CN112794369A - 纳米钴酸锂正极材料的制备方法及其应用 - Google Patents
纳米钴酸锂正极材料的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 150000001868 cobalt Chemical class 0.000 claims abstract description 24
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- FKBSHNBSEUWDAC-UHFFFAOYSA-L lithium sodium dihydroxide Chemical compound [Li+].[OH-].[OH-].[Na+] FKBSHNBSEUWDAC-UHFFFAOYSA-L 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010902 jet-milling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000001376 precipitating effect Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 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
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
-
- 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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- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本发明属于锂离子电池正极材料技术领域,公开一种纳米钴酸锂正极材料的制备方法及其应用,包括以下步骤:将碳酸盐溶液和分散剂混匀,加入钴盐溶液进行反应,再经过陈化、过滤,取滤渣干燥,得到纳米CoCO3粉末,再经过煅烧,得到Co3O4前驱体,将Co3O4前驱体与锂盐混合,再进行烧结、冷却、粉碎和过筛,即得纳米钴酸锂正极材料。本发明的主要优点体现在纳米CoCO3合成过程简单易控制,流程较短,不需要做特别精细的温度控制,反应过程中也不需精确控制pH值等条件,适合于大规模工业化生产。
Description
技术领域
本发明属于锂离子电池正极材料技术领域,具体涉及一种纳米钴酸锂正极材料的制备方法及其应用。
背景技术
近年来,随着新能源汽车行业的快速增长,以及传统储能领域和3C电源市场的持续扩张,对锂离子电池正极材料的需求量越来越大。在市场快速发展的同时,对正极材料性能特别是快速充放电的性能要求也越来越高。众所周知,提高正极材料快速充放电能力(即倍率性能)的一个重要方法就是将电极材料的颗粒尺寸尽量做到最小甚至纳米化。因为颗粒尺寸影响着Li离子传输的距离,也影响活性物质与电解液的接触面积。纳米化的电极材料有利于Li离子在材料内部的快速传输,也有利于扩大材料与电解液的接触面积,对于提高电极的倍率性能有着极大的帮助。
目前商品化的钴酸锂正极材料多为微米级球形颗粒,纳米级钴酸锂的合成大多还处于实验室研究阶段,并且都存在着操作过程精细复杂,反应条件控制困难,难以在实际生产中放大应用的问题。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出纳米钴酸锂正极材料的制备方法及其应用,产品易制备且适合大规模量产。
一种纳米钴酸锂正极材料的制备方法,包括以下步骤:
(1)将碳酸盐溶液和分散剂混匀,加入钴盐溶液进行反应,再经过陈化、过滤,取滤渣干燥,得到纳米CoCO3粉末,再经过煅烧,得到Co3O4前驱体;
(2)将所述Co3O4前驱体与锂盐混合,再进行烧结、冷却、粉碎和过筛,即得所述纳米钴酸锂正极材料;
所述钴盐溶液中Co2+的摩尔总量不超过碳酸盐溶液中碳酸根摩尔总量的1/5。碳酸盐溶液作为沉淀剂,CoCO3颗粒的尺寸与沉淀剂的过量倍数有关,沉淀剂过量5倍以上得到的CoCO3颗粒才能达到纳米级尺寸。
所述纳米钴酸锂正极材料的平均粒径为500-800nm,微观形貌为颗粒状或短棒状均匀分散颗粒。
所述纳米CoCO3固体粉末的平均粒径为100-1000nm。
优选地,步骤(1)中,所述钴盐溶液由钴盐溶于水中配制成,所述钴盐为硫酸钴、硝酸钴或氯化钴中的一种或多种;所述钴盐溶液的浓度为0.1-2.0mol/L。
