CN112768662A - 一种低温气相沉积包覆的高镍三元层状正极材料及其制备方法 - Google Patents
一种低温气相沉积包覆的高镍三元层状正极材料及其制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title claims abstract description 9
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 38
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims abstract description 32
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims abstract description 32
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000011669 selenium Chemical group 0.000 claims abstract description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 17
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 17
- 239000011630 iodine Chemical group 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011593 sulfur Chemical group 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 40
- 229910052593 corundum Inorganic materials 0.000 claims description 23
- 239000010431 corundum Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 claims description 2
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 claims description 2
- 102100024304 Protachykinin-1 Human genes 0.000 claims description 2
- 101800003906 Substance P Proteins 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- CWWARWOPSKGELM-SARDKLJWSA-N methyl (2s)-2-[[(2s)-2-[[2-[[(2s)-2-[[(2s)-2-[[(2s)-5-amino-2-[[(2s)-5-amino-2-[[(2s)-1-[(2s)-6-amino-2-[[(2s)-1-[(2s)-2-amino-5-(diaminomethylideneamino)pentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-5-oxopentanoyl]amino]-5 Chemical compound C([C@@H](C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCSC)C(=O)OC)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CCCN=C(N)N)C1=CC=CC=C1 CWWARWOPSKGELM-SARDKLJWSA-N 0.000 claims description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 claims 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 9
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- 238000009835 boiling Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000011888 foil Substances 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
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- 239000004570 mortar (masonry) Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 5
- 239000012982 microporous membrane Substances 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
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- 229910052786 argon Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000002345 surface coating layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
