CN116864645A - 一种包覆型钠离子电池正极材料及其制备方法 - Google Patents
一种包覆型钠离子电池正极材料及其制备方法 Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 20
- 239000012071 phase Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- -1 NaOH or Na Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- 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
- H01M4/48—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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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
本发明属于电极材料技术领域,具体公开了一种包覆型钠离子电池正极材料及其制备方法,包括如下步骤:将O3相结构钠电正极材料和钛酸异丙酯按比例均匀分散在溶剂中,然后将混合液中的溶剂加热蒸发,将所得固体粉料烘干后,得到二氧化钛包覆正极材料的复合粉体;将复合粉体在空气气氛下,650‑750℃高温烧结4‑6h,得到包覆型钠离子电池正极材料。通过液相包覆+高温固相烧结法实现纳米级二氧化钛/钛酸钠均匀包覆在正极材料表面,形成均匀的表层结构,非活性二氧化钛可以阻碍电解液与电极材料的直接接触,降低副反应的发生,改善在循环过程中的稳定性。
Description
技术领域
本发明属于电极材料技术领域,具体涉及一种包覆型钠离子电池正极材料及其制备方法。
背景技术
这里的陈述仅提供与本发明相关的背景技术,而不必然地构成现有技术。
钠离子电池(SIBs)充放电原理与锂离子电池类似,而且钠资源分布广泛且成本低廉,未来有望取代锂离子电池在大规模储能系统中得到广泛应用。正极材料作为钠离子电池中关键的组成部分,对整个电池的能量密度,循环寿命起到决定性作用,迄今为止,各种钠离子电池正极材料,如层状过渡金属氧化物、聚阴离子化合物和硫酸盐等已经在钠离子电池中进行了广泛研究。层状过渡金属氧化物(NaxTMO2,x≤1,TM为过渡金属)因其丰富的组成多样性以及可调控的电化学性质成为研究的热点,具有P2或者O3相结构的层状钠离子正极材料在钠离子电池正极材料中得到了广泛的关注,而O3相结构的层状氧化物正极材料凭借其较高的放电比容量和易于合成的潜力被认为是钠离子电池最有产业化应用前景的正极材料之一。
然而钠离子层状氧化物正极材料在产业化进程中仍有一些亟待解决的关键问题。例如,1、充放电过程中复杂的相转变,O3相钠离子正极材料在充放电过程经历O3→(O3+O′3)→P3→P′3→(P′3+P3″)→P3″的变化,这一系列相变会导致材料的结构发生坍塌,带来容量的快速衰减,尤其在脱钠25%左右时,发生O3→P3相变,改变钠离子的扩散机制,使钠离子脱出变得更加困难。2、环境敏感性,水是层状钠离子氧化物不稳定的根源,Na+与空气中H+发生离子交换,钠离子脱出与空气中的H2O或CO2发生反应,在材料表面形成相应的钠盐,如NaOH或Na2CO3,影响电池制备过程中的加工性能以及在循环过程中与电解液发生反应引起电池安全问题。
针对上述问题,研究者们多采用元素掺杂以及表面包覆改性手段来解决,元素掺杂可以巩固钠离子层状正极材料的晶体结构,从而改善材料的循环稳定性。表面包覆是一种常用的改性手段来解决材料的界面稳定性问题,包覆层可以避免电极材料与电解液的直接接触,抑制界面副反应,但是,常用包覆方式大多为干法包覆,在包覆过程中受到包覆物颗粒的影响,难以在正极材料表面形成均匀的包覆层,无法在材料表面构建稳定的表层结构,对材料的稳定性并未起到提升作用。
发明内容
针对现有技术存在的不足,本发明的目的是提供一种包覆型钠离子电池正极材料及其制备方法。
为了实现上述目的,本发明是通过如下的技术方案来实现:
第一方面,本发明提供一种包覆型钠离子电池正极材料的制备方法,包括如下步骤:
将O3相结构钠电正极材料和钛酸异丙酯按比例均匀分散在溶剂中,然后将混合液中的溶剂加热蒸发,将所得固体粉料烘干后,得到正极材料颗粒表面包覆有二氧化钛的复合粉体;
将复合粉体在氧气气氛下,650-750℃高温烧结4-6h,得到包覆型钠离子电池正极材料。
在氧气气氛下烧结,可以避免杂相的产生。
在一些实施例中,O3相结构钠电正极材料和钛酸异丙酯的摩尔比为100:0.05-0.5。
在一些实施例中,所述溶剂为甲醇、乙醇、丙醇、丙酮、四氢呋喃、正丁醇或乙醚。
优选的,混合液中,固体与液体的质量比为20-40:100。
在一些实施例中,将溶剂加热蒸发的温度为60-80℃。。
优选的,将溶剂加热蒸发的过程中,不断搅拌溶液。以保证溶剂蒸发的均匀性,并保证溶剂在加热蒸发过程中,得到的固体物质质地均匀。
在一些实施例中,固体粉料烘干的温度为100-150℃。
在一些实施例中,高温烧结的温度为680-720℃。
在一些实施例中,还包括将制备的包覆型钠离子电池正极材料进行辊破、研磨和过筛的步骤。
优选的,包覆型钠离子电池正极材料研磨后的粒径为300目。
第二方面,本发明提供一种包覆型钠离子电池正极材料,由所述制备方法制备而成。
上述本发明的一种或多种实施例取得的有益效果如下:
通过液相包覆+高温固相烧结法实现纳米级二氧化钛/钛酸钠均匀包覆在正极材料表面,形成均匀的表层结构,非活性二氧化钛可以阻碍电解液与电极材料的直接接触,降低副反应的发生,改善在循环过程中的稳定性。
同时在烧结过程中,高温固相反应可以促使活性材料表面的钠盐残碱如:NaOH和Na2CO3与二氧化钛在高温固相环境下形成钛酸钠,可以进一步降低表面残余碱量。
湿法包覆处理后的正极材料表面可以形成更小粒径的包覆物,有利于缩短充放电过程中的电荷扩散路径,提升其动力学性能,最后,与传统的干法包覆相比,湿法包覆可以提高包覆产品的均匀性与一致性,提高产品的批次稳定性,且易于实现规模化量产。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1为实施例1中所制备的包覆型正极材料NaNi1/3Fe1/3Mn1/3O2的扫描电镜图;
图2为实施例2中所制备的包覆型正极材料NaNi1/3Fe1/3Mn1/3O2的扫描电镜图;
图3为实施例3中所制备的包覆型正极材料NaNi1/3Fe1/3Mn1/3O2的扫描电镜图;
图4为对比例1中所制备的正极材料NaNi1/3Fe1/3Mn1/3O2的扫描电镜图;
图5为对比例2中所制备的包覆型正极材料NaNi1/3Fe1/3Mn1/3O2的扫描电镜图;
图6为实施例以及对比例中所制备的正极材料NaNi1/3Fe1/3Mn1/3O2的扣电循环性能对比图。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本发明提供进一步的说明。除非另有指明,本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
下面结合实施例对本发明作进一步说明。
实施例1
按照0.2%的摩尔比(是指钛酸异丙酯占活性材料的摩尔百分数)分别称取活性材料NaNi1/3Fe1/3Mn1/3O2与钛酸异丙酯,以乙醇溶液作为溶剂,置于搅拌罐中均匀搅拌,将固液质量比控制在35%;
将搅拌容器的搅拌速度设置为400r/min,温度控制在80℃;
待溶剂蒸发后,将所得固体粉料放置于真空干燥箱中120℃烘干,得到具有二氧化钛物质的表面包覆物负载于正极材料的复合粉体;
将复合材料粉体置于箱式炉中空气气氛下进行700℃高温烧结5h,烧结结束后,得到包覆型钠离子电池正极材料;
将制备得到的包覆型钠离子电池正极材料进行辊破、研磨、300目过筛,进行扣电制备测试。
实施例2
按照0.1%的摩尔比分别称取活性材料NaNi1/3Fe1/3Mn1/3O2与钛酸异丙酯,以乙醇溶液作为溶剂,置于搅拌罐中均匀搅拌,将固液比控制在35%;
将搅拌容器的搅拌速度设置为400r/min,温度控制在80℃;
待溶剂蒸发后,将所得固体粉料放置于真空干燥箱中120℃烘干,得到具有二氧化钛物质的表面包覆物负载于正极材料的复合粉体;
