CN103825028B - 一种锗包覆的锂离子电池三元复合正极材料的制备方法 - Google Patents
一种锗包覆的锂离子电池三元复合正极材料的制备方法 Download PDFInfo
- Publication number
- CN103825028B CN103825028B CN201410091305.8A CN201410091305A CN103825028B CN 103825028 B CN103825028 B CN 103825028B CN 201410091305 A CN201410091305 A CN 201410091305A CN 103825028 B CN103825028 B CN 103825028B
- Authority
- CN
- China
- Prior art keywords
- germanium
- composite cathode
- cathode material
- coated
- lini
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 30
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 239000011206 ternary composite Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 20
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 19
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims abstract description 5
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000008279 sol Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 239000012266 salt solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 238000011068 loading method Methods 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
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000000967 suction filtration 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Landscapes
- 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
本发明涉及一种锗包覆的锂离子电池三元复合正极材料的制备方法，该正极材料的化学式为LiNi1-x-yAlxCoyO2-zFz，其中：x=0.26-0.32，y=0.18-0.22，z=0.005-0.01，该方法包括如下步骤：（1）将草酸镍、草酸铝、草酸钴配制成混合溶液；将配制的上述金属离子溶液加入氩气氛围的搅拌，加热，将KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Ni1-x-yAlxCoy)(OH)2沉淀，过滤、洗涤，干燥，得到颗粒状(Ni1-x-yAlxCoy)(OH)2前驱体；（2）分别称取前驱体、氢氧化锂和氟化锂，球磨，干燥，烧结，得到三元复合正极材料LiNi1-x-yAlxCoyO2-zFz；（3）采用锗溶胶包覆得到氧化锗包覆的LiNi1-x-yAlxCoyO2-zFz。本发明制备正极材料，使用湿法制备三元材料前驱体，以获取较高的能量密度和物质活性；采用固相烧结的方法在材料中掺杂F，进一步提高材料的稳定性，最后采用锗包覆来增强材料整体性能。
Description
所属技术领域
本发明涉一种锗包覆的锂离子电池三元复合正极材料的制备方法。
背景技术
锂离子电池是一种新兴电源，由于其具有高电压、高容量、循环寿命长、安全性能好、绿色环保等优点，已广泛应用于便携式电子设备、动力装置、航空航天、空间技术等领域。锂电池主要由正极材料、负极材料、隔膜和电解液等构成。
目前市场上常用的锂电池正极材料主要有三种：钴酸锂（LiCoO2）,锰酸锂（LiMn2O4）和磷酸铁锂（LiFePO4）。钴酸锂（LiCoO2）具有层状晶体机构，储电容量约140mAh/g，循环性能比较优越，但是在由于原材料钴的昂贵价格，其应用局限于小容量电池，例如小型电子产品的充电电池。锰酸锂（LiMn2O4），具有尖晶石晶体结构，原材料成本比较低，但是其容量只有100mAh/g，比钴酸锂低40%左右。而且其循环性能大于50℃的较高温度下（电力汽车运行温度）会大大减弱，所以也不是未来电力汽车的首选材料。磷酸铁锂（LiFePO4），具有橄榄石晶体结构，容量约为150mAh/g。其原材料成本比较低，但是因其制备工艺极其复杂，最终成品电极材料价格还是比较高。磷酸铁锂因为其导电率非常差，需要制成纳米级别的粉末颗粒才会表现出比较好的电池循环性能，这就给制备工艺上造成很大的困难，国内有一些厂家在试图生产，但因其批次质量不稳定，一直不能大规模投产。
近来，三元材料得到迅速发展，此三元正极材料成本较低，安全性能好，且在容量发挥上已经超过LiCoO2，实际容量可以高达180～190mAh/g。但是，此类材料在实际应用中也存在一系列难以克服的缺陷。首先，此类三元材料的压实密度较低，仅为3.6g/cm3，因此，在相同容量下，正极片所占据的空间较大，导致电池内部的空间利用率低。其次，但作为锂电池正极材料，其循环性能较差，难以满足较高的锂电池产品的需要。