本发明属于电化学储能电池领域,具体涉及一种低温气相沉积包覆的高镍三元正极材料及其制备方法。正极材料为单质X(X分别为低熔沸点的磷、硫、硒、碲和碘等)包覆的LiNi1‑x‑ yCoxMnyO2,利用低温气相沉积的方法,将低熔沸点的单质X均匀包覆在高镍三元正极材料LiNi1‑x‑yCoxMnyO2表面。LiNi1‑x‑yCoxMnyO2界面的Ni,Co和Mn金属原子可以与上述单质X形成金属‑X化合键,通过其强烈的键合作用,确保了单质X在LiNi1‑x‑yCoxMnyO2表面的均匀完整紧密包覆。这种均匀完整紧密的包覆层能够有效降低高镍三元材料表面的残锂含量,同时抑制LiNi1‑x‑ yCoxMnyO2正极材料与电解液的接触反应,避免了电池充放电过程中的产气问题,提升了高镍三元正极材料LiNi1‑x‑yCoxMnyO2的循环稳定性和安全性能。
Description
技术领域
本发明属于电化学储能电池领域,具体涉及一种低温气相沉积包覆的高镍三元正极材料及其制备方法。
背景技术
可充电锂离子电池(LIB)在便携式电子设备和电动汽车等领域存在非常广泛的应用空间,前景诱人。特别是高镍的层状金属氧化物正极材料LiNi1-x-yCoxMnyO2(1-x-y≥0.6),与目前已经商业化的LiCoO2正极材料相比,具有更高的比容量和更低的成本,因而被认为是一种最具发展和应用前景的高能量密度正极材料。然而,高镍LiNi1-x-yCoxMnyO2正极材料目前存在库伦效率低、循环稳定性差和倍率容量低等缺陷问题。这些缺陷问题主要与高镍LiNi1-x-yCoxMnyO2的结构特性相关:(1)Li+(0.076nm)与Ni2+(0.069nm)的离子半径相近,在过渡金属层与Li层间发生的Li+/Ni2+离子混排程度高,导致Li+的扩散路径受阻、材料的可逆容量降低;(2)材料表面可与空气中的H2O和CO2发生反应,形成过多的LiOH/Li2CO3等含锂碱性化合物,使得电极涂膜时浆料容易产生凝胶化现象、电极制备难度增加;(3)残留的LiOH容易与电解液中的LiPF6发生反应生成HF,造成材料中金属离子溶解、气体析出,结构从层状向尖晶石晶相转变,从而使材料可逆容量衰减严重。为了解决这些缺陷问题,科学家采用了各种策略,包括材料形貌设计、离子掺杂和表面包覆等,来改善高镍LiNi1-x- yCoxMnyO2的循环稳定性。其中,在高镍LiNi1-x-yCoxMnyO2正极材料表面构建纳米尺寸的包覆层,比如Al2O3、V2O5、SiO2、LiF、CaF2、AlF3、硫化物、硒化物等纳米包覆层(Cho W.,Kim S.M.,SongJ.H.,et al.J.Power Sources 2015,282,45-50;Shi S.,Tu J.,Tang Y.,etal.J.Power Sources 2013,225,338-346:沈赟,方艳,于英超等,中国专利CN109473657A),可有效提高材料的电化学性能。首先,界面包覆层可以降低材料在空气中的裸露面积,从而减少高镍表面与H2O/CO2的副反应、减少LiOH/Li2CO3杂质的形成。再者,表面包覆层可以保护高脱锂态活性材料免受HF的破坏,阻止正极材料与电解液发生副反应,从而提高了高镍LiNi1-x-yCoxMnyO2正极材料的循环性能。然而,如果包覆层的电子/Li+传导率差,将会增大高镍LiNi1-x-yCoxMnyO2正极材料的电化学极化,导致材料比容量降低。此外,由于目前大多数表面包覆方法都是基于前驱体化合物的机械混合工艺,包覆层很难均匀完整地包覆在颗粒的整个表面。包覆材料与高镍LiNi1-x-yCoxMnyO2的表面能差异,导致包覆材料在基体表面容易形成大量微米颗粒,材料表面存在很多裸露面积。而且,由于高镍LiNi1-x- yCoxMnyO2容易和水发生副反应,基于水溶液体系的包覆技术可能会导致高镍LiNi1-x- yCoxMnyO2表面结构破坏和容量损失。因此,如何开发简单高效的包覆技术,在高镍LiNi1-x- yCoxMnyO2表面构建均匀高导的包覆层,依然是目前该领域面临的挑战。
发明内容
本发明的目的在于提供一种低温气相沉积包覆的高镍三元正极材料,所述正极材料为单质P、S、Se、Te和I包覆的LiNi1-x-yCoxMnyO2复合材料,式中0<x<0.4,0<y<0.4,1-x-y≥0.6,单质P、S、Se、Te和I包覆层的质量分数为0-10.0%。
优选的,所述材料的制备方法包括以下步骤:
(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)将单质P、S、Se、Te和I分别和LiNi1-x-yCoxMnyO2均匀混合,置于坩埚中,放入管式炉中,在氩气气氛下进行一步热处理,熔融态或者气态的单质在LiNi1-x-yCoxMnyO2的高吸附性界面均匀扩散,形成均匀紧密的单质包覆层,得到最终的上述单质包覆LiNi1-x-yCoxMnyO2正极材料。
优选的,所述步骤(1)中Ni1-x-yCoxMny(OH)2三元前驱体中,0<x<0.4、0<y<0.4和1-x-y≥0.6。
优选的,所述步骤(1)中锂源为氢氧化锂、碳酸锂、硝酸锂或者醋酸锂。
优选的,所述步骤(1)中热处理过程为:以1-10℃/min的速率升温至400-500℃,保温3-10h,再同样以1-5℃/min的速率升温至700-800℃,保温10-20h。
优选的,所述步骤(2)中单质P的混合加入量为红磷/LiNi1-x-yCoxMnyO2,混合物中的质量分数为0-10.0%,热处理温度为200-480℃,热处理时间为5-60min。
优选的,所述步骤(2)中单质S的混合加入量为硫/LiNi1-x-yCoxMnyO2,混合物中的质量分数为0-10.0%,热处理温度为200-400℃,热处理时间为5-60min。
优选的,所述步骤(2)中单质Se的混合加入量为硒/LiNi1-x-yCoxMnyO2,混合物中的质量分数为0-10.0%,热处理温度为200-350℃,热处理时间为5-60min。
