CN100417595C - 由碳酸盐前躯体制备锂过渡金属复合氧化物的方法 - Google Patents
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- -1 lithium transition metal Chemical class 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 29
- 239000002243 precursor Substances 0.000 title claims description 23
- 229910052723 transition metal Inorganic materials 0.000 title claims description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 19
- 239000002905 metal composite material Substances 0.000 title claims description 17
- 229910052744 lithium Inorganic materials 0.000 title abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910016482 Ni0.4Co0.2Mn0.4 Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229930013930 alkaloid Natural products 0.000 claims 2
- 150000003797 alkaloid derivatives Chemical class 0.000 claims 2
- 238000003837 high-temperature calcination Methods 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 125000003010 ionic group Chemical group 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000007873 sieving Methods 0.000 abstract description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229910018871 CoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
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- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
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- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Abstract
本发明涉及一种锂过渡金属复合氧化物的制备方法，包括如下步骤：①配制含有以钴、镍、锰为基本组分的混合金属元素离子的水溶液为A溶液，含有CO3 2-离子的水溶液为B溶液，含有水溶液性碱物质的水溶液为C溶液；②将A溶液、B溶液和选择性含有C溶液混合搅拌反应数小时，得到化学式为Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐的前躯体；③取Li2CO3与Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐混合均匀后，在空气中以500-800℃高温锻烧2-20小时；④冷却、粉碎上述煅烧物料；⑤再将粉碎的煅烧物料在空气中以700-950℃高温煅烧2-30小时；⑥冷却、球磨、筛分即可得到化学式为LiNi0.4Co0.2Mn0.4CO3的锂过渡金属复合氧化物；其中步骤①的反应条件为pH＝8-9、T＝30-90℃。制备得到LiNi0.4Co0.2Mn0.4CO3，其颗粒大小平均为10um，放电容量达到150mAh/g，循环寿命长，适合锂离子电池使用。
Description
技术领域
本发明涉及一种锂过渡金属复合氧化物的制备方法，具体地说，是涉及碳酸盐前躯体制备及由碳酸盐前躯体制备一种性能优异的锂过渡金属复合氧化物的方法。
背景技术
已知的商品化锂离子电池利用锂钴氧(LiCoO2)、锂镍氧(LiNiO2)、锂锰氧(LiMn2O4)等几种过渡金属复合氧化物作为正极材料，尤其以LiCoO2的应用最为普遍。虽然LiCoO2的综合性能最佳，但是其价格较高且随其稀缺有升高趋势，甚至有枯竭的可能，因此，以钴(Co)、镍(Ni)、锰(Mn)中至少二种过渡金属元素为基本组分的锂过渡金属氧化物的合成研究已为各国所关注，其中具有代表性的有：一、Zhaolin Lin等在J.Power Sources88-82(1999)416-419上公开了化学式为LiNi1-x-yCOXMnyO2的上述复合氧化物的合成方法；二、中国专利CN1271185A号于2000年10月25日公开了一种掺杂组分的LiCoO2、LiNiO2、LiMn2O4的制备方法。
