CN106904668B - 一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法 - Google Patents
一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 title description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 title 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims abstract description 18
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims abstract description 10
- 229930064664 L-arginine Natural products 0.000 claims abstract description 10
- 235000014852 L-arginine Nutrition 0.000 claims abstract description 10
- 235000019766 L-Lysine Nutrition 0.000 claims abstract description 9
- 239000004472 Lysine Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- BVPMZCWLVVIHKO-UHFFFAOYSA-N lithium cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Co+2].[Li+] BVPMZCWLVVIHKO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 18
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 18
- 229910001437 manganese ion Inorganic materials 0.000 claims description 18
- 229910001453 nickel ion Inorganic materials 0.000 claims description 18
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000001869 cobalt compounds Chemical class 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 150000002816 nickel compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 235000001014 amino acid Nutrition 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 229910002102 lithium manganese oxide Inorganic materials 0.000 abstract description 9
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- RRWITPGYJAEIKP-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Co+2].[Mn+2].[Li+] Chemical compound [O-2].[Mn+2].[Ni+2].[Co+2].[Mn+2].[Li+] RRWITPGYJAEIKP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229940071257 lithium acetate Drugs 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013909 LiNi0.3Co0.4Mn1.3O4 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron 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
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
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- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- 238000001694 spray drying Methods 0.000 description 1
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Abstract
本发明公开了一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法，所述方法先通过微波加热法制备得到镍钴锰酸锂晶种，然后再用水热法制备得到纳米级的镍钴锰酸锂；该方法利用微波的快速加热效果，得到的晶种细小均匀，作为后续水热步骤的晶体生长基点，有助于得到粒径小并且尺寸均匀的产物，而在水热过程中，选用L‑精氨酸或L‑赖氨酸作为沉淀剂以及软模板剂，得到具有十四面体结构的纳米级镍钴锰酸锂。本发明得到的十四面体形纳米镍钴锰酸锂作为锂离子电池正极材料，由于其特殊的形貌对离子扩散的影响以及对颗粒堆积的影响，提高了功率密度和电池比容量，具有广阔的应用前景。