优选的,所述步骤(2)中单质Te的混合加入量为碲/LiNi1-x-yCoxMnyO2,混合物中的质量分数为0-10.0%,热处理温度为200-500℃,热处理时间为5-60min。
优选的,所述步骤(2)中单质I的混合加入量为碘/LiNi1-x-yCoxMnyO2,混合物中的质量分数为0-10.0%,热处理温度为100-210℃,热处理时间为5-60min。
与现有技术相比,本发明的有益效果是:
(1)本发明所述低温气相沉积包覆的高镍三元正极材料中,LiNi1-x-yCoxMnyO2界面的Ni,Co和Mn原子可以与单质红磷、硫、硒、碲和碘原子形成金属-单质化合键,通过其强烈的键合作用,确保了单质红磷、硫、硒、碲和碘在LiNi1-x-yCoxMnyO2表面的均匀紧密包覆。
(2)这种均匀紧密的红磷、硫、硒、碲和碘包覆层能够有效减小高镍三元材料表面残锂的碱性,同时抑制LiNi1-x-yCoxMnyO2正极材料与电解液的接触反应,避免产生大量的气体,提升材料的安全性能。因此,与未包覆的LiNi1-x-yCoxMnyO2正极材料相比,红磷、硫、硒、碲和碘包覆的LiNi1-x-yCoxMnyO2正极材料具有更好的循环性能、倍率性能和安全性能,有望推进高镍三元正极材料的产业化应用。
附图说明
图1为本发明实施例1产物纯LiNi0.8Co0.1Mn0.1O2和实施例5产物碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料在0.1C时的充放电曲线;
图2为本发明实施例1产物纯LiNi0.8Co0.1Mn0.1O2和实施例5产物碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料在0.1C时的首次充放电容量曲线;
图3为本发明实施例5产物碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料在0.1C时的前三个循环的充放电容量曲线。
具体实施方式
下面结合实例对本发明进行进一步的说明。
实施例1
分别称取3.00g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、1.40g一水合氢氧化锂,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氧气的管式炉中,以2℃/min的速率升温至480℃,保温6h,再同样以2℃/min的速率升温至750℃,保温16h,自然冷却,得到LiNi0.8Co0.1Mn0.1O2正极材料。
将制备的LiNi0.8Co0.1Mn0.1O2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 2500微孔膜为隔膜,在手套箱中装配成纽扣电池。
实施例2
分别称取3.00g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、1.40g一水合氢氧化锂,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氧气的管式炉中,以2℃/min的速率升温至480℃,保温6h,再同样以2℃/min的速率升温至750℃,保温16h,自然冷却,得到LiNi0.6Co0.2Mn0.2O2正极材料。
分别称取2.00g LiNi0.8Co0.1Mn0.1O2锂离子正极材料和0.04g单质红磷,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氩气的管式炉中,以5℃/min的速率一步升温至430℃,保温20min,自然冷却,得到红磷包覆的LiNi0.8Co0.1Mn0.1O2正极材料。将制备的红磷包覆的LiNi0.8Co0.1Mn0.1O2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。以制备的红磷包覆的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,Celgard2500微孔膜为隔膜,在手套箱中装配成纽扣电池。
实施例3
分别称取3.00g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、1.40g一水合氢氧化锂,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氧气的管式炉中,以2℃/min的速率升温至480℃,保温6h,再同样以2℃/min的速率升温至750℃,保温16h,自然冷却,得到LiNi0.8Co0.1Mn0.1O2正极材料。
分别称取2.00g LiNi0.8Co0.1Mn0.1O2锂离子正极材料和0.04g单质碲,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氩气的管式炉中,以5℃/min的速率一步升温至500℃,保温20min,自然冷却,得到碲包覆的LiNi0.8Co0.1Mn0.1O2正极材料。将制备的碲包覆的LiNi0.8Co0.1Mn0.1O2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。以制备的碲包覆的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 2500微孔膜为隔膜,在手套箱中装配成纽扣电池。
实施例4
分别称取3.00g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、1.40g一水合氢氧化锂,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氧气的管式炉中,以2℃/min的速率升温至480℃,保温6h,再同样以2℃/min的速率升温至750℃,保温16h,自然冷却,得到LiNi0.8Co0.1Mn0.1O2正极材料。