优选地,步骤(1)中,所述碳酸盐溶液由碳酸盐溶于水中配制成,所述碳酸盐为碳酸钠、碳酸氢钠、碳酸铵、碳酸氢铵、碳酸钾或碳酸氢钾中的一种或多种;所述碳酸盐溶液的浓度为1.0-2.0mol/L。
优选地,步骤(1)中,所述分散剂为甲醇、乙醇、乙二醇、丙醇或丙三醇中的一种或多种。
优选地,步骤(1)中,所述钴盐溶液中Co2+的摩尔总量不超过碳酸盐溶液中碳酸根摩尔总量的1/10,碳酸盐溶液的过量倍数越高,越能抑制CoCO3颗粒的长大。
优选地,步骤(1)中,所述反应的温度为0-70℃,更优选为20-30℃。
优选地,步骤(1)中,所述煅烧的温度为300-800℃,更优选为400-600℃。
优选地,步骤(1)中,所述陈化的时间为2-3h。
优选地,步骤(2)中,所述锂盐为碳酸锂、氢氧化钠锂、硝酸锂、硫酸锂或草酸锂中的一种或几种。
优选地,步骤(2)中,所述Co3O4前驱体中钴元素与锂盐中锂元素的摩尔比为1:(1.0-1.2)。
优选地,步骤(2)中,所述烧结的温度为900-1200℃,烧结的时间为6-18h。
本发明还提供上述的制备方法在制备锂离子电池中的应用。
有益效果:
1、本发明的主要优点体现在纳米CoCO3合成过程简单易控制,流程较短,不需要做特别精细的温度控制,反应过程中也不需精确控制pH值等条件,适合于大规模工业化生产。
2、合成出的纳米CoCO3颗粒粒度均匀,分散性好,不会产生团聚,材料易于加工和使用,最终得到的纳米钴酸锂既具有纳米特性又有钴酸锂正极材料的特性,平均粒径为100-1000nm,具有较短的Li离子传输路径和较大的与电解质接触面积,使电极能够快速大量的进行离子传输,放电容量高,倍率性能好,5C倍率下的放电比容量达到160mAh/g以上,适用于快充型或高功率型锂离子电池。
附图说明
下面结合附图和实施例对本发明做进一步的说明,其中:
图1为本发明实施例1中纳米CoCO3粉末的SEM图;
图2为本发明实施例1中纳米Co3O4前驱体SEM图;
图3为本发明实施例1中纳米钴酸锂正极材料的SEM图;
图4为本发明对比例1中碳酸钴粉末的SEM图;
图5为本发明对比例1中钴酸锂的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例制备了一种纳米钴酸锂正极材料,具体过程为:
(1)将硫酸钴溶于水配制成0.75mol/L浓度的钴盐溶液,将碳酸氢铵溶于水配制成1.65mol/L浓度的碳酸盐溶液;
(2)将400L碳酸盐溶液注入600L体积的反应釜内,并加入50L乙醇作为分散剂,反应釜开机搅拌,将碳酸盐溶液和分散剂充分搅拌均匀,保持反应釜温度为室温25℃,以20L/h的流量向反应釜内注入钴盐溶液,4个小时共注入钴盐溶液80L后停止注入,继续保持搅拌,物料在反应釜内陈化2小时后,打入离心机脱水洗涤,再经过烘干得到纳米CoCO3粉末,将纳米CoCO3粉末在400℃下煅烧4小时得到纳米Co3O4前驱体;
(3)按照1:1.05钴锂摩尔比称取碳酸锂1685g,纳米Co3O4前驱体3500g,将称取的碳酸锂与纳米Co3O4前驱体在混料机内混合均匀,将混合后的物料置于马弗炉中,在空气气氛1020℃下煅烧9h,自然冷却后经气流粉碎和过筛即得纳米钴酸锂正极材料。
实施例2
本实施例制备了一种纳米钴酸锂正极材料,具体过程为:
(1)将氯化钴溶于水配制成0.8mol/L浓度的钴盐溶液,将碳酸氢钠溶于水配制成1.65mol/L浓度的碳酸盐溶液;
(2)将400L碳酸盐溶液注入600L体积的反应釜内,并加入60L乙二醇作为分散剂,反应釜开机搅拌,将碳酸盐溶液和分散剂充分搅拌均匀,保持反应釜温度为室温20℃,以30L/h的流量向反应釜内注入钴盐溶液,2.5个小时共注入钴盐溶液75L后停止注入,继续保持搅拌,物料在反应釜内陈化2小时后,打入离心机脱水洗涤,再经过烘干得到纳米CoCO3粉末,将CoCO3粉末在450℃下煅烧4小时得到纳米Co3O4前驱体;
(3)按照1:1.06钴锂摩尔比称取氢氧化锂1660g,纳米Co3O4前驱体3000g,将称取的氢氧化锂与纳米Co3O4前驱体在混料机内混合均匀,将混合后的物料置于马弗炉中,在空气气氛1010℃下煅烧10h,自然冷却后经气流粉碎和过筛即得纳米钴酸锂正极材料。
实施例3
本实施例制备了一种纳米钴酸锂正极材料,具体过程为:
(1)将硝酸钴溶于水配制成0.70mol/L浓度的钴盐溶液,将碳酸钠溶于水配制成1.5mol/L浓度的碳酸盐溶液;
(2)将350L碳酸盐溶液注入600L体积的反应釜内,并加入50L丙醇作为分散剂,反应釜开机搅拌,将碳酸盐溶液和分散剂充分搅拌均匀,保持反应釜温度为室温20℃,以20L/h的流量向反应釜内注入钴盐溶液,3个小时共注入钴盐溶液60L后停止注入,继续保持搅拌,物料在反应釜内陈化2小时后,打入离心机脱水洗涤,再经过烘干得到纳米CoCO3粉末,将CoCO3粉末在430℃下煅烧5小时得到纳米Co3O4前驱体;
