CN101378126B - 镍锰基包钴锂离子正极材料的制备方法 - Google Patents
镍锰基包钴锂离子正极材料的制备方法 Download PDFInfo
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 8
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910016783 Ni0.5Mn0.5(OH)2 Inorganic materials 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract 4
- 229910021311 NaFeO2 Inorganic materials 0.000 abstract 1
- 238000002288 cocrystallisation Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- WRWZNPYXEXPBAY-UHFFFAOYSA-N azane cobalt Chemical compound N.[Co] WRWZNPYXEXPBAY-UHFFFAOYSA-N 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 description 2
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种镍锰基包钴锂离子正极材料的制备方法，为α-NaFeO2结构镍锰基锂离子电池正极材料LiNi0.5-xCo2xMn0.5-xO2，其中0.03＜x≤0.4的制备方法。先用共结晶的方法制备Ni0.5Mn0.5(OH)2前驱体，然后采用梯度包覆的方式对其进行包覆钴的处理，得到y[Ni0.5Mn0.5(OH)2]·(1-y)[Co(OH)2]前驱体，其中0.2≤y≤0.8的前驱体，包覆后的前驱体经预处理后，加锂在750-1000℃烧结8～24小时，即得到镍锰基锂离子电池LiNi0.5-xCo2xMn0.5-xO2。本发明具有比容高、循环性能稳定、成本低、操作方便易于工业化生产。
Description
技术领域
本发明涉及一种锂离子电池的制备方法。
背景技术
上世纪末，日本索尼公司成功开发出锂离子电池引起世界范围的广泛关注。由于它工作电压高、体积小、无记忆效应、长循环寿命等优点，开始逐步取代传统的二次电池如铅酸电池、镍镉电池、镍氢电池。其中正极材料的研究是锂离子蓄电池研究和开发中一个非常重要的环节。目前，使用的正极材料主要有LiCoO2、LiNiO2、LiNi1-xCoO2、LiMnO2和LiMn2O4。商品化的锂离子蓄电池正极材料有LiCoO2、LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.8Co0.2O2、LiMn2O4。LiCoO2的循环性能优良，合成容易，但可逆容量低，价格昂贵，对环境污染大。LiNiO2具有价格便宜，污染小，可逆容量大的优点，但其循环性能差，合成困难。尖晶石型LiMn2O4在高温下存在严重的容量衰减问题，不管充电还是放电都有不可逆容量损失。LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2虽然价格比LiCoO2低了很多，但是高含量还是较高。
国外友人Shaju发现通过共沉淀合成的LiNi0.5Mn0.5O2材料在2.5～4.3V电压范围内比容量可达到150mA·h/g。Kang等专家发现在LiNi0.5Mn0.5O2材料中掺入Al，Ti和Co均可提高LiNi0.5Mn0.5O2材料放电容量以及电导率，在这些掺杂离子中Co的加入对性能改善最为明显。
迄今为止，使用本方法制备包覆型LiNi0.5-xCo2xMn0.5-xO2(0.03＜x≤0.4)镍锰基正极材料锂离子正极材料的方法，未见报道。
发明内容
本方明的目的诣在提供一种镍锰基包钴锂离子正极材料的制备方法，达到制备的价格低廉、电性能优良的包覆型镍锰基正极材料LiNi0.5-xCo2xMn0.5-xO2(0.03＜x≤0.4＝，本发明的目的是采用如下的技术方案实现的。
一种镍锰基包钴锂离子正极材料的制备方法，其设计要点是采用梯度包覆的方法在Ni0.5Mn0.5(OH)2基体外层包覆一层氢氧化钴，得到y[Ni0.5Mn0.5(OH)2]·(1-y)[Co(OH)2]前驱体，其中0.2≤y≤0.8的前驱体，加锂烧结后得到包覆型LiNi0.5-xCo2xMn0.5-xO2，其中0.03＜x≤0.4的镍锰基正极材料；
本方法的具体步骤是：
(1)配制浓度为0.1～3mol/L的钴盐水溶液；
(2)配制浓度为1～10mol/L的NaOH溶液或KOH溶液；
(3)配制配制浓度为1～10mol/L的金属离子络合剂氨水或硫酸铵或氯化铵；
(4)称取一定量的Ni0.5Mn0.5(OH)2基体待用；
(5)把步骤(3)中的络合剂缓慢加入到步骤(1)中配制的钴盐水溶液中，调节PH到7～9，充分搅拌均匀后，缓慢加入步骤(4)中已经准确称量的Ni0.5Mn0.5(OH)2基体，加完继续搅拌，充分浸透后，缓慢加入步骤(2)中已经配制好的碱溶液，控制反应终点的PH值为10～13；控制反应温度30～80℃，所使用钴盐与Ni0.5Mn0.5(OH)2基体的摩尔比为1∶9，反应结束后继续搅拌保温陈化12～24小时；
(6)将步骤(5)中所得到的产物转入固液分离器中，用去离子水洗涤钴盐水溶液，分离所得固体产物至洗涤水的PH值小于8为止，洗涤后的固体产物在干燥器中80～120℃干燥，得到包覆钴的Ni0.5Mn0.5(OH)2前驱体；
(7)按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在750～1000℃下烧结8-24小时，得到镍锰基LiNi0.5-xCo2xMn0.5-xO2，其中0.03＜x≤0.4的镍锰基正极材料。
