CN113488632B - 一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料及其制备方法 - Google Patents
一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料及其制备方法 Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 10
- 229910001416 lithium ion Inorganic materials 0.000 title description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 238000003892 spreading Methods 0.000 claims 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 abstract description 20
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 abstract description 20
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 abstract description 20
- 238000004090 dissolution Methods 0.000 abstract description 5
- 229910013716 LiNi Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 abstract description 2
- 229910018068 Li 2 O Inorganic materials 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 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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Abstract
本发明公开了一种Li1‑xTMO4‑yNy/Li2SO4包覆的高镍三元正极材料及其制备方法，所述正极材料为Li1‑xTMO4‑yNy/Li2SO4包覆的LiNi1‑xyCoxMnyO2复合材料，所述方法为：1）将Ni1‑x‑yCoxMny(OH)2三元前驱体和锂源均匀混合后，在氧气氛围下热处理，得到LiNi1‑x‑yCoxMnyO2正极材料；2）将硫酸铵和LiNi1‑x‑yCoxMnyO2分别放入两个烧舟中，通过固体受热分解产生气体NH3和SO3，NH3和SO3与正极材料表面发生反应，SO3与材料表面的残余锂反应，并夺取正极材料次表面的锂源Li2O反应Li2SO4，造成材料表面产生锂空位，从而由层状结构向尖晶石结构转变，最终获得Li1‑xTMO4‑yNy/Li2SO4包覆LiNi1‑x‑yCoxMnyO2正极材料。这种改性方法能提高层状LiNi1‑x‑yCoxMnyO2结构稳定性，从而提高材料循环稳定和抑制正极材料循环过程中过渡金属溶解，这种制备方法简单、成本低、环境友好，适用于大规模工业生产。
Description
技术领域
本发明涉及锂离子电池电极材料制备技术领域，具体是一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料及其制备方法。
背景技术
随着石油能源的不断消耗，储能技术也在不断发展。因此，高能量密度的锂离子电池正受到越来越多的关注。正极材料是锂离子电池最重要的组成部分。考虑到高镍含量正极材料LiNi1-x-yCoxMnyO2，这些材料被认为是未来锂离子电池的正极材料。然而，它们严重的容量衰减限制了它们的进一步应用，这主要是因为粒子中的Ni3+离子极不稳定，特别是暴露在潮湿的环境中，会自发地缓慢地还原为Ni2+。同时，正极材料表面容易吸收空气水分和二氧化碳，产生LiOH、Li2CO3等杂质，严重影响电化学性能。LiNi1-x-yCoxMnyO2表现出优越的电化学和热力学稳定性。然而，仍然存在诸如高速率循环后容量快速损耗等限制。在溶解过程中，活性的Ni3+被氧化成不稳定的、不活性的Ni4+，其中部分Ni4+在随后的锂化过程中难以还原为Ni3+，导致可逆容量严重损失。同时，由于Ni4+的高氧化态，其表面的Ni4+会氧化电解液，引起主体材料与电解液之间的副反应，导致表面膜电阻和界面电阻增大。表面涂层能有效解决表面问题。一般情况下，在表面均匀地涂覆稳定的化合物或快离子导体可以有效抑制活性物质与电解质之间的副反应，从而提高循环稳定性和热力学性能。