(3)按照1:1.04钴锂摩尔比称取碳酸锂1912g、纳米Co3O4前驱体4000g,将称取的碳酸锂与纳米Co3O4前驱体在混料机内混合均匀,将混合后的物料置于马弗炉中,在空气气氛1050℃下煅烧8h,自然冷却后经气流粉碎和过筛即得纳米钴酸锂正极材料。
对比例1
本对比例制备了一种钴酸锂正极材料,具体过程为:
(1)将硫酸钴溶于水配制成1.5mol/L浓度的钴盐溶液,将碳酸氢钠溶于水配制成2mol/L的碳酸盐溶液;
(2)在间歇式600L体积反应釜内加入400L水,启动搅拌和加热,保持反应釜温度在50℃,同时开始注入钴盐溶液和碳酸盐溶液,反应釜内物料通过浓缩机排走清液,碳酸钴颗粒在反应釜内不断生长,当颗粒粒度中粒径达到D50=6.0um时停止进液,将釜内物料打入离心机脱水洗涤,再经过烘干得到CoCO3粉末,将CoCO3粉末在400℃下煅烧6小时得到Co3O4前驱体;
(3)按照1:1.05钴锂摩尔比称取碳酸锂1930g、Co3O4前驱体4000g,将称取的碳酸锂与Co3O4前驱体在混料机内混合均匀,将混合后的物料置于马弗炉中,在空气气氛1070℃下煅烧10h,自然冷却后经气流粉碎即得钴酸锂正极材料。
对比例1与实施例的主要区别在于步骤(2)CoCO3粉末的制备过程不同且所得颗粒的粒径是微米级。
对比例2
本对比例制备了一种钴酸锂正极材料,具体过程为:
(1)将氯化钴溶于水配制成1.5mol/L浓度的钴盐溶液,将碳酸氢铵溶于水配制成2mol/L的碳酸盐溶液;
(2)在间歇式600L体积反应釜内加入400L水,启动搅拌和加热,保持反应釜温度在45℃,同时开始注入钴盐溶液和碳酸盐溶液,反应釜内物料通过浓缩机排走清液,碳酸钴颗粒在反应釜内不断生长,当颗粒粒度中粒径达到D50=6.0um时停止进液,将釜内物料打入离心机脱水洗涤,再经过烘干得到CoCO3粉末,将CoCO3粉末在450℃下煅烧4.5小时得到Co3O4前驱体;
(3)按照1:1.06钴锂摩尔比称取氢氧化锂1936g、Co3O4前驱体3500g,将称取的氢氧化锂与Co3O4前驱体在混料机内混合均匀,将混合后的物料置于马弗炉中,在空气气氛1080℃下煅烧9h,自然冷却后经气流粉碎即得钴酸锂正极材料。
对比例2与实施例的主要区别在于步骤(2)CoCO3粉末的制备过程不同且所得颗粒的粒径是微米级。
对比例3
本对比例通过水热法制备了一种纳米Co3O4,具体过程为:
将一定量醋酸钴溶解于二甘醇(DEG)中,加入一定量PVP表面活性剂,再加入一定量尿素,搅拌成均匀溶液后,放入密封的水热釜内,经过高温高压的环境,反应得到规则形貌的CoCO3纳米颗粒,再将得到的CoCO3颗粒高温煅烧,制备出规则形貌的Co3O4纳米颗粒。通过控制尿素的加入量,最终得到花生状、胶囊状、方块状的不同形貌纳米颗粒。
对比例3与实施例的主要区别在于CoCO3纳米颗粒的制备过程,即使最终都能得到纳米颗粒,但是本对比例的操作过程精细复杂,反应条件控制困难,难以在实际生产中放大应用。
性能测试
对以上实施例1-3及对比例1-2进行以下理化指标测试:
粒度测试方法使用马尔文3000激光粒度仪,按照GB/T 19077《粒度分析激光衍射法》国家标准进行测量。电性能测试按照以下方法:以实施例及对比例制备的钴酸锂材料为活性材料,乙炔黑为导电剂,PVDF为粘结剂,以92:4:4的比例称取活性材料、导电剂、粘结剂,并加入一定量的有机溶剂NMP,搅拌后涂覆于铝箔上制成正极片,负极采用金属锂片,在充满氩气的手套箱内制成CR2430型纽扣电池。在CT2001A型蓝电测试系统进行电性能测试。测试条件:3.0-4.48V,电流密度1C=180mAh/g测试温度为25±1℃。
测试结果如表1所示:
从表1可以看出,对比例1-2的材料的中值粒度在6μm左右,实施例1-3材料的粒度均在1um以下达到了纳米级别,远小于对比例;实施例的首次放电比容量表现在低倍率下(0.1C)与对比相差不大,而在高倍率下(2C、5C)下明显高于对比例。
图1为实施1的纳米CoCO3粉末的SEM图片,从图中可以看出,颗粒成均匀的短棒状形貌,颗粒尺寸在1μm以下。图2为实施例1中纳米Co3O4前驱体的SEM图片,从图中可以看出,前驱体形貌基本继承了CoCO3粉末的形貌,仍保持纳米短棒状。图3为实施例1纳米钴酸锂的SEM图片,从图中可以看出,颗粒成分散的颗粒状,粒度均小于1μm。图4为对比例1中碳酸钴粉末的SEM图片,从图中可以看出所制得的碳酸钴颗粒成类球形,粒度大约为6μm。图5为对比例1中钴酸锂的SEM图片,从图中可以看出对比例1所制得的钴酸锂颗粒成表面光滑的颗粒状形貌,粒度大约在4~8μm。由此可见,本发明的制备方法可以得到颗粒粒度均匀,分散性好,不会产生团聚的纳米钴酸锂颗粒。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