发明内容
本发明提供一种锗包覆的锂离子电池三元复合正极材料的制备方法，使用该方法制备的正极材料，具有较高能量密度的同时，还具良好的循环性能。
为了实现上述目的，本发明提供的一种锗包覆的锂离子电池三元复合正极材料的制备方法，该三元复合正极材料的化学式为LiNi1-x-yAlxCoyO2-zFz，其中：x=0.26-0.32，y=0.18-0.22，z=0.005-0.01，该方法包括如下步骤：
（1）湿法制备前驱体(Ni1-x-yAlxCoy)(OH)2
将草酸镍、草酸铝、草酸钴按Ni：Al：Co的摩尔比=1-x-y：x：y配成水溶液，最终所有正离子的浓度总和为0.5-1mol/L的金属离子溶液；
将配制的上述金属离子溶液加入氩气氛围的搅拌反应器中，搅拌器搅拌速度为600-800rpm，加热温度控制在75-90℃；
将浓度为0.1-0.2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Ni1-x-yAlxCoy)(OH)2沉淀，在整个反应过程中，搅拌器中反应溶液的pH值控制在10-12；
反应结束后，将产物过滤、洗涤，在100-120℃干燥，得到颗粒状(Ni1-x-yAlxCoy)(OH)2前驱体；
（2）固相法三元复合正极材料
按照摩尔比1:1-z：z分别称取上述前驱体、氢氧化锂和氟化锂，将称取的前驱体和氢氧化锂混合后在行星球磨机中以转速400-500r/min球磨10-15h，干燥；
将干燥后的物料置于空气中烧结，烧结温度在500-600℃之间，保温3-5h；
冷却后至室温后，加入上述称取的氟化锂，在行星球磨机中以转速400-500r/min球磨5-6h球磨，干燥后，在空气中烧结，烧结温度在900-1000℃之间，保温6-8h，得到三元复合正极材料LiNi1-x-yAlxCoyO2-zFz；
（3）表面包覆氧化锗
将所得到的三元复合正极材料LiNi1-x-yAlxCoyO2-zFz置于搅拌反应器中，加入纯乙醇，固液比为3：1-2，搅拌后缓慢加入锗溶胶，锗溶胶使用异丙醇锗溶于丙酮溶液中形成，溶胶浓度控制在30-35%，锗溶胶加入的量控制在最终的氧化锗质量占整个复合正极材料产物的1.5-2wt%；
加入锗溶胶后，混合搅拌3-4h，将料浆转移入干燥设备中，抽真空烘干；
将上烘干物料在空气中550-650℃，加热10-12h，得到氧化锗包覆的LiNi1-x-yAlxCoyO2-zFz。
本发明制备的稀土元素掺杂的三元复合正极材料，使用湿法制备三元材料前驱体，以获取较高的能量密度和物质活性；采用固相烧结的方法在材料中掺杂F，进一步提高材料的稳定性，最后采用锗包覆来增强材料整体性能。因此该复合材料在用于锂离子电池时，具有较高的比容量和较长的使用寿命。
具体实施方式
实施例一
本实施例制备的三元复合正极材料的化学式为LiNi0.56Al0.26Co0.18O1.995F0.005。
将草酸镍、草酸铝、草酸钴按Ni：Al：Co的摩尔比=0.56：0.26：0.18配成水溶液，最终所有正离子的浓度总和为0.5mol/L的金属离子溶液；将配制的上述金属离子溶液加入氩气氛围的搅拌反应器中，搅拌器搅拌速度为600rpm，加热温度控制在75℃；将浓度为0.1mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生Ni0.56Al0.26Co0.18)(OH)2沉淀，在整个反应过程中，搅拌器中反应溶液的pH值控制在10；反应结束后，将产物过滤、洗涤，在100℃干燥，得到颗粒状(Ni0.56Al0.26Co0.18)(OH)2前驱体。
按照摩尔比1:1.995：0.005分别称取上述前驱体、氢氧化锂和氟化锂，将称取的前驱体和氢氧化锂混合后在行星球磨机中以转速400r/min球磨15h，干燥；将干燥后的物料置于空气中烧结，烧结温度在500℃之间，保温5h；冷却后至室温后，加入上述称取的氟化锂，在行星球磨机中以转速400r/min球磨6h球磨，干燥后，在空气中烧结，烧结温度在900℃之间，保温8h，得到三元复合正极材料LiNi0.56Al0.26Co0.18O1.995F0.005。
将所得到的三元复合正极材料LiNi0.56Al0.26Co0.18O1.995F0.005置于搅拌反应器中，加入纯乙醇，固液比为3：1，搅拌后缓慢加入锗溶胶，锗溶胶使用异丙醇锗溶于丙酮溶液中形成，溶胶浓度控制在30%，锗溶胶加入的量控制在最终的氧化锗质量占整个复合正极材料产物的1.5wt%；加入锗溶胶后，混合搅拌3h，将料浆转移入干燥设备中，抽真空烘干；将上烘干物料在空气中550℃，加热12h，得到氧化锗包覆的LiNi0.56Al0.26Co0.18O1.995F0.005。
实施例二
本实施例制备的三元复合正极材料的化学式为LiNi0.46Al0.32Co0.22O1.99F0.01。
将草酸镍、草酸铝、草酸钴按Ni：Al：Co的摩尔比=0.46：0.32：0.22配成水溶液，最终所有正离子的浓度总和为1mol/L的金属离子溶液；将配制的上述金属离子溶液加入氩气氛围的搅拌反应器中，搅拌器搅拌速度为800rpm，加热温度控制在90℃；将浓度为0.2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Ni0.46Al0.32Co0.22)(OH)2沉淀，在整个反应过程中，搅拌器中反应溶液的pH值控制在12；反应结束后，将产物过滤、洗涤，在120℃干燥，得到颗粒状(Ni0.46Al0.32Co0.22)(OH)2前驱体。
按照摩尔比1:1.99：0.01分别称取上述前驱体、氢氧化锂和氟化锂，将称取的前驱体和氢氧化锂混合后在行星球磨机中以转速500r/min球磨10h，干燥；将干燥后的物料置于空气中烧结，烧结温度在600℃之间，保温3h；冷却后至室温后，加入上述称取的氟化锂，在行星球磨机中以转速500r/min球磨5h球磨，干燥后，在空气中烧结，烧结温度在1000℃之间，保温6h，得到三元复合正极材料LiNi0.46Al0.32Co0.22O1.99F0.01。