目前，对NCM进行了大量的改进工作。离子掺杂是一种典型的方法，可以抑制Li+/Ni2+无序，提高结构稳定性，但活性材料的溶解问题仍有待解决因此，表面改性作为减轻结构退化和改善循环性能的另一种有效方法被广泛研究。一般情况下，各种涂层材料如Al2O3、TiO2、SiO2、和SnO2等都被深入研究，以缓解电解质与主体材料之间的副反应。然而，大多数改性材料都是仅形成均匀涂层的锂离子绝缘子，表现出低的Li+/电子输运性或限制了自结构稳定性，导致改性效果有限，倍率性能较差。要实现优良的改性层，同时又具有快速的Li+导电性和高的化学稳定性，是一项巨大的挑战。
发明内容
本发明的目的是针对现有技术的不足，而提供一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料及其制备方法。这种正极材料能提高层状LiNi1-x-yCoxMnyO2结构稳定性，提高材料的循环稳定性性能和抑制正极材料循环过程中过渡金属溶解，这种制备方法简单、成本低、环境友好，适用于大规模工业生产。
实现本发明目的的技术方案是：
一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料，所述正极材料为Li1-xTMO4- yNy/Li2SO4包覆的LiNi1-xyCoxMnyO2复合材料，式中0<x<0.4，0<y<0.4，1-x-y≥0.6，其中，Li1- xTMO4-yNy/Li2SO4包覆的LiNi1-xyCoxMnyO2复合材料中，Li1-xTMO4-yNy/Li2SO4包覆层的质量分数为0-10％。
上述的Li1-xTMO4-yNy/Li2SO4包覆高镍三元正极材料的制备方法，包括如下步骤：
1)将Ni1-x-yCoxMny(OH)2三元前驱体和锂源均匀混合后，置于刚玉坩埚中，放入管式炉中，在氧气氛围下热处理，得到LiNi1-x-yCoxMnyO2正极材料；
2)将硫酸铵和LiNi1-x-yCoxMnyO2正极材料称量后分别放入两个烧舟中，即Li1- xTMO4-yNy/Li2SO4放入一个烧舟中但不混合，LiNi1-x-yCoxMnyO2正极材料放入另一个烧舟中均匀铺平，放入管式炉中，在惰性气氛下进一步进行热处理，硫酸铵和LiNi1-x-yCoxMnyO2分别放入两个烧舟中，通过硫酸铵固体受热分解产生气体NH3和SO3，NH3和SO3与正极材料表面发生反应，实现N3-掺杂，并且SO3夺取材料表面锂源并与表面残余锂发生反应生成Li2SO4，从而促使LiNi1-x-yCoxMnyO2正极材料表面由层状结构向尖晶石结构的转变，最终获得Li1-xTMO4-yNy/Li2SO4包覆LiNi1-x-yCoxMnyO2正极材料，此反应于惰性气Ar或N2气氛下，热处理时升温速度为2℃/min-5℃/min，升温至500℃-700℃、保温2h，自然冷却至室温后，即得到Li1-xTMO4-yNy/Li2SO4包覆LiNi1-x-yCoxMnyO2正极材料。
步骤1)中所述的锂源为碳酸锂、氢氧化锂、硝酸锂或乙酸锂中的一种或几种。
步骤2)中所述硫酸铵的加入量为(NH4)2SO4/LiNi1-x-yCoxMnyO2混合物中的质量分数为0-10％。
步骤2)中所述的热处理温度为500-700℃，热处理时间为5-30min。
用上述制备方法制得的用Li1-xTMO4-yNy/Li2SO4表面修饰LiNi1-x-yCoxMnyO2正极材料表面的化学式为：NCM@SN、且包覆层的质量为LiNi0.8Co0.1Mn0.1O2质量的0-10％。
用上述制备方法制得的用Li1-xTMO4-yNy/Li2SO4修饰表面的正极材料，应用于CR2025扣式电池时以LiNi1-x-yCoxMnyO2@Li1-xTMO4-yNy/Li2SO4锂离子正极材料、super-p导电剂和聚偏氟乙烯粘结剂按质量比8：1：1，加入N-甲基-2-吡咯烷酮混合成均匀浆料，用涂覆法均匀涂布在铝箔上，烘干滚压后，冲成圆形的电极片，120℃真空干燥12h，以制备的LiNi0.8Co0.1Mn0.1O2锂离子正极材料电极为正极，金属锂片为负极，1M LiPF6和体积比为1：1：1的EC/DMC/EMC为电解液、Celgard23250微孔膜为隔膜，在手套箱中装配成纽扣电池。
这种正极材料能提高层状结构LiNi0.8Co0.1Mn0.1O2结构稳定性、循环性能和抑制循环过程中过渡金属溶解的缺陷，这种制备方法简单、成本低、环境友好，适用于大规模工业生产。
附图说明
图1为实施例中表面修饰前纯相LiNi0.8Co0.1Mn0.1O2正极材料SEM图；
图2为实施例制备的NCM@SN正极材料的SEM图；
图3为实施例制备的NCM@SN正极材料的XRD图谱；
图4为实施例制备的NCM@SN正极材料组装成的CR2025型半电池在2.7-4.5V、1C电流密度下的放电循环曲线示意图；