1.一种纳米钴酸锂正极材料的制备方法,其特征在于,包括以下步骤:
(1)将碳酸盐溶液和分散剂混匀,加入钴盐溶液进行反应,再经过陈化、过滤,取滤渣干燥,得到纳米CoCO3粉末,再经过煅烧,得到Co3O4前驱体;
(2)将所述Co3O4前驱体与锂盐混合,再进行烧结、冷却、粉碎和过筛,即得所述纳米钴酸锂正极材料;
所述钴盐溶液中Co2+的摩尔总量不超过碳酸盐溶液中碳酸根摩尔总量的1/5。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述钴盐溶液由钴盐溶于水中配制成,所述钴盐为硫酸钴、硝酸钴或氯化钴中的一种或多种;所述钴盐溶液的浓度为0.1-2.0mol/L。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述碳酸盐溶液由碳酸盐溶于水中配制成,所述碳酸盐为碳酸钠、碳酸氢钠、碳酸铵、碳酸氢铵、碳酸钾或碳酸氢钾中的一种或多种;所述碳酸盐溶液的浓度为1.0-2.0mol/L。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述分散剂为甲醇、乙醇、乙二醇、丙醇或丙三醇中的一种或多种。
5.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述钴盐溶液中Co2+的摩尔总量不超过碳酸盐溶液中碳酸根摩尔总量的1/10。
6.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述反应的温度为0-70℃。
7.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述煅烧的温度为300-800℃。
8.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述锂盐为碳酸锂、氢氧化钠锂、硝酸锂、硫酸锂或草酸锂中的一种或几种。
9.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述烧结的温度为900-1200℃,烧结的时间为6-18h。
10.权利要求1-9任一项所述的制备方法在制备锂离子电池中的应用。
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CN115872456A (zh) * | 2022-11-18 | 2023-03-31 | 贵州雅友新材料有限公司 | 一种纳米球形碳酸钴的制备方法与应用 |
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WO2022151977A1 (zh) * | 2021-01-12 | 2022-07-21 | 广东邦普循环科技有限公司 | 纳米钴酸锂正极材料的制备方法及其应用 |
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CN116332243A (zh) * | 2023-02-09 | 2023-06-27 | 贵州梅岭电源有限公司 | 一种氟钒离子共掺杂的纳米钴酸锂正极材料制备方法及其应用 |
CN116332243B (zh) * | 2023-02-09 | 2024-06-14 | 贵州梅岭电源有限公司 | 一种氟钒离子共掺杂的纳米钴酸锂正极材料制备方法及其应用 |
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ES2953759A2 (es) | 2023-11-15 |
DE112021005980T5 (de) | 2023-08-31 |
WO2022151977A1 (zh) | 2022-07-21 |
GB202310095D0 (en) | 2023-08-16 |
HUP2200268A1 (hu) | 2022-11-28 |
US20230331584A1 (en) | 2023-10-19 |
MA61500A1 (fr) | 2023-09-27 |
GB2618229A (en) | 2023-11-01 |
CN112794369B (zh) | 2023-03-10 |
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