2、如权利要求1所述的制备方法，其特征在于步骤(1)中所述的钴盐为硫酸钴、氯化钴、醋酸钴、硝酸钴中的一种。
3、如权利要求1所述的制备方法，其特征在于步骤(2)中所述的碱水溶液为氢氧化钠或氢氧化钾溶液。
4、如权利要求1所述的制备方法，其特征在于步骤(3)中所述的络合剂为氨水或硫酸铵或氯化铵或柠檬酸钠。
本方法制备的正极材料具有比容高、循环性能稳定、正极材料容量高、循环性能好、成本低，操作方便易于工业化生产。
具体实施方式
实施例1
将配制好的100L0.5mol/L的硫酸钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入15L5mol/L的氨水，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为11，继续搅拌陈化12小时，控制反应温度为40℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在850℃下烧结12小时，得到包覆型的LiNi0.45Co0.1Mn0.45O2正极材料。
实施例2
将配制好的100L1mol/L的氯化钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入15L5mol/L的氨水，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为11，继续搅拌陈化12小时，控制反应温度为40℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在850℃下烧结12小时，得到包覆型的LiNi0.4Co0.2Mn0.4O2正极材料。
实施例3
将配制好的100L1.5mol/L的氯化钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入20L5mol/L的氯化铵，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为11，继续搅拌陈化12小时，控制反应温度为40℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在850℃下烧结12小时，得到包覆型的LiNi1/3Co1/3Mn1/3O2正极材料。
实施例4
将配制好的100L0.5mol/L的硫酸钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入10L5mol/L的硫酸铵，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为11，继续搅拌陈化12小时，控制反应温度为40℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在850℃下烧结12小时，得到包覆型的LiNi0.45Co0.1Mn0.45O2正极材料。
实施例5
将配制好的100L0.5mol/L的硫酸钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入15L5mol/L的氨水，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为11，继续搅拌陈化12小时，控制反应温度为60℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在850℃下烧结12小时，得到包覆型的LiNi0.45Co0.1Mn0.45O2正极材料。
实施例6
将配制好的100L0.5mol/L的硫酸钴溶液，加入200L的反应釜中，在强烈搅拌的条件下，使用蠕动泵缓慢加入15L5mol/L的氨水，调节PH到8左右，加完氨水后，搅拌半小时形成均匀的钴氨络合液，缓慢加入已经称量好的Ni0.5Mn0.5(OH)2基体41.78kg，加完后，搅拌一小时，充分浸透后，用恒流泵恒速加入5mol/L的氢氧化钠溶液，直到终点PH为10，继续搅拌陈化12小时，控制反应温度为30℃，分离、洗涤后，在80℃恒温干燥箱中烘干24小时，包覆钴的Ni0.5Mn0.5(OH)2前驱体。按Li/(Ni+Mn+Co)＝1.05∶1.0进行配锂在850℃下烧结12小时，得到包覆型的LiNi0.45Co0.1Mn0.45O2正极材料。
Claims (4)
1.一种镍锰基包钴锂离子正极材料的制备方法，其特征是采用梯度包覆的方法在Ni0.5Mn0.5(OH)2基体外层包覆一层氢氧化钴，得到y[Ni0.5Mn0.5(OH)2]·(1-y)[Co(OH)2]前驱体，其中0.2≤y≤0.8的前驱体，加锂烧结后得到包覆型LiNi0.5-xCo2xMn0.5-xO2，其中0.03＜x≤0.4的镍锰基正极材料；
本方法的具体步骤是：
(1)配制浓度为0.1～3mol/L的钴盐水溶液；
(2)配制浓度为1～10mol/L的NaOH溶液或KOH溶液；
(3)配制配制浓度为1～10mol/L的金属离子络合剂氨水或硫酸铵或氯化铵；
(4)称取一定量的Ni0.5Mn0.5(OH)2基体待用；
(5)把步骤(3)中的络合剂缓慢加入到步骤(1)中配制的钴盐水溶液中，调节PH到7～9，充分搅拌均匀后，缓慢加入步骤(4)中已经准确称量的Ni0.5Mn0.5(OH)2基体，加完继续搅拌，充分浸透后，缓慢加入步骤(2)中已经配制好的碱溶液，控制反应终点的PH值为10～13；控制反应温度30～80℃，所使用钴盐与Ni0.5Mn0.5(OH)2基体的摩尔比为1∶9，反应结束后继续搅拌保温陈化12～24小时；
(6)将步骤(5)中所得到的产物转入固液分离器中，用去离子水洗涤钴盐水溶液，分离所得固体产物至洗涤水的PH值小于8为止，洗涤后的固体产物在干燥器中80～120℃干燥，得到包覆钴的Ni0.5Mn0.5(OH)2前驱体；