图5为实施例制备的NCM@SN正极材料组装成的CR2025型半电池在2.7-4.5V不同倍率下的倍率性能曲线示意图。
具体实施方式
下面结合附图和实施例对本发明的内容作进一步的阐述，但不是对本发明的限定。
实施例：
一种用Li1-xTMO4-yNy/Li2SO4表面修饰层状结构LiNi1-x-yCoxMnyO2正极材料的制备方法，包括如下步骤：
1)分别称取5g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、2.40g一水合氢氧化锂，在研钵中研磨均匀后，置于烧舟中，放入充满氧气的管式炉中，以5℃/min的速率升温至480℃，保温5h，再同样以5℃/min的速率升温至750℃，保温15h，自然冷却得到LiNi0.8Co0.1Mn0.1O2正极材料，如图1所示；
2)将硫酸铵和步骤1)制备LiNi0.8Co0.1Mn0.1O2正极材料称量后分别放入两个烧舟中，即硫酸铵放入一个烧舟中但不混合，LiNi0.8Co0.1Mn0.1O2正极材料放入另一个烧舟中均匀铺平，放入管式炉中，在惰性气氛下进一步进行热处理，通过硫酸铵固体受热分解产生气体NH3和SO3，NH3和SO3与正极材料表面发生反应，实现N3-掺杂，并且SO3夺取材料表面锂源并与表面残余锂发生反应生成Li2SO4，从而促使材料表面由层状结构向尖晶石结构的转变，最终获得Li1-xTMO4-yNy/Li2SO4包覆LiNi1-x-yCoxMnyO2正极材料，通过XRD图可以得知，表面改性并没有影响材料的本体结构，结果如图2和图3所示。
参见图2、图3，用上述制备方法制得的用Li1-xTMO4-yNy/Li2SO4表面修饰LiNi1-x- yCoxMnyO2正极材料表面的化学式为：NCM@SN、且包覆层的质量为LiNi0.8Co0.1Mn0.1O2质量的0-10％。
参见图4、图5，将步骤2)制备的LiNi0.8Co0.1Mn0.1O2@Li1-xTMO4-yNy/Li2SO4锂离子正极材料、super-p导电剂和聚偏氟乙烯粘结剂按质量比8：1：1，加入N-甲基-2-吡咯烷酮混合成均匀浆料，用涂覆法均匀涂布在铝箔上，烘干滚压后，冲成圆形的电极片，120℃真空干燥12h，以制备的LiNi0.8Co0.1Mn0.1O2锂离子正极材料电极为正极，金属锂片为负极，1M LiPF6和EC/DMC/EMC(体积比为1：1：1)为电解液，Celgard 23250微孔膜为隔膜，在手套箱中装配成纽扣电池，从电化学性能图中，可以得出表面改性可以有效的提高材料的电化学性能。
Claims (2)
1.一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料，其特征在于，所述材料的采用以下方法制备：
1)分别称取5g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、2.40g一水合氢氧化锂，在研钵中研磨均匀后，置于烧舟中，放入充满氧气的管式炉中，以5℃/min的速率升温至480℃，保温5h，再同样以5℃/min的速率升温至750℃，保温15h，自然冷却得到LiNi0.8Co0.1Mn0.1O2正极材料；
2)将硫酸铵和步骤1)制备LiNi0.8Co0.1Mn0.1O2正极材料称量后分别放入两个烧舟中，即硫酸铵放入一个烧舟中但不混合，LiNi0.8Co0.1Mn0.1O2正极材料放入另一个烧舟中均匀铺平，放入管式炉中，在惰性气氛下进一步进行热处理，通过硫酸铵固体受热分解产生气体NH3和SO3，NH3和SO3与正极材料表面发生反应，实现N3-掺杂，并且SO3夺取材料表面锂源并与表面残余锂发生反应生成Li2SO4，从而促使材料表面由层状结构向尖晶石结构的转变，最终获得Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料；其中，包覆层的质量为LiNi0.8Co0.1Mn0.1O2质量的大于0至小于10％。
2.如权利要求1所述的一种Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料的应用，其特征在于，应用于CR2025扣式电池，以所述Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料、super-p导电剂和聚偏氟乙烯粘结剂按质量比8：1：1，加入N-甲基-2-吡咯烷酮混合成均匀浆料，用涂覆法均匀涂布在铝箔上，烘干滚压后，冲成圆形的电极片，120℃真空干燥12h，以所述Li1-xTMO4-yNy/Li2SO4包覆的高镍三元正极材料为正极，金属锂片为负极，1M LiPF6和体积比为1：1：1的EC/DMC/EMC为电解液、Celgard 23250微孔膜为隔膜，在手套箱中装配成纽扣电池。
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