CN104393281B - 一种锰镍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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052744 lithium Inorganic materials 0.000 title abstract description 8
- 229910052759 nickel Inorganic materials 0.000 title abstract description 7
- 239000010406 cathode material Substances 0.000 title abstract 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 title abstract 6
- 239000000126 substance Substances 0.000 claims abstract description 12
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000013543 active substance Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 229940099607 manganese chloride Drugs 0.000 claims description 8
- 235000002867 manganese chloride Nutrition 0.000 claims description 8
- 239000011565 manganese chloride Substances 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000010295 mobile communication Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种锰镍锂正极材料的制备方法，该正极材料包括核心物质和磷酸铝包覆层，所述核心活性物质的化学式为Li1.05Mn1‑x‑ yNixTiyO2Fz，其中：x=0.25‑0.35，y=0.05‑0.1，z=0.02‑0.03该方法包括如下步骤：（1）制备核心活性物质，（2）包覆磷酸铝。本发明制备的正极材料，采用湿法制备特定配比锰镍钛前驱体，然后使用固相烧结法以获取较高的能量密度、F掺杂的活性物质，最后再活性物质表面覆盖磷酸铝层，使得该材料具备较高的比容量和电化学稳定性。因此该复合材料在用于锂离子电池时，具有较高容量和较长使用寿命。
Description
技术领域
本发明涉一种锰镍锂正极材料的制备方法。
背景技术
随着近来移动通讯及电讯工业的发展，高容量、轻小和较轻的锂二次电池在需求上大幅增加。然而，随着便携式或移动电子装置功能的多样化，因而伴随的是装置能量需求的增加，对于电池的高功率及高容量的实现同样存在强烈需求。
目前，研究用作锂离子电池正极材料的体系很多，但真正大规模工业化的还只有钻酸锂(LiCoO2)。LiMn2O4较LiCoO2原料相对低廉、材料热稳定性稍高，但是LiMn2O4的容量较低。LiFePO4合成原料资源丰富，成本低，对环境友好，容量高、循环性能好，但是其体积能量密度较低。LiNiO2则因其合成困难及比LiCoO2更差的过充安全问题而限制了它的应用。
因此急需研制一种能够综合上述正极材料优点的正极材料。
发明内容
本发明提供一种锰镍锂正极材料的制备方法，使用该方法制备的正极材料，兼具较高的比容量和高循环稳定性。
为了实现上述目的，本发明提供的一种锰镍锂正极材料的制备方法，该正极材料包括核心物质和磷酸铝包覆层，所述核心物质的化学式为Li1.05Mn1-x-yNixTiyO2Fz，其中： x=0.25-0.35，y=0.05-0.1，z=0.02-0.03；该方法包括如下步骤：
（1）制备核心物质
配制摩尔比为Mn：Ni：Ti= 1-x-y：x：y的氯化锰、硝酸镍、氯化钛的混合溶液，混合溶液中三种金属离子的总浓度为1-1.5 mol/L；