本发明人研究发现，虽然方法一的产物相比于将钴、镍、锰等过渡金属元素的盐或氢氧化物与锂盐混合后热分解制备的复合氧化物，在粒径分布、密度、电化学容量等性能方法更优，但该法制备的中间产物Ni1-x-yCOXMny(OH)2为球形，且要求球的粒径分布要窄所得的复合氧化物才具有上述优良性能，这需要控制严格的沉淀条件，在实际操作上很难；方法二则采用钴、镍、锰等过渡金属元素与锂的可溶盐、碱液或碳酸盐以喷雾方式混合得到复合晶体，再热分解得到的掺杂组分的LiCoO2、LiNiO2、LiMn2O4，但该法在操作上也很难，因为Li2CO3的容度积接近10-3，常温下在水中的溶解度约1克，对于复合晶体的洗涤以清除负离子的步骤必然导致部分Li2CO3的溶解，使锂的含量减少，得不到按LiCoO2、LiNiO2、LiMn2O4式计量的产物。
发明内容
本发明的目的在于改进现有方法的缺陷，而提供一种以化学式为Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐为前躯体，通过与锂盐热分解的两步法制备性能优异的锂过渡金属复合氧化物的方法。
本发明可以通过以下方法实现：
一种由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其特征在于：它包括如下步骤：
(1)碳酸盐前躯体的制备：
①、配制含有以钴(Co)、镍(Ni)、锰(Mn)为基本组分的混合金属元素离子(以Men+表示)的水溶液为A溶液，含有CO3 2-离子的水溶液为B溶液，含有水溶液性碱的水溶液为C溶液；
②、将A溶液、B溶液和选择性含有C溶液混合搅拌反应数小时，得到化学式为Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐的前躯体；
其中反应条件为：pH7.5-10，反应温度30-90℃，搅拌速度20-120转/分，反应时间2-30小时；
(2)锂过渡金属复合氧化物的合成：
③、取Li2CO3与上述的Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐混合均匀后，在空气中高温煅烧数小时；
④、冷却、粉碎上述煅烧物料；
⑤、再将粉碎的煅烧物料在空气中高温煅烧数小时；
⑥、冷却、球磨、筛分即可得到化学式为LiNi0.4Co0.2Mn0.4CO3锂过渡金属复合氧化物；
其中步骤(1)的A溶液为钴、镍、锰盐混合水溶液，B溶液为CO3 2-离子的水溶液，C溶液为水溶液性碱物质的水溶液，调节流量使反应在pH＝8-9、温度30-90℃条件下均匀进行。
其中反应条件为：③步骤的煅烧工序温度500-800℃，时间2-20小时；⑤步骤的煅烧工序温度700-950℃，时间2-30小时。
优选步骤(1)的A溶液的离子浓度为0.1-3.0mol/l，Men+来源于由硫酸盐、硝酸盐、盐酸盐、醋酸盐、其它水溶性无机盐、其它水溶性有机酸盐所组成的物质组中的至少一种原料。进一步优选步骤(1)的A溶液含有Ga、Mg、Zn、Y、Ga、In元素的离子组中至少一种的掺杂组分，掺杂组分相对于基本组分的摩尔分数为0-10％。
优选步骤(1)的B溶液的CO3 2-离子浓度为0.1-3.0mol/l，CO3 2-来源于由Na2CO3、K2CO3、(NH4)2CO3、其它水溶液性碳酸盐、相应的以HCO3 -存在的水溶性盐所组成的物质组中的至少一种原料。
优选步骤(1)的pH值由C溶液调节，所述C溶液为1.0-6.0mol/l的NaOH、KOH、NH3、其它水溶液性碱的物质组中至少一种的水溶液，在搅拌下，A溶液、B溶液、C溶液同时往反应器添加混合。
或更优选步骤(1)的A溶液为钴、镍、锰硫酸盐混合水溶液，B溶液为(NH4)2CO3，C溶液为NH3.H2O水溶液，调节流量使反应在pH＝8-9、温度30-90℃条件下均匀进行。
优选步骤(2)的Li2CO3与所述的Ni0.4Co0.2Mn0.4CO3混合先干料混合再加水或乙醇等有机溶剂湿混，充分搅拌使混合均匀；其中的③步骤的煅烧工序温度550-700℃，时间10-25小时。
本发明与现有的方法相比，具有如下优点：
1、计量投料能得到化学式为Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐的前躯体，再与Li2CO3热分解，可能由于Li的充分迁移及Ni、Co、Mn的重排，才得到化学式为LiNi0.4Co0.2Mn0.4CO3的上述复合氧化物，即最终产物具有稳定的化学组成及结构；
2、工艺易于控制，制备Ni、Co、Mn复合氢氧化物的中间体呈球形的活性才好，但条件不易控制；
3、在碱性条件下的前躯体产物严格来说是Ni0.4Co0.2Mn0.4CO3的碱式盐，其在高温分解时，由于非球形外观、碳酸盐和氢氧化物不同的分解特点，使分解产物具有晶格缺陷和大量的内微孔，因此有比容量大、应用寿命长、颗粒径分布窄等优异性能。