将所得到的LiNi0.46Al0.32Co0.22O1.99F0.01置于搅拌反应器中，加入纯乙醇，固液比为3：2，搅拌后缓慢加入锗溶胶，锗溶胶使用异丙醇锗溶于丙酮溶液中形成，溶胶浓度控制在35%，锗溶胶加入的量控制在最终的氧化锗质量占整个复合正极材料产物的2wt%；加入锗溶胶后，混合搅拌4h，将料浆转移入干燥设备中，抽真空烘干；将上烘干物料在空气中650℃，加热10h，得到氧化锗包覆的LiNi0.46Al0.32Co0.22O1.99F0.01。
比较例
以乙酸锂，乙酸锰，乙酸钴及草酸为起始原料，将0.3270g乙酸锰、4.4836g乙酸钴、2.5305g乙酸锂溶于无水乙醇，得乙醇的金属盐溶液；再将比化学计量比过量20％的草酸4.8021g溶于无水乙醇；将草酸的乙醇溶液加入乙醇的金属盐溶液中，搅拌1h后抽滤并于100℃干燥3h后将其研磨成粉末装入坩埚；于箱式炉内以4℃/min的升温速度升温到900℃下加热12h，并于室温下退火，即可得到Li1.033Mn0.067Co0.9O2粉体材料。
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8∶1∶1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25℃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19-25%，使用寿命提高到30%以上。
Claims (1)
1.一种锗包覆的锂离子电池三元复合正极材料的制备方法，该三元复合正极材料的化学式为LiNi1-x-yAlxCoyO2-zFz，其中：x=0.26-0.32，y=0.18-0.22，z=0.005-0.01，该方法包括如下步骤：
（1）湿法制备前驱体(Ni1-x-yAlxCoy)(OH)2
将草酸镍、草酸铝、草酸钴按Ni：Al：Co的摩尔比=1-x-y：x：y配成水溶液，最终所有正离子的浓度总和为0.5-1mol/L的金属离子溶液；
将配制的上述金属离子溶液加入氩气氛围的搅拌反应器中，搅拌器搅拌速度为600-800rpm，加热温度控制在75-90℃；
将浓度为0.1-0.2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Ni1-x-yAlxCoy)(OH)2沉淀，在整个反应过程中，搅拌器中反应溶液的pH值控制在10-12；
反应结束后，将产物过滤、洗涤，在100-120℃干燥，得到颗粒状(Ni1-x-yAlxCoy)(OH)2前驱体；
（2）固相法三元复合正极材料
按照摩尔比1:1-z：z分别称取上述前驱体、氢氧化锂和氟化锂，将称取的前驱体和氢氧化锂混合后在行星球磨机中以转速400-500r/min球磨10-15h，干燥；
将干燥后的物料置于空气中烧结，烧结温度在500-600℃之间，保温3-5h；
冷却后至室温后，加入上述称取的氟化锂，在行星球磨机中以转速400-500r/min球磨5-6h球磨，干燥后，在空气中烧结，烧结温度在900-1000℃之间，保温6-8h，得到三元复合正极材料LiNi1-x-yAlxCoyO2-zFz；
（3）表面包覆氧化锗
将所得到的三元复合正极材料LiNi1-x-yAlxCoyO2-zFz置于搅拌反应器中，加入纯乙醇，固液比为3：1-2，搅拌后缓慢加入锗溶胶，锗溶胶使用异丙醇锗溶于丙酮溶液中形成，溶胶浓度控制在30-35%，锗溶胶加入的量控制在最终的氧化锗质量占整个复合正极材料产物的1.5-2wt%；
加入锗溶胶后，混合搅拌3-4h，将料浆转移入干燥设备中，抽真空烘干；
将上烘干物料在空气中550-650℃，加热10-12h，得到氧化锗包覆的LiNi1-x-yAlxCoyO2-zFz。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091305.8A CN103825028B (zh) | 2014-03-12 | 2014-03-12 | 一种锗包覆的锂离子电池三元复合正极材料的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091305.8A CN103825028B (zh) | 2014-03-12 | 2014-03-12 | 一种锗包覆的锂离子电池三元复合正极材料的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103825028A CN103825028A (zh) | 2014-05-28 |
| CN103825028B true CN103825028B (zh) | 2015-11-25 |
Family
ID=50759970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410091305.8A Active CN103825028B (zh) | 2014-03-12 | 2014-03-12 | 一种锗包覆的锂离子电池三元复合正极材料的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103825028B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112447967B (zh) * | 2019-09-02 | 2022-03-08 | 宁德时代新能源科技股份有限公司 | 正极活性材料、正极极片及锂离子二次电池 |