配制浓度为4-6 mol/L的KOH溶液，0.5-1mol/L的氨水溶液；
用恒流泵将氯化锰、硝酸镍、氯化钛的混合溶液和氨水溶液分别加入到高速搅拌的氮气气氛的反应容器中，滴加KOH溶液调节反应溶液的pH为11-13，控制合成温度为40-50℃，陈化7-10h，其中混合溶液与氨水的体积比为1：2-3；
将上述步骤陈化得到的沉淀充分洗涤、抽滤后，在110-120℃真空中干燥10-12h，得到锰镍钛氢氧化物前驱体Mn1-x-yNixTiy(OH)2；
将上述锰镍钛氢氧化物前驱体、碳酸锂和氟化锂按照摩尔比（1.05-z）/2:1：z球磨混合充分，然后分两步烧结：第一步在氧气气氛中以5-7℃/min的速度升温加热，在500-550℃煅烧10-15h，第二步在空气气氛中再以10-15℃/min的速度升温至800-850℃保温6-10h，随炉冷却至室温，制得活性物质Li1.05Mn1-x-yNixTiyO2Fz；
（2）包覆磷酸铝
配制浓度为0.2-0.5mol/L的氯化铝溶液，将上述活性物质Li1.05Mn1-x-yNixTiyO2Fz处理成粒径为10-15μm的颗粒后加入该氯化铝溶液中，形成混合物，磷酸二氢铵溶液加入该混合物进行反应，使该正极活性物质颗粒表面形成磷酸铝层，其中该磷酸铝包覆层在该正极复合材料颗粒中的质量百分比为0.5-2%，在500-660℃下热处理该表面具有磷酸铝层的活性物质颗粒，得到正极材料。
本发明制备的正极材料，采用湿法制备特定配比锰镍钛前驱体，然后使用固相烧结法以获取较高的能量密度、F掺杂的活性物质，最后再活性物质表面覆盖磷酸铝层，使得该材料具备较高的比容量和电化学稳定性。因此该复合材料在用于锂离子电池时，具有较高容量和较长使用寿命。
具体实施方式
实施例一
本实施例制备的核心物质的化学式为Li1.05Mn0.7Ni0.25Ti0.05O2F0.02。
配制摩尔比为Mn：Ni：Ti= 0.7：0.25：0.05的氯化锰、硝酸镍、氯化钛的混合溶液，混合溶液中三种金属离子的总浓度为1 mol/L；配制浓度为4 mol/L的KOH溶液，0.5mol/L的氨水溶液；用恒流泵将氯化锰、硝酸镍、氯化钛的混合溶液和氨水溶液分别加入到高速搅拌的氮气气氛的反应容器中，滴加KOH溶液调节反应溶液的pH为11，控制合成温度为40℃，陈化10h，其中混合溶液与氨水的体积比为1：2；将上述步骤陈化得到的沉淀充分洗涤、抽滤后，在110℃真空中干燥12h，得到锰镍钛氢氧化物前驱体Mn0.7Ni0.25Ti0.05 (OH)2。
将上述锰镍钛氢氧化物前驱体、碳酸锂和氟化锂按照摩尔比0.515:1：0.02球磨混合充分，然后分两步烧结：第一步在氧气气氛中以5℃/min的速度升温加热，在500℃煅烧15h，第二步在空气气氛中再以10℃/min的速度升温至800℃保温10h，随炉冷却至室温，制得活性物质Li1.05 Mn0.7Ni0.25Ti0.05O2F0.02。
配制浓度为0.2mol/L的氯化铝溶液，将上述活性物质Li1.05 Mn0.7Ni0.25Ti0.05O2F0.02处理成粒径为10-15μm的颗粒后加入该氯化铝溶液中，形成混合物，磷酸二氢铵溶液加入该混合物进行反应，使该正极活性物质颗粒表面形成磷酸铝层，其中该磷酸铝包覆层在该正极复合材料颗粒中的质量百分比为0.5%，在500℃下热处理该表面具有磷酸铝层的活性物质颗粒，得到正极材料。
实施例二
本实施例制备的核心物质的化学式为Li1.05Mn0.55Ni0.35Ti0.1O2F0.03。
配制摩尔比为Mn：Ni：Ti= 0.55：0.35：0.1的氯化锰、硝酸镍、氯化钛的混合溶液，混合溶液中三种金属离子的总浓度为1.5 mol/L；配制浓度为6 mol/L的KOH溶液， 1mol/L的氨水溶液；用恒流泵将氯化锰、硝酸镍、氯化钛的混合溶液和氨水溶液分别加入到高速搅拌的氮气气氛的反应容器中，滴加KOH溶液调节反应溶液的pH为13，控制合成温度为50℃，陈化7h，其中混合溶液与氨水的体积比为1：3；将上述步骤陈化得到的沉淀充分洗涤、抽滤后，在120℃真空中干燥10h，得到锰镍钛氢氧化物前驱体Mn0.55Ni0.35Ti0.1 (OH)2。
