CN105529458B - 一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法 - Google Patents
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 title abstract description 5
- 239000010406 cathode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 48
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 230000032050 esterification Effects 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 30
- 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 21
- 239000002245 particle Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910017003 Fe1−yPO4 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- -1 mercaprol Chemical compound 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 7
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 abstract 1
- 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 abstract 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910003900 Li(Ni0.5Co0.2Mn0.3)O2 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- PAMMESUSQVJOMA-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] PAMMESUSQVJOMA-UHFFFAOYSA-L 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- H—ELECTRICITY
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- 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
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Abstract
本发明公开了一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面均匀复合而成,先将镍钴锰三元材料置于含‑COOH或‑OH的溶液中分散;将磷酸锰铁锂置于含‑OH或‑COOH的溶液中分散;将两溶液混合,并加入酯化催化剂进行酯化反应,得镍钴锰酸锂/磷酸锰铁锂复合正极材料。本发明将两种表面改性后的正极材料在酯化催化剂的作用下发生酯化反应,通过化学键的方式使两种材料连接实现均匀复合,在保证三元材料的高能量密度的前提下显著地提高三元材料的安全性能,可广泛的应用于锂离子电池,特别在于适用于动力锂离子电池领域。
Description
技术领域
本发明涉及锂离子电池材料制备领域,具体涉及一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法。
背景技术
锂离子电池以其高比能量、长寿命、自放电小、无记忆效应和绿色环保等优点已广泛应用于各种电动工具和便携式电器中,近年来也开始作为新能源汽车的动力电池得到开发和利用,其中高能量密度的锂电池正极材料的开发是进一步推广新能源汽车的关键所在。
三元层状镍钴锰酸锂材料以其较高的放电比容量和平台电压而成为新能源汽车动力电池材料的发展趋势。然而三元层状镍钴锰酸锂材料在新能源汽车领域应用的安全问题成为其推广的瓶颈。橄榄石结构的磷酸盐材料具有高安全性能的特点,磷酸铁锂(LiFeP04)是其中的一种,但存在放电电压平台低(约为3.4 V)、能量密度不高等缺点,从而限制了电动汽车的续驶里程。磷酸锰铁锂(LiMnFeP04)作为橄榄石结构磷酸盐材料的一种,其结构中含有铁原子、锂原子和锰原子,其中锰原子和铁原子相互固溶,形成具有斜方晶的橄榄石型结构,其安全性能和循环性能良好。Mn3+/Mn4+电对在4. 0 V ( v.s. Li '+/ Li)附近可以实现Li+的嵌脱,获得4. 0 V平台的容量,可有效提高电池的能量密度。
将镍钴锰酸锂和磷酸锰铁锂混合,用作锂离子电池正极材料,可解决后者比表面积较大导致的加工困难,同时又可改善前者的循环性能和安全性能,有望制备具有高能量密度、高安全性能和良好循环性能的锂离子动力电池。袁万颂等(袁万颂,王赞霞,高文超,孙晓宾.LiNi0.5Co0.2Mn0.3O2-LiMn0.7Fe0.3PO4混合正极电池性能研究[J].电池,2014,6(44):331-334)提出通过机械混合的方式制备LiNi0.5Co0.2Mn0.3O2-LiMn0.7Fe0.3PO4混合正极材料,但普通机械混合方式实现的复合存在复合稳定性较差的风险,将直接影响到复合材料性能的发挥。
