偏氟乙烯按质量比95:3:2混合均匀,涂布于铝箔上制成电池正极,石墨作负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,将上述实施例7得到的碳包覆氧化铝陶瓷材料涂覆于PE膜上作电池隔膜,在手套箱中组装成扣式电池。
实施例9
将锰酸锂、炭黑、聚偏氟乙烯按质量比95:3:2混合均匀,涂布于铝箔上制成电池正极,石墨作电池负极,1M LiPF6的EC/DMC/EMC(体积比1:1:1)溶液作电解液,将LLTO与实施例7中得到的碳包覆氧化铝陶瓷材料按质量比9:1混合均匀,涂覆于PE膜上作为电池隔膜,在手套箱中组装成扣式电池。
性能测试
对上述实施例2、3、5、6、8、9和对比例的扣式电池进行测试,包括不同倍率下放电下电池表面中心点的温度升高值,在不同荷电状态时的内阻,结果列于下表1。
表1
从测试结果可以看出,各实施例的扣式电池的倍率放电温升均小于对比例,不同荷电状态下的电阻均低于对比例,说明实施例得到的碳包覆氧化铝陶瓷材料能有效降低内阻,降低放电温升,进而降低锂电池热失控的风险。
本发明的碳包覆氧化铝陶瓷材料可用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料,能够降低电池内阻,提高锂离子电池的安全性能。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种碳包覆氧化铝陶瓷材料,其特征在于,所述碳包覆氧化铝陶瓷材料为表面包裹有碳层的氧化铝颗粒;
所述碳包覆氧化铝陶瓷材料的颗粒大小为11nm-124μm,其中,被包裹的氧化铝颗粒大小为10nm-120μm,碳层的平均厚度为1nm-2μm,所述碳层为连续薄膜;所述碳层对氧化铝颗粒表面的覆盖率为100%;所述碳包覆氧化铝陶瓷材料中碳与氧化铝质量比为(0.002-0.6):1;
所述碳包覆氧化铝陶瓷材料通过湿法制备方法获得,具体为:将氧化铝粉末与碳源粉末加入混合设备中,并加入溶剂、助剂均匀混合成浆料,将浆料烘干得到的固体前驱体,放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料;
所述碳源粉末包括活性炭、乙炔黑、介孔碳、石墨烯、酚醛树脂、糠醛树脂、环氧树脂、脲醛树脂、沥青、柠檬酸、葡萄糖、蔗糖、聚氯乙烯、聚乙烯醇缩丁醛中的一种或多种;
所述氧化铝为α-Al 2O3、β-Al 2O3、γ-Al 2O3中的一种或多种晶型的混合;
所述碳层为无定形碳或晶态碳中的一种或多种共存;
所述碳包氧化铝陶瓷材料为无规则形状。
2.一种上述权利要求1所述的碳包覆氧化铝陶瓷材料的制备方法,其特征在于,所述制备方法包括:将氧化铝粉末与碳源粉末混合均匀,置于300℃-1300℃的惰性气氛中热处理。
3.根据权利要求2所述的碳包覆氧化铝陶瓷材料的制备方法,其特征在于,所述材料制备方法为湿法制备方法;
所述湿法制备方法包括:将氧化铝粉末与碳源粉末按照质量比1:
(0.002-0.6)加入混合设备中,并加入溶剂、助剂均匀混合成浆料,将浆料烘干得到的固体前驱体,放入加热设备中,在300℃-1300℃的惰性气氛中热处理,即得到碳包覆氧化铝陶瓷材料。
4.根据权利要求2所述的碳包覆氧化铝陶瓷材料的制备方法,其特征在于,所述惰性气氛中的气体为氮气、氦气、氖气、氩气中的一种或多种。
5.根据权利要求2所述的碳包覆氧化铝陶瓷材料的制备方法,其特征在于,所述碳源包括活性炭、乙炔黑、介孔碳、石墨烯、酚醛树脂、糠醛树脂、环氧树脂、脲醛树脂、沥青、柠檬酸、葡萄糖、蔗糖、聚氯乙烯、聚乙烯醇缩丁醛中的一种或多种。
6.一种上述权利要求1所述的碳包覆氧化铝陶瓷材料的用途,其特征在于,所述碳包覆氧化铝陶瓷材料用于电池正极材料添加剂、隔膜涂层材料添加剂或隔膜涂层材料。
7.一种锂离子电池,其特征在于,所述锂离子电池包括上述权利要求1所述的碳包覆氧化铝陶瓷材料。
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