CN104393280B - 一种锰钴锂正极材料的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000010405 anode material Substances 0.000 title claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 239000011149 active material Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- FLOGAHIUJLPRMR-UHFFFAOYSA-L [Co](O)O.[Mg] Chemical compound [Co](O)O.[Mg] FLOGAHIUJLPRMR-UHFFFAOYSA-L 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- KYUOTPSBWVNTFR-UHFFFAOYSA-M O[Ni]O[Co] Chemical compound O[Ni]O[Co] KYUOTPSBWVNTFR-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CGYAAZGZXOWPNB-UHFFFAOYSA-L lithium nickel(2+) carbonate Chemical compound [Ni+2].C([O-])([O-])=O.[Li+] CGYAAZGZXOWPNB-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/13—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
- H01M4/362—Composites
-
- 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
-
- 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
Abstract
本发明涉及一种锰钴锂正极材料的制备方法，该正极材料的活性物质的化学式为Li1.02Mn1‑x‑yCoxMgyO2Iz，其中：x=0.32‑0.36，y=0.1‑0.15，z=0.01‑0.02，该方法包括如下步骤：（1））制备活性物质Li1.02Mn1‑x‑yCoxMgyO2Iz，（2）表面改性。本发明制备的正极材料，采用湿法制备和固相烧结法结合以获取较高的能量密度的活性物质，并使用I掺杂以及表面改性处理提高材料的高温循环稳定性，使得该材料具备较高的比容量和高温电化学稳定性。因此该复合材料在用于锂离子电池时，尤其是在高温应用场合时，具有较高容量和较长使用寿命。
Description
技术领域
本发明涉一种锰钴锂正极材料的制备方法。
背景技术
锂离子电池作为一种绿色二次电池，具有重量轻、体积小、放电平台高、容量大、循环寿命长、无记忆效应等优点，已广泛应用于手机、相机、笔记本电脑等移动式电子电器，同时也正越来越多地用于人造卫星、航空航天、电动汽车等领域。
目前商品化锂离子二次电池主要选用LiCoO2为正极材料,但钴元素相对贫乏导致原料成本高，LiMnO2和LiCoO2具有相同的层状结构并且资源丰富、成本低，无环境污染，是一种理想的替代LiCoO2后选材料，但是LiMnO2在合成过程中不易准确控制化学计量比，充放电过程中Ni3+已转化成Ni4+将严重影响其循环寿命，热稳定性差，甚至氧化分解电解质带来安全隐患。研究表明,掺入Co元素可以改善LiMnO2结构的稳定性,且20%左右的Ni被Co取代制得的正极材料电性能良好。
但是目前纯锰钴锂材料的高温安全性能和高温循环性能不是很好。
发明内容
本发明提供一种锰钴锂正极材料的制备方法，使用该方法制备的正极材料，具有较高的比容量和高温循环稳定性。