| CN113764653B (zh) * | 2021-08-30 | 2023-01-06 | 浙江帕瓦新能源股份有限公司 | 双重氧化物包覆修饰的低钴三元正极材料及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901906A (zh) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | 锂离子二次电池及其正极材料 |
| CN102195042A (zh) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | 一种高性能锂离子电池正极材料锰酸锂及其制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7608365B1 (en) * | 1999-05-25 | 2009-10-27 | Samsung Sdi Co., Ltd. | Positive active material composition for rechargeable lithium battery and method of preparing positive electrode using same |
| JP4743752B2 (ja) * | 2005-04-11 | 2011-08-10 | 日立マクセル株式会社 | リチウムイオン二次電池 |
| US9350018B2 (en) * | 2010-09-30 | 2016-05-24 | Kawasaki Jukogyo Kabushiki Kaisha | Negative electrode for use in secondary battery and secondary battery including the same |
-
2014
- 2014-03-12 CN CN201410091305.8A patent/CN103825028B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195042A (zh) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | 一种高性能锂离子电池正极材料锰酸锂及其制备方法 |
| CN101901906A (zh) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | 锂离子二次电池及其正极材料 |
Non-Patent Citations (2)
| Title |
|---|
| Capacity fade of LiNi(1-x-y)CoxAlyO2 cathode for lithium-ion batteries during accelerated calendar and cycle life test.I.Comparison analysis between LiNi(1-x-y)CoxAlyO2 and LiCoO2 cathodes in cylindrical lithium-ion cells during long term storage test;Shoichiro Watanabe et al.;《Journal of Power Sources》;20140201;第247卷;全文 * |
| LiCoO2/LiNi0.8Co0.15Ah0.05O2混合正极材料过充电行为研究;王力臻等;《电池工业》;20090630;第14卷(第3期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103825028A (zh) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102306779B (zh) | 一种锂离子电池正极材料富锂型掺杂钼酸锂及其制备方法 | |
| CN104134790B (zh) | 一种镍钴锰酸锂改性材料及其制备方法及其应用 | |
| CN101308926B (zh) | 正硅酸盐包覆的锂离子电池复合正极材料及其制备方法 | |
| CN107069030B (zh) | 一种形貌和尺寸双可控的富锂锰基正极材料的制备方法 | |
| CN105140492A (zh) | 一种表面包覆锆酸锂的镍钴锰酸锂复合正极材料及制备方法 | |
| CN109119624B (zh) | 一种磷酸钛锂包覆富锂锰基正极材料的制备方法 | |
| CN105514373A (zh) | 一种高容量锂离子电池正极材料及其制备方法 | |
| CN102646831A (zh) | 复合xLi2MnO3·(1-x)LiMO2材料及其制备方法、含该材料的锂离子电池 | |
| CN102368547A (zh) | 一种锂离子电池及其正极活性材料 | |
| CN101172599A (zh) | 一种碳包覆的磷酸铁锂的制备方法 | |
| CN106169566A (zh) | 一种层状富锂正极材料的制备方法 | |
| CN103078099A (zh) | 一种锂离子电池正极材料及其制备方法 | |
| CN102664255B (zh) | 锂镍锰氧材料及其制备方法、含该材料的锂离子电池 | |
| CN104979549A (zh) | 片状富锂锰基锂离子电池正极材料及其制备方法和应用 | |
| CN102723494A (zh) | 一种掺杂改性高温锰酸锂正极材料及其制备方法 | |
| CN103367733A (zh) | 锂离子电池正极材料及其制备方法、电池 | |
| CN104037412A (zh) | 高性能锂离子二次电池负极材料多级结构纳米空心球的制备方法 | |
| CN108110242A (zh) | 一种锂离子电池用镍锰钴复合材料的制备方法 | |
| CN103187566B (zh) | 一种管状富锂正极材料及其制备方法和应用 | |
