CN104638259B - 改善镍锰酸锂锂离子正极材料循环性能的方法 - Google Patents
改善镍锰酸锂锂离子正极材料循环性能的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000010406 cathode material Substances 0.000 title claims abstract description 9
- PBGXDIRQMIKXNU-UHFFFAOYSA-N [Li+].[O-2].[Mn+2].[Ni+2].[Li+].[O-2].[O-2] Chemical compound [Li+].[O-2].[Mn+2].[Ni+2].[Li+].[O-2].[O-2] PBGXDIRQMIKXNU-UHFFFAOYSA-N 0.000 title abstract 3
- 230000001351 cycling effect Effects 0.000 title abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 50
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 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
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 33
- 239000010405 anode material Substances 0.000 claims description 28
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 18
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000002908 manganese Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 238000001035 drying Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 abstract 7
- 239000002243 precursor Substances 0.000 abstract 5
- 238000002156 mixing Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 17
- 125000005909 ethyl alcohol group Chemical group 0.000 description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 238000005253 cladding Methods 0.000 description 15
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical group O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 12
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 8
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 compound nickel lithium manganate Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 1
- 229910011312 Li3VO4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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
本发明涉及一种改善镍锰酸锂锂离子正极材料循环性能的方法,该方法主要包括镍锰酸锂前驱体的制备和镍锰酸锂材料表面的钒酸锂修饰改性。该方法采用固相法进行镍锰酸锂的合成和表面修饰,制备工艺包括以下步骤:⑴将镍源和锰源与锂源研磨混合均匀后,经过干燥、低温烧结后得到镍锰酸锂前驱体;⑵将制备好的镍锰酸锂前驱体与锂源与钒源以及分散剂混合均匀后,经过干燥、高温烧结后得到表面经过钒酸锂修饰改性的镍锰酸锂正极材料。经过修饰过的镍锰酸锂材料极化小,同时具有良好的循环性能,且此方法适于大规模生产镍锰酸锂锂离子正极材料。
Description
技术领域
本发明涉及锂离子电池正极材料技术领域,具体涉及一种利用钒酸锂改善镍锰酸锂锂离子正极材料循环性能的方法。
背景技术
尖晶石型镍锰酸锂(LiNi0.5Mn1.5O4)锂离子正极材料的可逆容量为147mAh/g,电压平台为4.7V,是目前被认为最优发展前景的高电压锂离子正极材料。与目前市场化的钴酸锂相比具有高电压、低成本、无污染等优点,与磷酸铁锂材料相比具有制备工艺简单、生产一致性较好、输出电压范围较宽等优点,是未来长寿命、高安全、高容量电动汽车和储能电池的正极首选材料。但镍锰材料也存在着自身的缺点,主要表现为循环性能较差、容量衰减较快以及倍率性能较差等,最近研究发现通过对镍锰材料表面修饰能够有效改善镍锰材料的电化学性能。
