CN103943824B - 一种稀土元素掺杂的锂离子电池三元复合正极材料的制备方法 - Google Patents
一种稀土元素掺杂的锂离子电池三元复合正极材料的制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 18
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
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- 229940063656 aluminum chloride Drugs 0.000 claims abstract description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
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- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims abstract description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229960004756 ethanol Drugs 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
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- 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
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Abstract
本发明涉及一种稀土元素掺杂的锂离子电池三元复合正极材料的制备方法，该稀土元素掺杂三元复合正极材料的化学式为LiMn1-x-y- zAlxCoyGdzO2 -aFa，其中：x＝0.2-0.3，y＝0.25-0.5，z＝0.02-0.03，a＝0.05-0.08，该方法包括如下步骤：(1)将氯化锰、氯化铝、氯化钴和硝酸钆配成水溶液，将配置的上述金属离子溶液加入氮气氛围的搅拌反应器中，将KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Mn1-x-y- zAlxCoyGdz)(OH)2沉淀，过滤、洗涤，干燥，得到颗粒状(Mn1-x-y- zAlxCoyGdz)(OH)2前驱体；(2)称取上述前驱体、氢氧化锂和氟化锂，球磨，干燥，烧结得到产品。本发明制备的稀土元素掺杂的三元复合正极材料，使用湿法制备掺杂有稀土元素Gd的三元材料前驱体，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。
Description
所属技术领域
本发明涉一种稀土元素掺杂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，它具有电压高、容量大、安全及环保等诸多有点，因此在二次电池领域受到广泛应用。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。
多元正极材料一定程度上克服可上述材料的缺点，并具有较高容量，但其循环性能较差，难以满足较高的锂电池产品的需要。
发明内容
本发明提供一种稀土元素掺杂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，具有高比容量同时，还具良好的循环性能。
为了实现上述目的，本发明提供的一种稀土元素掺杂的锂离子电池三元复合正极材料的制备方法，该稀土元素掺杂三元复合正极材料的化学式为LiMn1-x-y-zAlxCoyGdzO2-aFa，其中：x＝0.2-0.3，y＝0.25-0.5，z＝0.02-0.03，a＝0.05-0.08，该方法包括如下步骤：
(1)制备前驱体(Mn1-x-y-zAlxCoyGdz)(OH)2
将氯化锰、氯化铝、氯化钴和硝酸钆按Mn：Al：Co：Gd的摩尔比＝1-x-y-z：x：y：z配成水溶液，最终所有正离子的浓度总和为1-2mol/L的金属离子溶液；
将配置的上述金属离子溶液加入氮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1-2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Mn1-x-y-zAlxCoyGdz)(OH)2沉淀，在滴入KOH水溶液的同时，缓慢滴入浓度为2-4mol/L氨水，在整个反应过程中，搅拌器中反应溶液的pH值控制在10-12，的浓度控制在0.4-0.5mol/L；
反应结束后，将沉淀下来的(Mn1-x-y-zAlxCoyGdz)(OH)2颗粒产物过滤、洗涤，在100-120℃干燥，得到颗粒状(Mn1-x-y-zAlxCoyGdz)(OH)2前驱体；
(2)固相法制备稀土元素掺杂三元复合正极材料
按照摩尔比1:1-a：a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12-20h，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4-6h；
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8-10h球磨，干燥后，在空气中烧结，烧结温度在900-1000℃之间，保温8-10h，得到产品。
本发明制备的稀土元素掺杂的三元复合正极材料，使用湿法制备掺杂有稀土元素Gd的三元材料前驱体，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。此外，制备过程采用湿法和干法结合的方式，提升了材料的振实密度。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