为了实现上述目的，本发明提供的一种锰钴锂正极材料的制备方法，该正极材料的活性物质的化学式为Li1.02Mn1-x-yCoxMgyO2Iz，其中： x=0.32-0.36，y=0. 1-0.15，z=0.01-0.02，该方法包括如下步骤：
（1）制备活性物质Li1.02Mn1-x-yCoxMgyO2Iz
配制摩尔比为Mn：Co = 1-x-y：x的硫酸锰、硫酸钴的混合溶液，混合溶液中两种金属离子的总浓度为2-3 mol/L；
配制浓度为4-6 mol/L的KOH溶液，0.5-1mol/L的氨水溶液，按照NH3·H2O∶KOH＝0.3-0.4的比例将KOH溶液和氨水溶液混合成混合碱溶液；
将两种混合溶液并行加入反应釜中，在氮气或惰性气体的保护下，以连续反应的方式控制反应，PH值控制11-13，温度50-60℃，过滤洗涤至洗水PH值小于7.5，在105-110℃下烘干，即得锰钴氢氧化物前驱体。
将上述锰钴氢氧化物前驱体、氢氧化锂、碳酸镁和碘化锂按照摩尔比（1-y）:1.02：y：z球磨混合充分，在空气气氛中，在950-1000℃下保温10-15h，自然降温至室温，粉碎分级，制得活性物质Li1.02Mn1-x-yCoxMgyO2Iz；
（2）表面改性
在丙酮溶剂中配制浓度为0.1-0.2mol/L的异丙醇铝溶液，将上述活性物质Li1.02Mn1-x-yCoxMgyO2Iz处理成粒径为10-15μm的颗粒后加入该异丙醇铝溶液，控制丙酮溶剂的质量为活性物质Li1.02Mn1-x-yCoxMgyO2Iz质量的2-3倍，搅拌10-20min，使其混合均匀，然后将混合物干燥，在500-660℃下热处理干燥物4-6h，得到正极材料。
本发明制备的正极材料，采用湿法制备和固相烧结法结合以获取较高的能量密度的活性物质，并使用I掺杂以及表面改性处理提高材料的高温循环稳定性，使得该材料具备较高的比容量和高温电化学稳定性。因此该复合材料在用于锂离子电池时，尤其是在高温应用场合时，具有较高容量和较长使用寿命。
具体实施方式
实施例一
本实施例的正极材料的活性物质的化学式为Li1.02Mn.58Co0.32Mg0.1O2I0.01。
配制摩尔比为Mn：Co = 0.58：0.32的硫酸锰、硫酸钴的混合溶液，混合溶液中三种金属离子的总浓度为2 mol/L；配制浓度为4 mol/L的KOH溶液，0.5mol/L的氨水溶液，按照NH3·H2O∶KOH＝0.3的比例将KOH溶液和氨水溶液混合成混合碱溶液。
将两种混合溶液并行加入反应釜中，在氮气或惰性气体的保护下，以连续反应的方式控制反应，PH值控制11，温度50℃，过滤洗涤至洗水PH值小于7.5，在105℃下烘干，即得锰钴氢氧化物前驱体。
将上述锰钴氢氧化物前驱体、氢氧化锂、碳酸镁和碘化锂按照摩尔比1.01:0.9：0.1：0.01球磨混合充分，在空气气氛中，在950℃下保温15h，自然降温至室温，粉碎分级，制得活性物质Li1.02Mn.58Co0.32Mg0.1O2I0.01。
在丙酮溶剂中配制浓度为0.1-0.2mol/L的异丙醇铝溶液，将上述活性物质Li1.02Mn.58Co0.32Mg0.1O2I0.01处理成粒径为10-15μm的颗粒后加入该异丙醇铝溶液，控制丙酮溶剂的质量为活性物质Li1.02Mn.58Co0.32Mg0.1O2I0.01质量的2倍，搅拌20min，使其混合均匀，然后将混合物干燥，在500℃下热处理干燥物6h，得到正极材料。
实施例二
本实施例的正极材料的活性物质的化学式为Li1.02Mn0.49Co0.36Mg0.15O2I0.02。
配制摩尔比为Mn：Co = 0.49：0.36的硫酸锰、硫酸钴的混合溶液，混合溶液中三种金属离子的总浓度为3 mol/L；配制浓度为6 mol/L的KOH溶液， 1mol/L的氨水溶液，按照NH3·H2O∶KOH＝0.4的比例将KOH溶液和氨水溶液混合成混合碱溶液。
将两种混合溶液并行加入反应釜中，在氮气或惰性气体的保护下，以连续反应的方式控制反应，PH值控制13，温度60℃，过滤洗涤至洗水PH值小于7.5，在110℃下烘干，即得锰钴氢氧化物前驱体。
