CN115893363A - 一种复合正极材料及其制备方法和应用 - Google Patents
一种复合正极材料及其制备方法和应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 claims abstract description 31
- 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 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 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 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 claims abstract description 3
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 43
- 239000011247 coating layer Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000013132 MOF-5 Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000013255 MILs Substances 0.000 claims description 2
- 239000013118 MOF-74-type framework Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01G53/00—Compounds of nickel
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- C01G53/00—Compounds of nickel
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- 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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Abstract
本发明提供了一种复合正极材料及其制备方法和应用,所述制备方法包括以下步骤:(1)将第一锂源、锰源、铁源和磷源与溶剂混合,得到磷酸铁锰锂前驱体,将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料,将镍钴锰氢氧化物和第二锂源混合,经烧结处理得到镍钴锰酸锂正极材料;(2)将步骤(1)得到的磷酸锰铁锂粉料、镍钴锰酸锂正极材料与MOF材料混合进行搅拌得到混合粉料;(3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料,本发明以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池,表现出良好的高倍率性能、高温存储和高温循环性能。
Description
技术领域
本发明属于电池领域,涉及一种复合正极材料及其制备方法和应用。
背景技术
近年来“碳中和”已经受到全世界各国重点关注,新能源汽车蓬勃发展,带动了锂离子动力电池需求的迅速增长。目前,锂离子动力电池的正极材料主要磷酸铁锂(LFP)和三元材料(NCM)。其中,LFP凭借高性价比、高安全性以及资源瓶颈小等优势,逐渐成为储能和动力电池企业的优先选择,然而其存在能量密度低的问题;三元材料因高能量密度,然后其在安全性上饱受诟病。
磷酸锰铁锂(LMFP)是在LFP的基础上添加锰元素后获得的一种正极材料,锰的掺杂可使LMFP具有更高的电压平台(4.1Vvs3.4V),电池的能量密度提升15%左右,是一种具有极大应用前景的正极材料。当前LMFP正极材料还处于产业化初期,其主要原因是LMFP具有双平台,循环性能差,这严重影响其商业落地。因此,消除其双放电平台,提高LMFP材料的电循环稳定性是当前的技术关键。
CN111129463A公开了一种MOF包覆的单晶三元正极材料及其前驱体的制备方法,该方法内核采用共沉淀法合成的高镍低锰前驱体,外壳采用Mn与有机物羧酸盐配位合成Mn-MOF,外壳的Mn在原子级别的均匀性。