Description
技术领域
本发明涉及一种用作电池正极材料的镍钴锰酸锂的制备方法，特别是涉及一种电池正极材料十四面体形的纳米镍钴锰酸锂的制备方法。
背景技术
近年来，各种电子设备飞速发展，对于电池的要求越来越高，而锂离子电池被视作最好的新型能源，大到电动汽车，小到笔记本、手机，都离不开锂电池。
锰酸锂(LiMn2O4)由于具有电压高、价格低廉、资源丰富、与环境友好等特点，成为最有前途的锂离子电池正极材料之一，得到广泛的研究与应用。但是锰酸锂在循环过程中容量有较大的衰减，严重阻碍了其商业化的应用。经研究发现，影响锰酸锂的容量衰减的因素主要在于：(1)相结构的纯度及稳定性、微观形貌的不规则；(2)材料在深度放电时产生Jahn-Teller效应；(3)锰酸锂在充放电时容易发生歧化反应，产生三价锰离子溶解到电解液中等。
相比于LiFePO4、LiCoO2等正极材料，锰酸锂由于原材料丰富，价格优势明显，并且其制备工艺相对简单，安全性能高。因此，目前对该材料的研究只要集中在掺杂改性等方面，以提高其循环性能。其中，用Fe、Co、Ni、Zn等金属掺杂以稳定尖晶石结构、提高循环性能是较为有效的方法。尤其是双掺杂的锰酸锂，其性能较为优异，得到了广泛的关注和研究。
目前，合成镍钴锰酸锂的方法主要有高温固相法、共沉淀法、溶胶凝胶法等、喷雾干燥法等。其中，利用共沉淀法制备得到的镍钴锰酸锂电化学性能指标较好，但是在制备过程中难以实现分子水平的均匀混合，一定程度上影响到其电化学性能。
作为电池正极材料，镍钴锰酸锂的电化学性能与锰离子的价态(+3价和 +4价)、Mn/(Ni+Co)比例、颗粒形貌、表面位面、表面组成等相关。
纳米材料是近年来研究的热点，纳米正极材料具有大的比表面积，增大了材料与电解液的接触程度，小粒径也缩短了锂离子固相扩散的路径，都有利于提高材料的功率密度。另外，不同的形貌以及结晶度及规则程度，也会对电化学性能带来较大的影响，规则的微粒可以减小团聚和粒子架桥现象，降低颗粒堆积填充时的粒子碱洗，进而有利于锂离子电池比容量的提高。
发明内容
本发明的目的在于提供一种十四面体形的纳米镍钴锰酸锂，作为锂离子电池正极材料时，由于其独特的形貌而有助于提高电池的功率密度和电池比容量。
本发明的目的通过以下技术方案实现：
一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法，其特征在于，包括如下步骤：
(1)微波法制备晶种：将可溶性锂化合物、可溶性镍化合物、可溶性钴化合物和可溶性锰化合物分别溶解于去离子水中，形成浓度均为 0.05-0.07mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为1∶x∶y∶(2-x-y)的比例将四种溶液混合并搅拌均匀，然后再加入浓度为0.1mol/L的尿素水溶液，搅拌 10-30min得到混合溶液，将上述混合溶液经微波加热，得到晶种溶液；其中，微波加热功率为约5～6kW，频率为2500MHz，时间为2～6分钟，尿素与锂离子的摩尔比为6-8∶1；
(2)镍钴锰酸锂的制备：将可溶性锂化合物、可溶性镍化合物、可溶性钴化合物和可溶性锰化合物分别溶解于去离子水中，形成浓度均为 0.1-0.3mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为1∶x∶y∶(2-x-y)的比例将四种溶液混合并搅拌均匀，再加入步骤(1)得到的晶种溶液充分搅拌至混合均匀，最后再加入0.2mol/L的氨基酸水溶液，将得到的混合反应物放入水热反应釜中在140-180℃下水热反应2～5h，取出反应产物，过滤，洗涤，并在50-60℃下干燥，得到十四面体形纳米镍钴锰酸锂；
其中，步骤(1)和(2)中所述的可溶性锂化合物为硝酸锂或醋酸锂、所述的可溶性镍化合物为硝酸镍或醋酸镍，所述的可溶性钴化合物为硝酸钴或醋酸钴，所述的可溶性锰化合物为硝酸锰或醋酸锰，0.2≤x≤0.4，0.2≤y≤0.4；步骤(2)中所述的氨基酸溶液为L-精氨酸水溶液或L-赖氨酸水溶液，L-精氨酸或L-赖氨酸与锂离子的摩尔比为7-10∶1。
本发明公开的电池正极材料镍钴锰酸锂的制备方法，通过两步法制备得产物，其原理如下：
第一步为晶种的制备，即对制备好的反应原料采用微波的方法进行加热得到颗粒细小的晶种。由于选用的微波加热设备频率为2500MH，原料中的极性分子在其作用下每秒钟变换方向2.5×109次，分子来回转动，与周围分子相互碰撞摩擦，迅速升温，原料中的尿素作为沉淀剂释放出OH-，与锂离子和镍离子、钴离子、锰离子快速反应得到晶种，另一方面，由于微波加热的均匀性并通过控制反应时间以及反应原料的浓度，有效地避免了晶种的长大，得到大量细小的镍钴锰酸锂晶种颗粒。
第二步为纳米镍钴锰酸锂产物的制备，即利用上一步骤中得到的晶种，与反应原料混合，在常规的水热反应釜中进行反应，得到产物十四面体形的纳米镍钴锰酸锂。该步骤在大量细小的晶种作为生长基点的基础上，通过传统的水热法，将原料锂离子、镍离子、钴离子和锰离子反应，得到产物纳米级的镍钴锰酸锂，其粒径分布均匀。该步骤中，将反应原料的浓度适当提高，加快其反应与晶体生长速度，而水溶性的氨基酸L-精氨酸或L-赖氨酸一方面作为具有缓释效果的沉淀剂保证反应的进行，另一方面，L-精氨酸或L-赖氨酸也作为软模板剂，促进镍钴锰酸锂晶体结构的发育，形成十四面体形。至于得到十四面体形的机理，发明人猜测可能是由于L-精氨酸或L-赖氨酸的位阻效应，或者是由于其上的基团，如-COOH、-NH2，与水中氢键、范德华力，共同促进纳米镍钴锰酸锂的组装与成形。