发明内容
本发明的目的在于克服现有技术中镍钴锰酸锂/磷酸锰铁锂之间存在的复合稳定性差的问题,提供一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的其制备方法,以提高复合材料的性能。
为了实现上述目的,本发明所采用的技术方案是:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面均匀复合而成,其步骤如下:
(1)将镍钴锰三元材料置于含-COOH或-OH的溶液中分散后并充分吸附-COOH或-OH;
(2)将磷酸锰铁锂置于含-OH或-COOH的溶液中分散后并充分吸附-OH或-COOH;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为1~5:1进行混合,并加入酯化催化剂进行酯化反应;将反应后的产品过滤、洗涤、干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
优选方案,所述镍钴锰三元材料的分子式为Li(NiaCobMn1-a-b)O2,其中a<1、b<1、a+b<1;所述磷酸锰铁锂的分子式为Li1-xMxMnyFe1-yPO4,式中0≤x≤0.1,0.4≤y<1,M选自元素周期表中第一行的过渡金属或其混合物。
优选方案,所述磷酸锰铁锂的粒径大小为2~3μm;所述镍钴锰三元材料的粒径大小为8~10μm。
优选方案,所述步骤(1)与步骤(2)中含-COOH溶液指巯基乙酸、3-巯基丙酸、巯基丙酸中的至少一种;含-OH溶液指巯基乙醇、巯基丙醇、2-巯基乙醇中的至少一种。
优选方案,所述步骤(3)中酯化催化剂为二环己基碳二亚胺(DCC)或氯化亚砜。
优选方案,所述步骤(3)中酯化反应的温度为80~120℃、时间为30min~2h;所述干燥的温度为70-100 ℃。
优选方案,所述磷酸锰铁锂在镍钴锰三元材料表面均匀复合是指小粒径的磷酸锰铁锂在大粒径镍钴锰三元材料的表面通过化学键酯键进行均匀复合。
磷酸锰铁锂Li1-xMxMnyFe1-yPO4中M选自元素周期表第一行的过渡金属或其混合物,元素周期表第一行的过渡金属为Sc-钪、Ti-钛、V-钒、Cr-铬、Mn-锰、Fe-铁、Co-钴、Ni-镍 、Cu-铜 、Zn-锌。
本发明通过酯化反应将磷酸锰铁锂在镍钴锰酸锂三元材料的表面通过化学键酯键进行复合制备出复合材料。即本发明通过化学处理分别在镍钴锰三元材料表面改性引入羧基(-COOH)或羟基(-OH),同时在磷酸锰铁锂表面改性引入羟基(-OH)或羧基(-COOH),随后将两者溶液相混合后加入酯化催化剂,使磷酸锰铁锂表面的羟基(-OH)与镍钴锰三元材料表面的羧基(-COOH) 发生酯化反应,或使磷酸锰铁锂表面的羧基(-COOH) 与镍钴锰三元材料表面的羟基(-OH)发生酯化反应,进而实现将小粒径的磷酸锰铁锂在大粒径的镍钴锰酸锂三元材料表面通过化学键酯键均匀复合。所以本发明制备的镍钴锰酸锂/磷酸锰铁锂复合正极材料,可以在保证镍钴锰三元材料的高能量密度的前提下显著地提高镍钴锰三元材料的安全性能,可广泛的应用于锂离子电池,特别在于适用于动力锂离子电池领域。
具体实施方式
以下结合实施例,对本发明进行较为详细的说明。
实施例1:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面通过化学键酯键进行均匀复合而成,其步骤如下:
(1)将粒径大小为8μm的镍钴锰三元材料Li(Ni1/3Co1/3Mn1/3)O2置于巯基乙酸溶液中分散;
(2)将粒径大小为2μm的磷酸锰铁锂LiMn0.8Fe0.2PO4置于巯基乙醇溶液中分散;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为5:1进行混合,并加入酯化催化剂二环己基碳二亚胺(DCC)进行酯化反应,酯化反应的温度为80℃、时间为2h;将反应后的产品过滤、洗涤后在100 ℃进行干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
实施例2:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面通过化学键酯键进行均匀复合而成,其步骤如下:
(1)将粒径大小为10μm的镍钴锰三元材料Li(Ni1/3Co1/3Mn1/3)O2置于含2-巯基乙醇的溶液中分散;
(2)将粒径大小为3μm的磷酸锰铁锂LiMn0.8Fe0.2PO4置于含3-巯基乙酸的溶液中分散;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为4:1进行混合,并加入酯化催化剂二环己基碳二亚胺(DCC)进行酯化反应,酯化反应的温度为120℃、时间为30min;将反应后的产品过滤、洗涤后在70 ℃进行干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
实施例3:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面通过化学键酯键进行均匀复合而成,其步骤如下:
(1)将粒径大小为10μm的镍钴锰三元材料Li(Ni0.5Co0.2Mn0.3)O2置于含巯基乙酸的溶液中分散;
(2)将粒径大小为3μm的磷酸锰铁锂LiMn0.7Fe0.3PO4置于含巯基乙醇的溶液中分散;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为3:1进行混合,并加入酯化催化剂二环己基碳二亚胺(DCC)或氯化亚砜进行酯化反应,酯化反应的温度为100℃、时间为1h;将反应后的产品过滤、洗涤后在90 ℃进行干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
实施例4:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面通过化学键酯键进行均匀复合而成,其步骤如下:
(1)将粒径大小为9μm的镍钴锰三元材料Li(Ni0.5Co0.2Mn0.3)O2置于含巯基丙醇的溶液中分散;
(2)将粒径大小为2.5μm的磷酸锰铁锂LiMn0.7Fe0.3PO4置于含巯基丙酸的溶液中分散;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为2:1进行混合,并加入酯化催化剂氯化亚砜进行酯化反应,酯化反应的温度为100℃、时间为1h;将反应后的产品过滤、洗涤后在100 ℃进行干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
将本实施例制备的镍钴锰酸锂/磷酸锰铁锂复合正极材料和三元镍钴锰正极材料Li(Ni0.5Co0.2Mn0.3)O2的电化学性能进行对比,根据GB/T 31486-2015测试标准,测试结果如下表1所示,磷酸锰铁锂的引入能够提高电池的能量密度。另外,对其各自制备的电池进行针刺试验, 三元镍钴锰正极材料制作的电池针刺不通过,而镍钴锰酸锂/磷酸锰铁锂复合正极材料制作的电池可以通过针刺测试。
表1电化学性能对比
样品 | 中值电压 (V) | 克容量 (mAh/g) | 能量密度(Wh/kg) |
Li(Ni0.5Co0.2Mn0.3)O2 | 3.76 | 169.0 | 635.4 |
镍钴锰酸锂/磷酸锰铁锂复合正极材料 | 3.84 | 166.0 | 637.4 |
实施例5:
一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面通过化学键酯键进行均匀复合而成,其步骤如下:
(1)将粒径大小为10μm的镍钴锰三元材料Li(Ni0.6Co0.2Mn0.2)O2置于含3-巯基丙酸的溶液中分散;
(2)将粒径大小为2μm的磷酸锰铁锂LiCo0.05Mn0.0.7Fe0.295PO4置于含巯基丙酸的溶液中分散;
(3)将步骤(1)得到的溶液与步骤(2)得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为1:1进行混合,并加入酯化催化剂氯化亚砜进行酯化反应,酯化反应的温度为90℃、时间为1.5h;将反应后的产品过滤、洗涤后在100 ℃进行干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料。
以上所述的实例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (5)
1.一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法,其是由磷酸锰铁锂在镍钴锰三元材料表面均匀复合而成,其特征在于:步骤如下:
(1)将镍钴锰三元材料置于含-COOH的溶液中分散,再将磷酸锰铁锂置于含-OH的溶液中分散;或将镍钴锰三元材料置于含-OH的溶液中分散,再将磷酸锰铁锂置于含-COOH的溶液中分散;
(2)将上述两种分散得到的溶液按镍钴锰三元材料和磷酸锰铁锂的摩尔比为1~5:1进行混合,并加入酯化催化剂进行酯化反应;将反应后的产品过滤、洗涤、干燥,即可得镍钴锰酸锂/磷酸锰铁锂复合正极材料;
所述磷酸锰铁锂的粒径大小为2~3μm;所述镍钴锰三元材料的粒径大小为8~10μm;
含-COOH溶液指巯基乙酸、3-巯基丙酸、巯基丙酸中的至少一种;含-OH溶液指巯基乙醇、巯基丙醇、2-巯基乙醇中的至少一种。
2.根据权利要求1所述的制备方法,其特征在于:所述镍钴锰三元材料的分子式为Li(NiaCobMn1-a-b)O2,其中a<1、b<1、a+b<1;所述磷酸锰铁锂的分子式为Li1-xMxMnyFe1-yPO4,式中0≤x≤0.1,0.4≤y<1,M选自元素周期表中第一行的过渡金属或其混合物。
3.根据权利要求1所述的制备方法,其特征在于:所述步骤(2)中酯化催化剂为二环己基碳二亚胺(DCC)或氯化亚砜。
4.根据权利要求1所述的制备方法,其特征在于:所述步骤(2)中酯化反应的温度为80~120℃、时间为30min~2h;所述干燥的温度为70-100 ℃。
5.根据权利要求1所述的制备方法,其特征在于:所述磷酸锰铁锂在镍钴锰三元材料表面均匀复合是指小粒径的磷酸锰铁锂在大粒径镍钴锰三元材料的表面通过化学键酯键进行均匀复合。
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