CN114620708A公开了一种改性Al基MOF衍生物包覆锂离子电池正极材料的制备方法,先将Al基MOF材料浸渍在含Z元素的溶液中,以获得改性Al基MOF材料,再和锂离子电池正极材料干法包覆,最终得到多元素(Al、Z)包覆改性的锂离子电池正极材料。
上述方案所述正极材料存在有生产条件苛刻,成本高,且高镍三元材料的循环性能、安全性能较差的问题,阻碍了在电池领域的大规模应用。
发明内容
本发明的目的在于提供一种复合正极材料及其制备方法和应用,本发明以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池,表现出良好的高倍率性能、高温存储和高温循环性能。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供了一种复合正极材料的制备方法,所述制备方法包括以下步骤:
(1)将第一锂源、锰源、铁源和磷源与溶剂混合,得到磷酸铁锰锂前驱体,将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料,将镍钴锰氢氧化物和第二锂源混合,经烧结处理得到镍钴锰酸锂正极材料;
(2)将步骤(1)得到的磷酸锰铁锂粉料、镍钴锰酸锂正极材料与MOF材料混合进行搅拌得到混合粉料;
(3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料。
本发明所述复合正极材料通过磷酸锰铁锂粉料和三元镍钴锰正极材料复合包覆MOF材料制得,磷酸锰铁锂掺混三元正极材料后,当磷酸锰铁锂材料占主导时,可改善其双平台问题;当三元正极材料材料为主导,可兼顾安全与成本。在其表面包覆MOF后,MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质,均匀地包覆在复合正极材料表面,起到桥联作用,形成电子传递通道,提高LMFP电极材料的导电性;另一方面MOF作为保护涂层覆盖在正极材料表面,减少活性物质和电解液之间的副反应,增强材料的结构稳定性,进而提高电极材料的循环性能。
本发明所述方法制备的MOF材料包覆层具有良好的均匀性、一致性与导电性,该方法制备过程简单可控,易于大规模工业化生产。
优选地,步骤(1)所述第一锂源包括碳酸锂和/或磷酸二氢锂。
优选地,所述锰源包括硫酸锰、碳酸锰、硝酸锰、醋酸锰或草酸锰中的任意一种或至少两种的组合。
优选地,所述铁源包括磷酸铁和/或铁粉。
优选地,所述磷源包括磷酸和/或磷酸二氢铵。
优选地,所述溶剂包括水。
优选地,所述热处理的温度为600~950℃,例如:600℃、700℃、800℃、900℃或950℃等。
优选地,所述热处理的时间为5~24h,例如:5h、10h、15h、20h或24h等。
优选地,步骤(1)所述第二锂源包括氢氧化锂和/或碳酸锂。
优选地,所述烧结处理的温度为450~1000℃,例如:450℃、500℃、600℃、700℃、800℃或1000℃等。
优选地,所述烧结处理的时间为5~12h,例如:5h、8h、10h、11h或12h等。
优选地,步骤(2)所述磷酸锰铁锂的化学式为LiMnxFe1-xPO4,0<x<1。
优选地,所述镍钴锰酸锂的化学式为LiNiaCobMn(1-a-b)O2,a=0.5~0.8,b=0.1~0.2。
优选地,步骤(2)所述磷酸锰铁锂粉料和镍钴锰正极材料的质量比为1:(0.1~10),例如:1:0.1、1:0.2、1:0.5、1:1、1:5或1:10等。
优选地,所述MOF材料包括IRMOFs、MILs、MOF-5、MOF-74或ZIF-8中的任意一种或至少两种的组合。
金属有机框架(MOF)材料是一种以金属离子为结点,有机配位体为联接桥,通过配位键自组装形成的具有周期性网络的多孔材料。MOF材料由于高比表面积、组分可设计性、拓扑结构多样性等优势,在催化、电池、能源存储等领域具有巨大的应用潜力。MOF的金属位点可氧化成为无定型氧化物,并且在纳米级别上高度有序,可使包覆层保持在纳米级别。
优选地,步骤(2)所述搅拌的速度为300~800rpm,例如:300rpm、400rpm、500rpm、600rpm或800rpm等。
优选地,所述搅拌的时间为0.5~5h,例如:0.5h、1h、2h、3h、4h或5h等。
优选地,步骤(3)所述煅烧处理的温度为200~600℃,例如:200℃、300℃、400℃、500℃或600℃等。
优选地,所述煅烧处理的时间为2~12h,例如:2h、5h、8h、10h或12h等。
第二方面,本发明提供了一种复合正极材料,所述复合正极材料通过如第一方面所述方法制得。