中国发明专利(杨刚,一种表面包覆的镍锰酸锂正极材料的制备方法,申请公告号:CN 103794777 A)通过共沉淀法制备得到镍锰材料前驱体,然后加入微波敏感物质氧化锆,在微波的作用下在镍锰材料表面生成锂离子导体Li2ZrO3,最终制备得到Li2ZrO3包覆的镍锰材料,此法虽然能够得到循环性能得到改善的镍锰材料,但微波只能通过对微波敏感的物质进行包覆,具有很大的局限性,控制过程较为复杂,同时此法不适用于大规模的工业生产。中国发明专利(毛文峰等,一种复合镍锰酸锂正极材料及其制备方法,申请公布号:CN103996844 A)通过溶液法在镍锰酸锂材料表面包覆导电聚合物来改善镍锰酸锂的电化学性能,虽然此法得到的材料倍率较好、中值电压稳定,但衰减还是很明显,达不到动力电池的要求,同时包覆过程操作复杂难以控制,同时溶液法在实现工业化生产较为困难。
发明内容
本发明目的之一是:采用固相法合成用钒酸锂表面修饰的镍锰酸锂锂离子正极材料,来改善镍锰酸锂的电化学性能,尤其是材料的循环稳定性,来满足未来动力电池对高容量、长寿命的要求;本发明的目的之二是:找到一种适用于工业化生产的包覆工艺,期望此包覆工艺在产业化规模生产中能够批量成产改性的镍锰酸锂锂离子正极材料。
为了达到以上目的,本发明采用如下技术方案:
一种改善镍锰酸锂锂离子正极材料循环性能的方法,包括以下步骤:
按照摩尔比Li:Ni:Mn=1~1.02:0.5:1.5称取锂源、镍源与锰源化合物,加入溶剂混合均匀后,经干燥、低温烧结后得到镍锰酸锂前驱体;
按照摩尔比Li:V=3~3.02:1称取锂源和钒源化合物,加入镍锰酸锂前驱体、溶剂以及分散剂混合均匀后经过干燥、烧结得到经钒酸锂表面修饰过的镍锰酸锂正极材料。
优选地,经钒酸锂表面修饰过的镍锰酸锂正极材料中钒酸锂的质量比重为1%~5%。
优选地,所述的步骤⑴、⑵中的镍源化合物为醋酸镍、硫酸镍、硝酸镍、氯化镍以及氧化镍中的一种或两种;所述的锰源化合物为醋酸锰、硝酸锰、硫酸锰、氯化锰及猛的氧化物中的一种或两种;锂源为硝酸锂、乙酸锂、氢氧化锂、碳酸锂中的一种或两种;钒源为钒酸铵或五氧化二钒中的一种。
优选地,所述的步骤⑴、⑵中的溶剂为去离子水、乙醇、丙酮的一种或两种。
优选地,所述的步骤⑴、⑵中浆料的固含量为40%~50%。
优选地,步骤⑴中镍锰酸锂前驱体的低温烧结温度为500~700℃,烧结时间为4~8h,步骤(2)中包覆钒酸锂的镍锰酸锂高温烧结温度为800~1000℃,烧结时间为8~12h。
优选地,步骤⑴、⑵中的锂离子比理论计算过量2%(摩尔量)。
优选地,所述的步骤⑵中的分散剂为PEG,分子量范围300~20000,加入量为镍锰酸锂前驱体质量的1%~5%。
本发明的有益效果在于:
(1)本发明中采用的钒酸锂(Li3VO4)是一种快导离子体,具有较快的离子迁移速率,包覆在镍锰酸锂表面能够很好地弥补镍锰酸理材料电导率差的缺陷。
(2)采用固相法合成镍锰酸锂前驱体在分散剂PEG作用下,表面均匀包覆一层钒酸锂前驱体,在高温烧结过程中PEG形成气体排出,镍锰酸锂表面均匀包覆一层钒酸锂快导离子体,经过此工艺处理得到钒酸锂包覆的镍锰酸锂材料极化现象减小,循环性能得到大大提高,从而提高了电池的使用寿命。
(3)通过固相法在镍锰酸锂表面包覆钒酸锂材料,控制过程较为简单,易操作,材料一致性较好,适合大规模的工业生产。
附图说明
图1为实施例1制备的钒酸锂包覆镍锰酸锂锂离子正极材料的X-射线衍射(XRD)图谱;
图2为实施例1制备的钒酸锂包覆镍锰酸锂锂离子正极材料的透射电镜图谱;
图3为未改善的和用实施例1的方法改善的镍锰酸锂锂离子正极材料的充放电曲线图;
图4为未改善的和用实施例1的方法改善的镍锰酸锂锂离子正极材料的循环曲线图。
具体实施方式
以下是改善镍锰酸锂锂离子正极材料循环性能的方法具体实验过程,以便对本发明作进一步详细说明
实施例1
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中600℃烧结6h得到镍锰酸锂前驱体;
称取成镍锰酸锂前驱体1500g,按照钒酸锂含量5%wt称取碳酸锂62.4g、偏钒酸铵64.6g、分散剂PEG4000 50g,加入1.6L无水乙醇在搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例2
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中500℃烧结8h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量5%wt称取碳酸锂62.4g、偏钒酸铵64.6g、分散剂PEG4000 50g,加入1.6L无水乙醇在10L搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例3
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中600℃烧结6h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量2%wt称取碳酸锂24.5g、偏钒酸铵25.9g、分散剂PEG4000 50g,加入1.6L无水乙醇在搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例4
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在10L搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中700℃烧结8h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量2%wt称取碳酸锂24.5、偏钒酸铵25.9g、分散剂PEG4000 50g,加入1.6L无水乙醇在10L搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例5