附图说明
图1是本发明实施例的Ni0.4Co0.2Mn0.4CO3前躯体放大1000倍照片；
图2是本发明实施例的Ni0.4Co0.2Mn0.4CO3前躯体的粒度分布；
图3是本发明实施例的LiNi0.4Co0.2Mn0.4CO3与Li2CO2的锂离子电池放电曲线；
图4是本发明实施例的LiNi0.4Co0.2Mn0.4O2循环曲线：
具体实施方式
以下结合附图对本发明详细说明：
以合成化学式为Ni0.4Co0.2Mn0.4CO3为例，计量配制1.0mol/l的钴、镍、锰混合硫酸盐水溶液、1.0mol/l Na2CO3水溶液、1.0mol/lNaOH水溶液，同时将上述溶液添加入反应器中，反应速度保持45℃、pH值控制在8.5-9，以40转/分速度搅拌反应时间10小时；经过滤、洗涤、烘干处理，得到Ni0.4Co0.2Mn0.4CO3前躯体，以图1的电镜照片可以看出，该前躯体为非球形、大小均一、分散无聚集体，图2现示粒度分布窄、颗粒大小平均为10um。
以合成化学式为LiNi0.4Co0.2Mn0.4O3为例，讲量加入Ni1-x-yCOXMnyCO3前躯体、Li2CO3以先干料混合后再加水湿混方式混合，充分搅拌使混合均匀后再移入于反应炉中，以温度550℃，煅烧时间6小时；冷却、粉碎后再以850℃温度锻烧时间20小时，冷却后经球磨即制备到LiNi0.4Co0.2Mn0.4O3，其粒度分布窄、颗粒大小平均为10um。用常规的方法做成锂离子电池，与Li2CoO2相比，电池放电曲线如图3所示，编号2与1分别代表本发明实施例电池与对比例电池，可以看出，本发明所制备的锂过渡金属复合氧化物放电容量高，达到720分钟，即合计为150mAh/g，且放电平台、中点电压接近Li2CoO2，循环寿命也达到500次。由于Co的用量降低，又不降低电池的性能，因此本发明由碳酸盐前躯体制备锂过渡复合氧化物具有新颖而显著的特点，应用价值大。
Claims (7)
1. 一种由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其特征在于：它包括如下步骤：
(1)碳酸盐前躯体的制备：
①、配制含有以钴、镍、锰为基本组分的混合金属元素离子的水溶液为A溶液，含有CO3 2-离子的水溶液为B溶液，含有水溶液性碱物质的水溶液为C溶液；
②、将A溶液、B溶液和选择性含有C溶液混合搅拌反应数小时，得到化学式为Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐的前躯体；
其中反应条件为：pH7.5-10，反应温度30-90℃，搅拌速度20-120转/分，反应时间2-30小时；
(2)锂过渡金属复合氧化物的合成：
③、取Li2CO3与上述的Ni0.4Co0.2Mn0.4CO3或其碱式碳酸盐混合均匀后，在空气中高温煅烧数小时；
④、冷却、粉碎上述煅烧物料；
⑤、再将粉碎的煅烧物料在空气中高温煅烧数小时；
⑥、冷却、球磨、筛分即可得到化学式为LiNi0.4Co0.2Mn0.4CO3锂过渡金属复合氧化物；
其中步骤(1)的A溶液为钴、镍、锰盐混合水溶液，B溶液为CO3 2离子水溶液，C溶液为水溶液性碱物质的水溶液，调节流量使反应在pH＝8-9、温度30-90℃条件下均匀进行；
其中反应条件为：③步骤的煅烧工序温度500-800℃，时间2-20小时；⑤步骤的煅烧工序温度700-950℃，时间2-30小时。
2. 根据权利要求1所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(1)的A溶液的离子浓度为0.1-3.0mol/l，混合金属元素离子来源于由硫酸盐、硝酸盐、盐酸盐、醋酸盐、其它水溶性无机盐、其它水溶性有机酸盐所组成的物质组中的至少一种原料。
3. 根据权利要求2所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(1)的A溶液含有Ca、Mg、Zn、Y、Ga、In元素的离子组中至少一种掺杂组分，掺杂组分相对于基本组分的摩尔分数为0-10％。
4. 根据权利要求1所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(1)的B溶液的CO3 2-离子浓度为0.1-3.0mol/l，CO3 2-来源于由Na2CO3、K2CO3、(NH4)2CO3、其它水溶液性碳酸盐、相应的以HCO3 -存在的水溶性盐所组成的物质组中的至少一种原料。
5. 根据权利要求1所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(1)的pH值由1.0-6.0mol/l的C溶液调节，所述C溶液为NaOH、KOH、NH3、其它水溶液性碱的物质组中至少一种的水溶液，在搅拌下，A溶液、B溶液、C溶液同时往反应器添加混合。