将上述锰镍钛氢氧化物前驱体、碳酸锂和氟化锂按照摩尔比0.51:1：0.03球磨混合充分，然后分两步烧结：第一步在氧气气氛中以7℃/min的速度升温加热，在550℃煅烧10h，第二步在空气气氛中再以15℃/min的速度升温至850℃保温6h，随炉冷却至室温，制得活性物质Li1.05 Mn0.55Ni0.35Ti0.1O2F0.03。
配制浓度为0.5mol/L的氯化铝溶液，将上述活性物质Li1.05 Mn0.55Ni0.35Ti0.1O2F0.03处理成粒径为10-15μm的颗粒后加入该氯化铝溶液中，形成混合物，磷酸二氢铵溶液加入该混合物进行反应，使该正极活性物质颗粒表面形成磷酸铝层，其中该磷酸铝包覆层在该正极复合材料颗粒中的质量百分比为2%，在660℃下热处理该表面具有磷酸铝层的活性物质颗粒，得到正极材料。
比较例
将乙酸镍、乙酸铝、乙酸锰、乙酸锂按摩尔比为1/3∶1/3∶1/3∶1溶于去离子水中，乙酸镍、乙酸铝、乙酸锰和乙酸锂的总浓度为0.5mol/L，混合均匀后加入浓度为0.6mol/L的柠檬酸水溶液，再加入质量百分浓度为20％的氨水溶液调节pH值为10；所述镍盐、铝盐和锰盐的总量与柠檬酸水的摩尔比为1∶1； 将得到的混合溶液于50℃的水浴中加热以蒸发水分，加热时间为18小时，并不断搅拌，搅拌速度为200转/分钟，得到凝胶体； 将凝胶体于鼓风干燥箱中烘干，烘干温度为80℃，烘干时间为30小时，得到干燥的凝胶体； 将干燥的凝胶体进行预烧，预烧温度为200℃，预烧时间为20小时，得到前驱体；前驱体自然冷却至室温后于球磨机中研磨0.5小时，将研磨后的前驱体在650℃下进行煅烧，煅烧时间为30小时，煅烧后自然冷却至室温后再次在球磨机上研磨0.5小时，即得到所述的锂离子电池多元正极材料LiNi1/3Al1/3Mn1/3O2。
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45℃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18-20%，使用寿命提高到50%以上。
Claims (1)
1.一种锰镍锂正极材料的制备方法，该正极材料包括核心物质和磷酸铝包覆层，所述核心物质的化学式为Li1.05Mn1-x-yNixTiyO2Fz，其中： x=0.25-0.35，y=0.05-0.1，z=0.02-0.03；该方法包括如下步骤：
（1）制备核心活性物质
配制摩尔比为Mn：Ni：Ti= 1-x-y：x：y的氯化锰、硝酸镍、氯化钛的混合溶液，混合溶液中三种金属离子的总浓度为1-1.5 mol/L；
配制浓度为4-6 mol/L的KOH溶液，0.5-1mol/L的氨水溶液；
用恒流泵将氯化锰、硝酸镍、氯化钛的混合溶液和氨水溶液分别加入到高速搅拌的氮气气氛的反应容器中，滴加KOH溶液调节反应溶液的pH为11-13，控制合成温度为40-50℃，陈化7-10h，其中混合溶液与氨水的体积比为1：2-3；
将上述步骤陈化得到的沉淀充分洗涤、抽滤后，在110-120℃真空中干燥10-12h，得到锰镍钛氢氧化物前驱体Mn1-x-yNixTiy(OH)2；
将上述锰镍钛氢氧化物前驱体、碳酸锂和氟化锂按照摩尔比（1.05-z）/2:1：z球磨混合充分，然后分两步烧结：第一步在氧气气氛中以5-7℃/min的速度升温加热，在500-550℃煅烧10-15h，第二步在空气气氛中再以10-15℃/min的速度升温至800-850℃保温6-10h，随炉冷却至室温，制得活性物质Li1.05Mn1-x-yNixTiyO2Fz；
（2）包覆磷酸铝
配制浓度为0.2-0.5mol/L的氯化铝溶液，将上述活性物质Li1.05Mn1-x-yNixTiyO2Fz处理成粒径为10-15μm的颗粒后加入该氯化铝溶液中，形成混合物，磷酸二氢铵溶液加入该混合物进行反应，使正极活性物质颗粒表面形成磷酸铝层，其中该磷酸铝包覆层在正极复合材料颗粒中的质量百分比为0.5-2%，在500-660℃下热处理该表面具有磷酸铝层的活性物质颗粒，得到正极材料。
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