(7)按Li/(Ni+Mn+Co)＝1.05∶1进行配锂在750～1000℃下烧结8-24小时，得到镍锰基LiNi0.5-xCo2xMn0.5-xO2，其中0.03＜x≤0.4的镍锰基正极材料。
2.如权利要求1所述的制备方法，其特征在于步骤(1)中所述的钴盐为硫酸钴、氯化钴、醋酸钴、硝酸钴中的一种。
3.如权利要求1所述的制备方法，其特征在于步骤(2)中所述的碱水溶液为氢氧化钠或氢氧化钾溶液。
4.如权利要求1所述的制备方法，其特征在于步骤(3)中所述的络合剂为氨水或硫酸铵或氯化铵或柠檬酸钠。
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| CN102214819B (zh) * | 2010-04-09 | 2013-10-16 | 北京化工大学 | 一种锂离子电池梯度正极活性材料钴镍锰酸锂的制备方法 |
| US9692039B2 (en) | 2012-07-24 | 2017-06-27 | Quantumscape Corporation | Nanostructured materials for electrochemical conversion reactions |
| WO2014104823A1 (ko) * | 2012-12-28 | 2014-07-03 | 주식회사 엘앤에프신소재 | 리튬 이차 전지용 양극 활물질의 제조 방법 및 리튬 이차전지용 양극 활물질 |
| CN103943841A (zh) * | 2013-01-23 | 2014-07-23 | 江南大学 | 阴离子掺杂改性的锂离子电池(4:4:2)型三元正极材料及其制备方法 |
| CN103296274B (zh) * | 2013-05-15 | 2016-06-15 | 中信国安盟固利电源技术有限公司 | 一种高容量、低残碱、低pH值的包覆型镍钴酸锂正极材料及其制备方法 |
| CN105932228A (zh) * | 2014-01-28 | 2016-09-07 | 泉州劲鑫电子有限公司 | 一种高容量锂离子电池正极片的制备方法 |
| EP3111493B1 (en) | 2014-02-25 | 2020-12-09 | QuantumScape Corporation | Hybrid electrodes with both intercalation and conversion materials |
| WO2016025866A1 (en) | 2014-08-15 | 2016-02-18 | Quantumscape Corporation | Doped conversion materials for secondary battery cathodes |
| WO2016106321A1 (en) * | 2014-12-23 | 2016-06-30 | Quantumscape Corporation | Lithium rich nickel manganese cobalt oxide (lr-nmc) |
| KR102460961B1 (ko) * | 2015-11-06 | 2022-10-31 | 삼성에스디아이 주식회사 | 리튬이차전지용 양극 활물질, 그 제조방법 및 이를 포함한 양극을 구비한 리튬이차전지 |
| KR101970207B1 (ko) * | 2016-01-05 | 2019-04-18 | 주식회사 에코프로비엠 | 코발트 코팅 전구체의 제조 방법, 이에 의하여 제조된 코발트 코팅 전구체 및 이를 이용하여 제조된 양극활물질 |
| CN105609755A (zh) * | 2016-02-29 | 2016-05-25 | 深圳市贝特瑞新能源材料股份有限公司 | 一种正极活性材料的制备方法、正极活性材料 |
| KR20200066645A (ko) | 2017-10-06 | 2020-06-10 | 바스프 에스이 | 전극 활물질, 그 제조 및 이용 |
| CN108288709A (zh) * | 2017-12-28 | 2018-07-17 | 华中科技大学 | 一种纳米片富锂正极材料及制备方法与应用 |
| CN110474026B (zh) * | 2019-07-03 | 2021-02-19 | 广东邦普循环科技有限公司 | 一种镍钴锰酸锂三元正极材料及其制备方法 |
| CN110405201B (zh) * | 2019-08-15 | 2021-09-17 | 中南大学 | 一种磁粉表面梯度包覆结构、包覆方法及软磁复合材料 |
| KR102586171B1 (ko) * | 2021-10-14 | 2023-10-13 | (주)에코프로머티리얼즈 | 양극 활물질 제조용 전구체 제조 시 미반응 금속을 이용한 표면 코팅 방법 |
| WO2023121838A1 (en) | 2021-11-30 | 2023-06-29 | Quantumscape Battery, Inc. | Catholytes for a solid-state battery |
| WO2023114436A1 (en) | 2021-12-17 | 2023-06-22 | Quantumscape Battery, Inc. | Cathode materials having oxide surface species |
| CN114261995B (zh) * | 2021-12-22 | 2023-12-08 | 远景动力技术(江苏)有限公司 | 正极活性材料及其制备方法和应用 |
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