6. 根据权利要求2、4或5所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(1)的A溶液为钴、镍、锰硫酸盐混合水溶液，B溶液为(NH4)2CO3，C溶液为NH3.H2O水溶液，调节流量使反应在pH＝8-9、温度30-90℃条件下均匀进行。
7. 根据权利要求1所述的由碳酸盐前躯体制备锂过渡金属复合氧化物的方法，其中步骤(2)的Li2CO3与所述的Ni0.4Co0.2Mn0.4CO3混合先干料混合后再加水或乙醇等有机溶剂湿混，充分搅拌使混合均匀；其中的③步骤的煅烧工序温度550-700℃，时间6-10小时；⑤步骤的煅烧工序温度750-900℃，时间10-25小时。
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| JP4172622B2 (ja) * | 2002-04-11 | 2008-10-29 | 日鉱金属株式会社 | リチウム含有複合酸化物並びにその製造方法 |
| US9190647B2 (en) * | 2005-03-17 | 2015-11-17 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery with high temperature and storage characteristics |
| CN119133604A (zh) | 2005-10-20 | 2024-12-13 | 三菱化学株式会社 | 锂二次电池以及其中使用的非水电解液 |
| CN101043076A (zh) * | 2006-03-13 | 2007-09-26 | 法拉赛斯能源公司 | 性能提高的金属氧化物阴极材料 |
| JP4963186B2 (ja) * | 2006-03-31 | 2012-06-27 | パナソニック株式会社 | 非水電解質二次電池 |
| CN100420073C (zh) * | 2006-11-06 | 2008-09-17 | 北京科技大学 | 一种锂离子电池用层状Li[Ni1/2Mn1/2]O2材料的制备方法 |
| JP4968944B2 (ja) * | 2008-02-01 | 2012-07-04 | 日本化学工業株式会社 | 複合炭酸塩およびその製造方法 |
| JP2009259798A (ja) * | 2008-03-19 | 2009-11-05 | Panasonic Corp | 非水電解質二次電池 |
| CN101355159B (zh) * | 2008-09-17 | 2010-06-16 | 金瑞新材料科技股份有限公司 | 一种锂离子电池正极材料镍钴锰酸锂的制备方法 |
| CN102044664B (zh) * | 2010-11-10 | 2012-12-12 | 湘西自治州兴湘科技开发有限责任公司 | 锂离子电池镍钴锰酸锂三元系正极材料的制备方法 |
| KR102057026B1 (ko) * | 2012-02-08 | 2019-12-18 | 바스프 에스이 | 수산화물(들) 을 함유할 수 있는 혼합 탄산염 제조 방법 |
| US9748565B2 (en) | 2012-03-09 | 2017-08-29 | Hitachi Maxell, Ltd. | Non-aqueous electrolyte secondary battery |
| CN102790208B (zh) * | 2012-08-17 | 2015-02-04 | 深圳市新昊青科技有限公司 | 三元前驱体的制备方法及该三元前驱体 |
| CN103000903B (zh) * | 2012-11-28 | 2015-01-28 | 哈尔滨工业大学 | 一种掺杂碳纳米材料的前驱体及制备方法和球形锂金属氧化物正极材料及制备方法 |
| TWI521778B (zh) | 2013-09-05 | 2016-02-11 | 烏明克公司 | 用於含高鋰和錳的陰極材料之碳酸鹽先質 |
| WO2016055910A1 (en) | 2014-10-08 | 2016-04-14 | Umicore | Carbonate precursors for lithium nickel manganese cobalt oxide cathode material and the method of making same |
| JP6482659B2 (ja) | 2014-10-08 | 2019-03-13 | ユミコア | 好ましい形態を有する不純物含有カソード材料及び不純物含有金属炭酸塩から調製するための方法 |
| CN105489842B (zh) * | 2015-12-18 | 2018-03-23 | 浙江天能能源科技股份有限公司 | 一种富锂锰基正极材料及其制备方法 |
| CN108011095B (zh) * | 2017-11-17 | 2020-05-05 | 中国科学院青岛生物能源与过程研究所 | 一种适用于动力型锂离子电池、高循环稳定性nca正极材料的制备方法 |
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