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中600℃烧结6h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量1%wt称取碳酸锂12.3g、偏钒酸铵13.0g、分散剂PEG4000 50g,加入2.0L无水乙醇在搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例6
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在10L搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中600℃烧结6h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量1%wt称取碳酸锂12.3g、偏钒酸铵13.0g、分散剂PEG4000 50g,加入2.0L无水乙醇在10L搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例7
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在10L搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中700℃烧结8h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量5%wt称取碳酸锂62.4g、偏钒酸铵64.6g、分散剂PEG4000 50g,加入2.0L无水乙醇在10L搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
实施例8
称取碳酸锂371.86g、氧化镍382.12g、二氧化锰1322.12g,加入2.1L无水乙醇在搅拌磨中混合4h搅拌均匀,在80℃鼓风干燥箱中干燥处理后在马弗炉中500℃烧结8h得到镍锰酸锂前驱体;
称取成品镍锰酸锂1500g,按照钒酸锂含量5%wt称取碳酸锂62.4g、偏钒酸铵64.6g、分散剂PEG4000 50g,加入2.0L无水乙醇在搅拌磨中混合4h,前驱体在80℃鼓风干燥箱中干燥处理后在马弗炉中900℃烧结12h得到钒酸锂包覆镍锰酸锂锂离子正极材料。
结合附图,以实施例1说明制备的钒酸锂包覆镍锰酸锂的电化学性能:
图1为实施例1制备钒酸锂包覆镍锰酸锂锂离子正极材料的X-射线衍射(XRD)图谱;其横坐标为X-射线衍射的测量角度,纵坐标为材料的在此衍射角度时的衍射峰强度。由图谱结果分析可知,合成材料的主相为镍锰酸锂,同时存在着一些钒酸锂的衍射峰,材料的结晶度和纯度都较高。
图2为实施例1制备的钒酸锂包覆镍锰酸锂锂离子正极材料的SEM图谱,可以看出分布着尖晶石的镍锰酸锂,表面有明显的颗粒附着,是形成的钒酸锂层。
如图3是材料包覆前后的充放电曲线,可知经过钒酸锂包覆后的镍锰酸锂极化变小,平台容量比例提升,表现出较好的电化学性能。
如图4可知:通过在2C电流密度下进行循环实验,由钒酸锂包覆的镍锰酸锂材料在经过400次循环后材料的比容量保持率仍达到90%以上,表现出良好的循环稳定性。
Claims (6)
1.一种改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,包括以下步骤:
⑴按照摩尔比Li:Ni:Mn=1~1.02:0.5:1.5称取锂源、镍源与锰源化合物,加入溶剂控制固含量为40~50%,混合均匀后干燥、经过500~700℃烧结4~8h后得到镍锰酸锂前驱体;
⑵按照摩尔比Li:V=3~3.02:1称取锂源和钒源化合物,加入镍锰酸锂前驱体和分子量范围300~20000的PEG为分散剂,加入溶剂控制固含量为40~50%,混合均匀后干燥,经过800~1000℃烧结8~12h后得到经钒酸锂表面修饰过的镍锰酸锂锂离子正极材料。
2.根据权利要求1所述的改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,经钒酸锂表面修饰过的镍锰酸锂正极材料中钒酸锂的质量比重为1%~5%。
3.根据权利要求1所述的改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,所述的步骤⑴、⑵中的镍源化合物为醋酸镍、硫酸镍、硝酸镍、氯化镍以及氧化镍中的一种或两种;所述的锰源化合物为醋酸锰、硝酸锰、硫酸锰、氯化锰及锰的氧化物中的一种或两种;锂源为硝酸锂、乙酸锂、氢氧化锂、碳酸锂中的一种或两种;钒源为钒酸铵或五氧化二钒中的一种。
4.根据权利要求1所述的改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,所述的步骤⑴、⑵中的溶剂为去离子水、乙醇、丙酮的一种或两种。
5.根据权利要求1所述的改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,步骤⑴、⑵中的锂离子比理论计算过量2%(摩尔量)。
6.根据权利要求1所述的改善镍锰酸锂锂离子正极材料循环性能的方法,其特征在于,所述的步骤⑵中的分散剂加入量为镍锰酸锂前驱体质量的1%~5%。
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