| CN102646830A (zh) | 金属氧化物包覆的富锂材料及其制备方法、含该材料的锂离子电池 | |
| CN102820463B (zh) | 掺杂富锂锰基正极材料及其制备方法、锂离子电池 | |
| CN107768628B (zh) | 一种锂离子电池正极材料及其制备方法 | |
| CN106410180A (zh) | 一种锂离子电池正极材料及其制备方法和应用 | |
| CN103219509B (zh) | 一种尖晶石锰酸锂正极材料的制备方法 | |
| CN104409705A (zh) | 一种碳包覆锗掺杂锰酸锂复合正极材料的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qian Hege Inventor before: Liu Yang |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150923 Address after: 243000 Ma'anshan economic and Technological Development Zone, Hongqi Road, No. 19, Anhui Applicant after: Qian Hege Address before: 518000 Guangdong Province, Shenzhen city Longgang District cloth Road Park four building 12 unit 1805 A Applicant before: Liu Yang |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Qian Inventor after: Qian Hege Inventor before: Qian Hege |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170425 Address after: Yicheng road 257000 Shandong city of Dongying province Dongying District No. 7 Patentee after: Shandong high Jiaxin Energy Co. Ltd. Address before: 243000 Ma'anshan economic and Technological Development Zone, Hongqi Road, No. 19, Anhui Patentee before: Qian Hege |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210322 Address after: No.7 Yicheng Road, Dongying City, Shandong Province 257000 Patentee after: Shandong Yicong new energy Co., Ltd Address before: No.7 Yicheng Road, Dongying District, Dongying City, Shandong Province 257000 Patentee before: SHANDONG GREEN NEW ENERGY Co.,Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140528 Assignee: Shandong wanmeng Energy Technology Co.,Ltd. Assignor: Shandong Yicong new energy Co., Ltd Contract record no.: X2021980013508 Denomination of invention: A preparation method of ternary composite cathode material for germanium coated lithium ion battery Granted publication date: 20151125 License type: Common License Record date: 20211126 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of ternary composite cathode material for germanium coated lithium ion battery Effective date of registration: 20220331 Granted publication date: 20151125 Pledgee: Dongying rural commercial bank Limited by Share Ltd. Shengli branch Pledgor: Shandong Yicong new energy Co.,Ltd. Registration number: Y2022980003694 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220526 Granted publication date: 20151125 Pledgee: Dongying rural commercial bank Limited by Share Ltd. Shengli branch Pledgor: Shandong Yicong new energy Co.,Ltd. Registration number: Y2022980003694 |