CN1176505C - 锂离子二次电池正极材料的制备方法 - Google Patents
锂离子二次电池正极材料的制备方法 Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- 238000004519 manufacturing process Methods 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910013595 LiCo0.5Ni0.5O2 Inorganic materials 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910013562 LiCo0.2Ni0.8O2 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 2
- 239000010406 cathode material Substances 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 229910013733 LiCo Inorganic materials 0.000 abstract description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—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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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及锂离子二次电池正极材料LiCo1-xNixO2(0≤x≤1)即LiCoO2、LiNiO2和LiCo1-xNixO2的制备方法。将金属钴、镍或合金钴镍，在电解质溶液中进行电解得中间产物，经抽滤，洗涤，烘干后，根据产物中钴、镍或钴镍含量的不同，与含锂的化合物，500℃-850℃下，烘烧10～20小时，产物研碎过400目筛，即得到性能优良且价格便宜的正极材料，具有巨大的经济意义。
Description
所属技术领域
本发明涉及锂离子二次电池材料正极的制备方法，特别是通过电解金属钴、镍或钴镍合金制备锂离子二次电池正极材料。
背景技术
随着科学技术的迅速发展，电子仪器及设备的小型化，家用电器，移动通讯，计算机，电动自行车以及电动汽车方面，对二次电池的性能提出了越来越高的要求。从综合性能看，锂离子二次电池是最具有发展和应用前景的高能二次电池，但唯一的缺点是价格较高。因为在制备LiCoO2时，大都使用钴的化合物如CoO，Co(OH)2，Co3O4，CoCO3等材料做前驱体。要使其价格降低，必须寻找制备价格便宜的方法，或是以金属镍来部分或全部取代钴。
发明内容
本发明的目的是提供一种新的锂离子二次电池材料正极的制备方法。产品性能优越，制备成本比传统方法低。本发明是制备通式LiCo1-xNixO2(0≤x≤1)，即钴酸锂，钴镍酸锂，镍酸锂的一种方法。
本发明的具体步骤是：以金属钴、金属镍或钴镍合金为原料，在电解质溶液中进行电解，将所得的电解产物经洗涤、烘干后，依据钴、镍或钴镍含量，与氢氧化锂或碳酸锂以原子比(Co+Ni)∶Li＝1∶1.1的比例进行混合，然后在管式炉或马辐炉中在空气或通氧气的情况下，于500℃-850℃下，烘烧10～20小时，将烘烧后产物经磨碎后，过400目筛，即得所需的产物LiCoO2、LiNiO2或LiCo1-xNixO2(0＜x＜1)。所述的电解质溶液的溶质是含锂、钠、钾的盐；浓度为30g/L-150g/L之间。电解时端电压1.9±0.1V；电流密度在400-1200A/m2之间，电解时间不做限制。
锂离子二次电池正极材料是LiCoO2、LiNiO2或LiCo1-xNixO2，0＜x＜1。
本发明的正极材料是LiNiO2、LiCo0.5Ni0.5O2或LiCo0.2Ni0.8O2，制备步骤是：以金属钴、金属镍或钴镍合金为原料，在电解质溶液中进行电解，将所得的电解产物经洗涤、烘干后，依据钴、镍或钴镍含量，与氢氧化锂或碳酸锂以原子比(Co+Ni)∶Li＝1∶1.1的比例进行混合，其特征在于：所述的电解产物是105～120℃下烘干，混合后的材料在空气或通氧气的情况下，于500℃-850℃下，烘烧10～20小时，将烘烧后产物经磨碎后，过400目筛，即得所需的产物。锂离子二次电池正极材料制备时使用纯度≥99.8％的金属钴、镍或钴镍合金，做电解用的初始原料。
本发明的积极效果是：(1)以金属钴、金属镍、合金钴镍为原料，电解的产物与含锂的化合物在高温下进行合成LiCoO2、LiNiO2和LiCo1-xNixO2；(2)合成的产品性能优越；(3)制备成本比传统方法降低较多。
附图说明
图1是LiCo0.5Ni0.5O2正极材料的XRD结构图；图2是LiCo0.5Ni0.5O2正极材料的循环充放电曲线；图3是LiCo0.2Ni0.8O2正极材料的循环充放电曲线；图4是LiCoO2正极材料的循环充放电曲线。
具体实施方式
本发明突出的实质性特点和显著进步可以从下述实施例中得以体现，但它们不是对本发明作任何限制。
实施例1：
将纯度为99.8％的金属钴镍合金Co0.5Ni0.5放在金属钛蓝中做阳极，金属镍板作阴极，电解质溶液的溶质是NaCl，浓度为140g/L，电极间距离为20mm，端电压2V，电流密度500A/m2，电解后，将电解产物过滤，并用去离子水进行洗涤，再在120℃的温度下烘干，分析产品中钴镍的含量，加入LiOH.H2O，使(Co+Ni)∶Li＝1∶1.1，混合研磨后，在管式炉中烧结20小时，冷却至室温将产品研磨，过400目筛，得到LiCo0.5Ni0.5O2，其结构及电化学性能见图1，图2。
实施例2：
将纯度为99.8％的金属钴镍合金Co0.2Ni0.8放在金属钛蓝中做阳极，金属镍板作阴极，电解质的溶质是NaCl，浓度为100g/L，电极间距离为25mm，端电压2V，电流密度800A/m2，电解后，将电解产物过滤，并用去离子水进行洗涤，再在110℃的温度下烘干，分析产品中钴镍的含量，加入LiOH.H2O，使(Co+Ni)∶Li＝1∶1.1，混合研磨后，在管式炉中烧结20小时，冷却至室温将产品研磨，过400目筛，得到LiCo0.2Ni0.8O2，其电化学性能见图3。
实施例3：
将纯度为99.8％的金属钴放在金属钛蓝中做阳极，金属镍板作阴极，电解质的溶质是KCl，浓度为80g/L，电极间距离为30mm，端电压2V，电流密度1000A/m2，电解六小时后，将电解产物过滤，并用去离子水进行洗涤，再在105℃的温度下烘干，分析产品中钴的含量，加入LiOH.H2O，使Co∶Li＝1∶1.1，混合研磨后，在管式炉中烧结20小时，冷却至室温将产品研磨，过400目筛，得到LiCoO2，其充放电曲线如图4所示。
Claims (1)
1、一种锂离子二次电池正极材料的制备方法，该正极材料是：LiCo0.2Ni0.8O2、LiCo0.5Ni0.5O2或LiNiO2，制备步骤是：以金属钴、金属镍或钴镍合金为原料，在电解质溶液中进行电解，将所得的电解产物经洗涤、烘干后，依据钴、镍或钴镍含量，与氢氧化锂或碳酸锂以原子比(Co+Ni)∶Li＝1∶1.1的比例进行混合，其特征在于：
所述的电解产物是105～120℃下烘干，混合后的材料在空气或通氧气的情况下，于500℃-850℃下，烘烧10～20小时，将烘烧后产物经磨碎后，过400目筛，即得所需的产物；
所述的电解质溶液的溶质是氯化钠或氯化钾；
所述的电解时端电压1.9±0.1V；电流密度在500-1000A/m2之间；
所述的电解质溶液的浓度在80g/L-150g/L之间。
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| CN111725499B (zh) * | 2020-06-29 | 2023-04-07 | 刘强 | 一种联用电解法共沉淀法制备锂电池正极材料ncm811的方法 |
| CN112490431A (zh) * | 2020-12-14 | 2021-03-12 | 鹏盛国能(深圳)新能源集团有限公司 | 一种硅锂电池及其制造方法 |
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