本发明得到的十四面体形纳米镍钴锰酸锂作为锂离子电池正极材料，由于其特殊的形貌对离子扩散的影响以及对颗粒堆积的影响，提高了功率密度和电池比容量，具有广阔的应用前景。
附图说明
图1是实施例1得到的十四面体形纳米镍钴锰酸锂的XRD图；
图2是实施例1得到的十四面体形纳米镍钴锰酸锂的SEM图。
具体实施方式
以下为本发明的具体实施方式，用以对本发明进行解释和说明。
实施例1
一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法，其特征在于，包括如下步骤：
(1)微波法制备晶种：将硝酸锂、硝酸镍、硝酸钴和醋酸锰分别溶解于去离子水中，形成浓度均为0.05mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为 1∶0.3∶0.3∶1.4的比例将四种溶液混合并搅拌均匀，然后再加入浓度为0.1mol/L 的尿素水溶液，搅拌30min得到混合溶液，将上述混合溶液经微波加热，得到晶种溶液；其中，微波加热功率为5kW，频率为2500MHz，时间为4分钟，尿素与锂离子的摩尔比为6∶1；
(2)镍钴锰酸锂的制备：将硝酸锂、醋酸镍、硝酸钴和醋酸锰分别溶解于去离子水中，形成浓度均为0.1mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为 1∶0.3∶0.3∶1.4的比例将四种溶液混合并搅拌均匀，再加入步骤(1)得到的晶种溶液充分搅拌至混合均匀，最后再按照L-赖氨酸与锂离子的摩尔比为7∶1，加入0.2mol/L的L-赖氨酸水溶液，将得到的混合反应物放入水热反应釜中在 150℃下水热反应4h，取出反应产物，过滤，洗涤，并在60℃下干燥，得到十四面体形纳米镍钴锰酸锂LiNi0.3Co0.3Mn1.4O4。
图1和2分别为制备出的十四面体形纳米镍钴锰酸锂的XRD和SEM图，从中可以确定，制备出的产物为镍钴锰酸锂LiNi0.3Co0.3Mn1.4O4晶体，晶粒尺寸分布均匀，形貌统一。
实施例2
一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法，其特征在于，包括如下步骤：
(1)微波法制备晶种：将醋酸锂、醋酸镍、醋酸钴和醋酸锰分别溶解于去离子水中，形成浓度均为0.07mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为 1∶0.3∶0.4∶1.3的比例将四种溶液混合并搅拌均匀，然后再加入浓度为0.1mol/L 的尿素水溶液，搅拌30min得到混合溶液，将上述混合溶液经微波加热，得到晶种溶液；其中，微波加热功率为6kW，频率为2500MHz，时间为2分钟，尿素与锂离子的摩尔比为8∶1；
(2)镍钴锰酸锂的制备：将醋酸锂、醋酸镍、醋酸钴和醋酸锰分别溶解于去离子水中，形成浓度均为0.3mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为 1∶0.3∶0.4∶1.3的比例将四种溶液混合并搅拌均匀，再加入步骤(1)得到的晶种溶液充分搅拌至混合均匀，最后再按照L-精氨酸与锂离子的摩尔比为10∶1，加入0.2mol/L的L-精氨酸水溶液，将得到的混合反应物放入水热反应釜中在 180℃下水热反应2.5h，取出反应产物，过滤，洗涤，并在50℃下干燥，得到十四面体形纳米镍钴锰酸锂LiNi0.3Co0.4Mn1.3O4。
Claims (1)
1.一种电池正极材料十四面体形纳米镍钴锰酸锂的制备方法，其特征在于，包括如下步骤：
(1)微波法制备晶种：将可溶性锂化合物、可溶性镍化合物、可溶性钴化合物和可溶性锰化合物分别溶解于去离子水中，形成浓度均为0.05-0.07mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为1∶x∶y∶(2-x-y)的比例将四种溶液混合并搅拌均匀，然后再加入浓度为0.1mol/L的尿素水溶液，搅拌10-30min得到混合溶液，将上述混合溶液经微波加热，得到晶种溶液；其中，微波加热功率为约5～6kW，频率为2500MHz，时间为2～6分钟，尿素与锂离子的摩尔比为6-8∶1；
(2)镍钴锰酸锂的制备：将可溶性锂化合物、可溶性镍化合物、可溶性钴化合物和可溶性锰化合物分别溶解于去离子水中，形成浓度均为0.1-0.3mol/L的锂离子溶液、镍离子溶液、钴离子溶液和锰离子溶液，然后按照锂离子、镍离子、钴离子和锰离子的摩尔比为1∶x∶y∶(2-x-y)的比例将四种溶液混合并搅拌均匀，再加入步骤(1)得到的晶种溶液充分搅拌至混合均匀，最后再加入0.2mol/L的氨基酸水溶液，将得到的混合反应物放入水热反应釜中在140-180℃下水热反应2～5h，取出反应产物，过滤，洗涤，并在50-60℃下干燥，得到十四面体形纳米镍钴锰酸锂；
其中，步骤(1)和(2)中所述的可溶性锂化合物为硝酸锂或醋酸锂、所述的可溶性镍化合物为硝酸镍或醋酸镍，所述的可溶性钴化合物为硝酸钴或醋酸钴，所述的可溶性锰化合物为硝酸锰或醋酸锰，0.2≤x≤0.4，0.2≤y≤0.4；步骤(2)中所述的氨基酸溶液为L-精氨酸水溶液或L-赖氨酸水溶液，L-精氨酸或L-赖氨酸与锂离子的摩尔比为7-10∶1。
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