将上述锰钴氢氧化物前驱体、氢氧化锂、碳酸镁和碘化锂按照摩尔比1:0.85：0.15：0.02球磨混合充分，在空气气氛中，在1000℃下保温10h，自然降温至室温，粉碎分级，制得活性物质Li1.02Mn1-x-yCoxMgyO2Iz。
在丙酮溶剂中配制浓度为0.2mol/L的异丙醇铝溶液，将上述活性物质Li1.02Mn0.49Co0.36Mg0.15O2I0.02处理成粒径为10-15μm的颗粒后加入该异丙醇铝溶液，控制丙酮溶剂的质量为活性物质Li1.02Mn0.49Co0.36Mg0.15O2I0.02质量的3倍，搅拌10min，使其混合均匀，然后将混合物干燥，在660℃下热处理干燥物4h，得到正极材料。
比较例
将硫酸镍、硫酸钴和硫酸铝按摩尔比Ni2+∶Co2+∶Al3+＝0.7∶0.25∶0.05混合配制成1mol/L的水溶液，将过硫酸钾配制成2mol/L的水溶液，将氢氧化钾配制成3mol/L 的溶液2L并加入0.5L 0.75mol/L的氨水。然后将配制好的混合盐溶液与过硫酸钾溶液均以10ml/min的流速并流加入带有搅拌装置的12L反应釜中，以450rpm的速度搅拌并加热至35℃，调节碱溶液的进料速度以控制反应体系的pH值在11-11.5之间，反应8h后结束，然后过滤出球形羟基氧化镍钴铝前驱体。再将球形羟基氧化镍钴铝用去离子水洗涤过滤6遍后，于120℃真空干燥箱中烘干12h得到前驱体。该前驱体形貌为球形和类球形；该前驱体X射线衍射图与标准卡06-0141一致。再将氢氧化锂与前驱体以1.06∶1的比例混合均匀后，置于流动纯氧气气氛炉中于700℃焙烧10h，冷却后破碎分级，得到掺铝镍钴酸锂材料。
将上述实施例一、二以及比较例所得产物分别和导电碳黑、粘结剂PVDF(聚偏氟乙烯)按质量比85∶10∶5混合，涂覆在铜箔上，以金属锂片为对极，电解液为1mol/L的LiPF6溶液，溶剂为EC、DEC和EMC的混合溶剂，体积比为1∶1∶1。在氩气保护的手套箱内将正极、负极、电解液、隔离膜与电池壳组装成扣式电池。在测试温度为50℃的高温环境下进行电性能测试，经测试该实施例一和二的材料与比较例的产物相比，首次比容量提高了22-25%，使用寿命提高到40%以上。
Claims (1)
1.一种锰钴锂正极材料的制备方法，该正极材料的活性物质的化学式为Li1.02Mn1-x- yCoxMgyO2Iz，其中： x=0.32-0.36，y=0. 1-0.15，z=0.01-0.02，该方法包括如下步骤：
（1）制备活性物质Li1.02Mn1-x-yCoxMgyO2Iz
配制摩尔比为Mn：Co = 1-x-y：x的硫酸锰、硫酸钴的混合溶液，混合溶液中两种金属离子的总浓度为2-3 mol/L；
配制浓度为4-6 mol/L的KOH溶液，0.5-1mol/L的氨水溶液，按照NH3·H2O∶KOH＝0.3-0.4的比例将KOH溶液和氨水溶液混合成混合碱溶液；
将两种混合溶液并行加入反应釜中，在氮气或惰性气体的保护下，以连续反应的方式控制反应，PH值控制11-13，温度50-60℃，过滤洗涤至洗水PH值小于7.5，在105-110℃下烘干，即得锰钴氢氧化物前驱体；
将上述锰钴氢氧化物前驱体、氢氧化锂、碳酸镁和碘化锂按照摩尔比（1-y）：（1.02-z）：y：z球磨混合充分，在空气气氛中，在950-1000℃下保温10-15h，自然降温至室温，粉碎分级，制得活性物质Li1.02Mn1-x-yCoxMgyO2Iz；
（2）表面改性
在丙酮溶剂中配制浓度为0.1-0.2mol/L的异丙醇铝溶液，将上述活性物质Li1.02Mn1-x- yCoxMgyO2Iz处理成粒径为10-15μm的颗粒后加入该异丙醇铝溶液，控制丙酮溶剂的质量为活性物质Li1.02Mn1-x-yCoxMgyO2Iz质量的2-3倍，搅拌10-20min，使其混合均匀，然后将混合物干燥，在500-660℃下热处理干燥物4-6h，得到正极材料。
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