本实施例制备的稀土元素掺杂三元复合正极材料的化学式为LiMn0.53Al0.2Co0.25Gd0.02O1.95F0.05。
将氯化锰、氯化铝、氯化钴和硝酸钆按Mn：Al：Co：Gd的摩尔比＝0.53：0.2：0.25：0.02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；将配置的上述金属离子溶液加入氮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1mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Mn0.53Al0.2Co0.25Gd0.02)(OH)2沉淀，在滴入KOH水溶液的同时，缓慢滴入浓度为2mol/L氨水，在整个反应过程中，搅拌器中反应溶液的pH值控制在10，的浓度控制在0.4mol/L；反应结束后，将沉淀下来的(Mn0.53Al0.2Co0.25Gd0.02)(OH)2颗粒产物过滤、洗涤，在100℃干燥，得到颗粒状(Mn0.53Al0.2Co0.25Gd0.02)(OH)2前驱体。
按照摩尔比1:1.95：0.05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20h，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6h；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10h球磨，干燥后，在空气中烧结，烧结温度在900℃之间，保温10h，得到产品。
实施例二
本实施例制备的稀土元素掺杂三元复合正极材料的化学式为LiMn0.17Al0.3Co0.5Gd0.03O1.92F0.08。
将氯化锰、氯化铝、氯化钴和硝酸钆按Mn：Al：Co：Gd的摩尔比＝0.17：0.3：0.5：0.03配成水溶液，最终所有正离子的浓度总和为2mol/L的金属离子溶液；将配置的上述金属离子溶液加入氮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2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Mn0.17Al0.3Co0.5Gd0.03)(OH)2沉淀，在滴入KOH水溶液的同时，缓慢滴入浓度为4mol/L氨水，在整个反应过程中，搅拌器中反应溶液的pH值控制在12，的浓度控制在0.5mol/L；反应结束后，将沉淀下来的(Mn0.17Al0.3Co0.5Gd0.03)(OH)2颗粒产物过滤、洗涤，在120℃干燥，得到颗粒状(Mn0.17Al0.3Co0.5Gd0.03)(OH)2前驱体。
按照摩尔比1:0.92：0.08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12h，干燥；将干燥后的物料置于空气中烧结，烧结温度在600℃，保温4h；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8h球磨，干燥后，在空气中烧结，烧结温度在1000℃，保温8h，得到产品。
比较例
以乙酸锂，乙酸锰，乙酸钴及草酸为起始原料，将0.9804g乙酸锰、0.9964g乙酸钴、1.2855g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2.1634g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Li1.2Mn0.4Co0.4O2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22-25％，使用寿命提高到27％以上。
Claims (1)
1.一种稀土元素掺杂的锂离子电池三元复合正极材料的制备方法，该稀土元素掺杂三元复合正极材料的化学式为LiMn1-x-y-zAlxCoyGdzO2-aFa，其中：x＝0.2-0.3，y＝0.25-0.5，z＝0.02-0.03，a＝0.05-0.08，该方法包括如下步骤：
(1)制备前驱体(Mn1-x-y-zAlxCoyGdz)(OH)2
将氯化锰、氯化铝、氯化钴和硝酸钆按Mn：Al：Co：Gd的摩尔比＝1-x-y-z：x：y：z配成水溶液，最终所有正离子的浓度总和为1-2mol/L的金属离子溶液；
将配置的上述金属离子溶液加入氮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1-2mol/L的KOH溶液非常缓慢的滴入搅拌反应器中，以产生(Mn1-x-y-zAlxCoyGdz)(OH)2沉淀，在滴入KOH水溶液的同时，缓慢滴入浓度为2-4mol/L氨水，在整个反应过程中，搅拌器中反应溶液的pH值控制在10-12，的浓度控制在0.4-0.5mol/L；
反应结束后，将沉淀下来的(Mn1-x-y-zAlxCoyGdz)(OH)2颗粒产物过滤、洗涤，在100-120℃干燥，得到颗粒状(Mn1-x-y-zAlxCoyGdz)(OH)2前驱体；
(2)固相法制备稀土元素掺杂三元复合正极材料
按照摩尔比1:1-a：a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12-20h，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4-6h；
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8-10h球磨，干燥后，在空气中烧结，烧结温度在900-1000℃之间，保温8-10h，得到产品。
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