本发明以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池,表现出良好的高倍率性能、高温存储和高温循环性能。
优选地,所述复合正极材料包括内核和设置于所述内核表面的包覆层。
优选地,所述内核包括镍钴锰三元正极材料和磷酸锰铁锂正极材料。
优选地,所述包覆层包括MOF材料。
优选地,以所述复合正极材料的质量为100%计,所述包覆层的质量分数为0.1~1.0%,例如:0.1%、0.2%、0.3%、0.5%或1.0%等。
第三方面,本发明提供了一种正极极片,所述正极极片包含如第二方面所述的复合正极材料。
第四方面,本发明提供了一种锂离子电池,所述锂离子电池包含如第三方面所述的正极极片。
相对于现有技术,本发明具有以下有益效果:
(1)本发明将磷酸锰铁锂粉料和三元镍钴锰正极材料复合,在其表面包覆MOF包覆层,可以兼顾材料安全、成本以及能量密度的同时,提高材料的倍率性能和循环性能。
(2)本发明提供了一种MOF包覆LMFP和NCM复合正极材料的制备方法,锰铁掺混三元后,当锰铁材料占主导时,可改善其双平台问题;当三元材料为主导,可兼顾安全与成本。在其表面包覆MOF后,MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质,均匀地包覆在复合正极材料表面,起到桥联作用,形成电子传递通道,提高LMFP电极材料的导电性;另一方面MOF作为保护涂层覆盖在正极材料表面,减少活性物质和电解液之间的副反应,增强材料的结构稳定性,进而提高电极材料的循环性能。以MOF包覆LMFP和NCM复合正极材料作为锂离子电池正极材料制成的电池,表现出良好的高倍率性能、高温存储和高温循环性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
本实施例提供了一种复合正极材料,所述复合正极材料的制备方法如下:
(1)按摩尔比Li:Mn:Fe:P=1.1:0.6:0.4:1称取碳酸锂、硫酸锰、铁粉、磷酸,加入到去离子水中分散搅拌球磨,得到前驱体,将所述前驱体放入箱式炉,在氮气保护下,以5℃/min的升温速率,升温至750℃,保温12h后,在氮气气氛下冷却至室温,得到磷酸锰铁锂(LiMn0.6Fe0.4PO4)粉料,取Ni0.5Co0.2Mn0.3(OH)2与氢氧化锂进行混合搅拌,在800℃煅烧8h,得到NCM523正极材料;
(2)将步骤(1)得到的磷酸锰铁锂粉料和三元镍钴锰正极材料按照质量比为7:3与IRMOFs材料混合在500rpm下搅拌2h得到混合粉料;
(3)对步骤(2)得到的混合粉料在400℃下煅烧6h,在氮气气氛下冷却至室温,获得所述复合正极材料;
所述复合正极材料中,MOF包覆层的质量占比为0.3%。
实施例2
本实施例提供了一种复合正极材料,所述复合正极材料的制备方法如下:
(1)按摩尔比Li:Mn:Fe:P=1.1:0.6:0.4:1称取碳酸锂、硫酸锰、铁粉、磷酸,加入到去离子水中分散搅拌球磨,得到前驱体,将所述前驱体放入箱式炉,在氮气保护下,以5℃/min的升温速率,升温至800℃,保温11h后,在氮气气氛下冷却至室温,得到磷酸锰铁锂粉料,取Ni0.8Co0.1Mn0.1(OH)2与氢氧化锂进行混合搅拌,在750℃煅烧8h,得到NCM811正极材料;
(2)将步骤(1)得到的磷酸锰铁锂粉料和三元镍钴锰正极材料按照质量比为3:7与MOF-5材料混合在600rpm下搅拌2h得到混合粉料;
(3)对步骤(2)得到的混合粉料在500℃下煅烧5h,在氮气气氛下冷却至室温,获得所述复合正极材料;
所述复合正极材料中,MOF包覆层的质量占比为0.5%。
实施例3
本实施例与实施例1区别就在于,所述复合材料中,MOF包覆层的质量占比为0.1%,其他条件与参数与实施例1完全相同。
实施例4
本实施例与实施例1区别就在于,所述复合材料中,MOF包覆层的质量占比为1.0%,其他条件与参数与实施例1完全相同。
对比例1
本对比例与实施例1区别仅在于,不加入磷酸锰铁锂正极材料,其他条件与参数与实施例1完全相同。
对比例2
本对比例与实施例1区别仅在于,不加入三元镍钴锰正极材料,其他条件与参数与实施例1完全相同。
对比例3
本对比例与实施例1区别仅在于,不加入MOF材料,其他条件与参数与实施例1完全相同。
性能测试:
使用实施例1-4和对比例1-3得到的正极材料,以石墨作为负极材料,搭配PE/PP高分子材料作为隔膜,采用卷绕或者叠片方式组装成卷芯,封装在铝壳或者铝塑膜中,并注入1M LiPF6/EC+EMC锂离子电解液,组装成软包锂离子电池。对得到的锂离子电池进行性能测试,测试结果如表1所示:
表1
由表1可以看出,由实施例1-2可得,LMFP和NCM的比例不同,材料的性能侧重不同,LMFP占比多,有利于循环、DCR和电压降;NCM占比多,有利于存储和倍率性能。
由实施例1和实施例3-4对比可得,本发明所述复合正极材料中,MOF包覆层的质量占比会影响其性能,将MOF包覆层的质量占比控制在0.1-1.0%,制得复合正极材料的性能较好,若MOF包覆层的质量占比过低,包覆效果不明显,无法很好的起到作用,若MOF包覆层的质量占比过高,活性物质占比降低进而导致克容量降低。
由实施例1和对比例1-2对比可得,本发明所述复合正极材料的内核由磷酸锰铁锂粉料和三元镍钴锰正极材料复合,当锰铁材料占主导时,可改善其双平台问题;当三元材料为主导,可兼顾安全与成本。
由实施例1和对比例3对比可得,MOF在惰性气氛下碳化后MOF中的有机成分形成碳基质,均匀地包覆在复合正极材料表面,起到桥联作用,形成电子传递通道,提高LMFP电极材料的导电性;另一方面MOF作为保护涂层覆盖在正极材料表面,减少活性物质和电解液之间的副反应,增强材料的结构稳定性,进而提高电极材料的循环性能。
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种复合正极材料的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将第一锂源、锰源、铁源和磷源与溶剂混合,得到磷酸铁锰锂前驱体,将所述磷酸锰铁锂经热处理得到磷酸锰铁锂粉料,将镍钴锰氢氧化物和第二锂源混合,经烧结处理得到镍钴锰酸锂正极材料;
(2)将步骤(1)得到的磷酸锰铁锂(LiMnxFe1-xPO4)粉料、镍钴锰酸锂(LiNiaCobMn(1-a-b)O2)正极材料与MOF材料混合进行搅拌得到混合粉料;
(3)对步骤(2)得到的混合粉料进行煅烧处理得到所述复合正极材料。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)所述第一锂源包括碳酸锂和/或磷酸二氢锂;
优选地,所述锰源包括硫酸锰、碳酸锰、硝酸锰、醋酸锰或草酸锰中的任意一种或至少两种的组合;
优选地,所述铁源包括磷酸铁和/或铁粉;
优选地,所述磷源包括磷酸和/或磷酸二氢铵;
优选地,所述溶剂包括水;
优选地,所述热处理的温度为600~950℃;
优选地,所述热处理的时间为5~24h。
3.如权利要求1或2所述的制备方法,其特征在于,步骤(1)所述第二锂源包括氢氧化锂和/或碳酸锂;
优选地,所述烧结处理的温度为450~1000℃;
优选地,所述烧结处理的时间为5~12h。
4.如权利要求1-3任一项所述的制备方法,其特征在于,步骤(2)所述磷酸锰铁锂的化学式为LiMnxFe1-xPO4,0<x<1;
优选地,所述镍钴锰酸锂的化学式为LiNiaCobMn(1-a-b)O2,a=0.5~0.8,b=0.1~0.2;
所述磷酸锰铁锂粉料和镍钴锰正极材料的质量比为1:(0.1~10);
优选地,所述MOF材料包括IRMOFs、MILs、MOF-5、MOF-74或ZIF-8中的任意一种或至少两种的组合。
5.如权利要求1-4任一项所述的制备方法,其特征在于,步骤(2)所述搅拌的速度为300~800rpm;
优选地,所述搅拌的时间为0.5~5h。
6.如权利要求1-5任一项所述的制备方法,其特征在于,步骤(3)所述煅烧处理的温度为200~600℃;
优选地,所述煅烧处理的时间为2~12h。
7.一种复合正极材料,其特征在于,所述复合正极材料通过如权利要求1-6任一项所述方法制得。
8.如权利要求7所述的复合正极材料,其特征在于,所述复合正极材料包括内核和设置于所述内核表面的包覆层;
优选地,所述内核包括镍钴锰三元正极材料和磷酸锰铁锂正极材料;
优选地,所述包覆层包括MOF材料;
优选地,以所述复合正极材料的质量为100%计,所述包覆层的质量分数为0.1~1.0%。
9.一种正极极片,其特征在于,所述正极极片包含如权利要求7或8所述的复合正极材料。
10.一种锂离子电池,其特征在于,所述锂离子电池包含如权利要求9所述的正极极片。
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WO2023179613A1 (zh) | 2023-09-28 |
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