分别称取2.00g LiNi0.8Co0.1Mn0.1O2锂离子正极材料和0.04g单质硒,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氩气的管式炉中,以5℃/min的速率一步升温至300℃,保温20min,自然冷却,得到硒包覆的LiNi0.8Co0.1Mn0.1O2正极材料。将制备的硒包覆的LiNi0.8Co0.1Mn0.1O2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。以制备的硒包覆的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 2500微孔膜为隔膜,在手套箱中装配成纽扣电池。
实施例5
分别称取3.00g Ni0.8Co0.1Mn0.1(OH)2三元前驱体材料、1.40g一水合氢氧化锂,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氧气的管式炉中,以2℃/min的速率升温至480℃,保温6h,再同样以2℃/min的速率升温至750℃,保温16h,自然冷却,得到LiNi0.8Co0.1Mn0.1O2正极材料。
分别称取2.00g LiNi0.6Co0.2Mn0.2O2锂离子正极材料和0.04g单质碘,在研钵中研磨均匀后,置于刚玉坩埚中,放入充满氩气的管式炉中,以5℃/min的速率一步升温至210℃,保温20min,自然冷却,得到碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料。将制备的碘包覆的LiNi0.8Co0.1Mn0.1O2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。以制备的碘包覆的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 2500微孔膜为隔膜,在手套箱中装配成纽扣电池。图1-3分别比较了纯LiNi0.8Co0.1Mn0.1O2和碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料在0.1C时的首次充放电容量、循环性能曲线,以及包覆的LiNi0.8Co0.1Mn0.1O2正极材料在0.1C时前三个循环的充放电容量曲线。
结果表明:碘包覆的LiNi0.8Co0.1Mn0.1O2在0.1C电流密度下的首次充电容量为234.2mAh g-1,首次放电容量为207.1mAh g-1,第90次循环的放电容量为181.5mAh g-1;前三个循环的放电容量分别为207.9mAh g-1、206.4mAh g-1和207.0mAh g-1。与纯LiNi0.8Co0.1Mn0.1O2正极材料相比,碘包覆的LiNi0.8Co0.1Mn0.1O2正极材料具有更高的放电容量和循环稳定。
Claims (10)
1.一种低温气相沉积包覆的高镍三元正极材料,其特征在于:所述正极材料为单质P、S、Se、Te和I包覆的LiNi1-x-yCoxMnyO2复合材料,式中0<x<0.4,0<y<0.4,1-x-y≥0.6,单质P、S、Se、Te和I包覆层的质量分数为0-10.0%。
2.一种如权利要求1所述低温气相沉积包覆的高镍三元正极材料,其特征在于:所述材料的制备方法包括以下步骤:
(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)将单质P、S、Se、Te和I分别和LiNi1-x-yCoxMnyO2均匀混合,置于坩埚中,放入管式炉中,在氩气气氛下进行一步热处理,熔融态或者气态的单质在LiNi1-x-yCoxMnyO2的高吸附性界面均匀扩散,形成均匀紧密的单质包覆层,得到最终的上述单质包覆LiNi1-x-yCoxMnyO2正极材料。
3.根据权利要求2所述制备方法,其特征在于:所述步骤(1)中Ni1-x-yCoxMny(OH)2三元前驱体中0<x<0.4,0<y<0.4,1-x-y≥0.6。
4.根据权利要求2所述制备方法,其特征在于:所述步骤(1)中锂源为氢氧化锂、碳酸锂、硝酸锂或者醋酸锂。
5.根据权利要求2所述制备方法,其特征在于:所述步骤(1)中热处理过程为:以1-10℃/min的速率升温至400-500℃,保温3-10h,再同样以1-5℃/min的速率升温至700-800℃,保温10-20h。
6.根据权利要求2所述制备方法,其特征在于:所述步骤(2)中单质P的混合加入量为红磷/LiNi1-x-yCoxMnyO2质量分数的0-10.0%,热处理温度为200-480℃,热处理时间为5-60min。
7.根据权利要求2所述制备方法,其特征在于:所述步骤(2)中单质S的混合加入量为硫/LiNi1-x-yCoxMnyO2质量分数的0-10.0%,热处理温度为200-400℃,热处理时间为5-60min。
8.根据权利要求2所述制备方法,其特征在于:所述步骤(2)中单质Se的混合加入量为硒/LiNi1-x-yCoxMnyO2质量分数的0-10.0%,热处理温度为200-350℃,热处理时间为5-60min。
9.根据权利要求2所述制备方法,其特征在于:所述步骤(2)中单质Te的混合加入量为碲/LiNi1-x-yCoxMnyO2质量分数的0-10.0%,热处理温度为200-500℃,热处理时间为5-60min。
10.根据权利要求2所述制备方法,其特征在于:所述步骤(2)中单质I的混合加入量为碘/LiNi1-x-yCoxMnyO2质量分数的0-10.0%,热处理温度为100-210℃,热处理时间为5-60min。
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