将复合材料粉体置于箱式炉中空气气氛下进行700℃高温烧结5h,烧结结束后,得到包覆型钠离子电池正极材料;
将制备得到的包覆型钠离子电池正极材料进行辊破、研磨、300目过筛,进行扣电制备测试。
实施例3
按照0.3%的摩尔比分别称取活性材料NaNi1/3Fe1/3Mn1/3O2与钛酸异丙酯,以乙醇溶液作为溶剂,置于搅拌罐中均匀搅拌,将固液比控制在35%;
将搅拌容器的搅拌速度设置为400r/min,温度控制在80℃;
待溶剂蒸发后,将所得固体粉料放置于真空干燥箱中120℃烘干,得到具有二氧化钛物质的表面包覆物负载于正极材料的复合粉体;
将复合材料粉体置于箱式炉中空气气氛下进行700℃高温烧结5h,烧结结束后,得到包覆型钠离子电池正极材料;
将制备得到的包覆型钠离子电池正极材料进行辊破、研磨、300目过筛,进行扣电制备测试。
对比例1
该对比例中的活性正极材料采用未经处理的O3相钠离子电池正极材料NaNi1/ 3Fe1/3Mn1/3O2。
对比例2
按照0.2%的摩尔比分别称取活性材料与二氧化钛,置于高速混料机中高速搅拌0.5h,得到混合物料A;
以坩埚装取物料A放置于箱式炉中,700℃保温5小时,保温烧结过程中持续通入空气,流量30L/min,得到包覆型钠离子电池正极材料;
将制备得到的包覆型钠离子电池正极材料进行辊破、研磨、300目过筛,进行扣电制备测试。
纽扣电池制备:将实施例与对比例中得到的材料作为正极活性材料,与导电炭黑、聚偏氟乙烯(PVDF)粘结剂按照质量比为8:1:1的比例混合后溶于N-甲基吡咯烷酮(NMP)溶剂中制成正极浆料,在涂布机上将浆料均匀的涂在铝箔上做成极片。将涂好的极片放入温度为120℃真空干燥箱中真空干燥6小时,取出极片在辊压机上对辊,备用。
纽扣电池装配在氩气氛围下的手套箱中进行,电解液为1MNaPF6溶解于EC(碳酸乙烯酯)和DMC(碳酸二甲酯)混合物(按照体积比EC:DMC=1:1)中形成的电解液,金属钠片为对电极。容量测试在美国ArbinBT2000型电池测试仪上进行,充放电电压范围为2.0-4.0V,首次充放电速率为0.1C,循环性能测试充放电速率为0.5C循环50周。
从SEM图中可以看出,与干法包覆相比,正极材料经过湿法包覆后,表面会形成更小粒径,更加均匀一致的包覆物,干法包覆会造成正极材料表面包覆不均匀,如图1-5所示。
结合循环性能对比图图6来看,虽然在前期可以起到改善循环的作用,但是随着循环次数的增加,不均匀的包覆层导致动力学性能下降,循环性能恶化,得益于湿法包覆均匀的表面包覆层,正极材料表现出良好的循环性能。包覆量较少的时候,难以在表面形成全面包覆,包覆量较多的时候又会导致包覆层厚度过厚,严重影响钠离子的传输速率,从而弱化材料的稳定性。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种包覆型钠离子电池正极材料的制备方法,其特征在于:包括如下步骤:
将O3相结构钠电正极材料和钛酸异丙酯按比例均匀分散在溶剂中,然后将混合液中的溶剂加热蒸发,将所得固体粉料烘干后,得到二氧化钛包覆正极材料的复合粉体;
将复合粉体在氧气气氛下,650-750℃高温烧结4-6h,得到包覆型钠离子电池正极材料。
2.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:O3相结构钠电正极材料和钛酸异丙酯的摩尔比为100:0.05-0.5。
3.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:所述溶剂为甲醇、乙醇、丙醇、丙酮、四氢呋喃、正丁醇或乙醚。
4.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:混合液中,固体与液体的质量比为20-40:100。
5.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:将溶剂加热蒸发的温度为70-90℃。
6.根据权利要求5所述的包覆型钠离子电池正极材料的制备方法,其特征在于:将溶剂加热蒸发的过程中,不断搅拌溶液。
7.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:固体粉料烘干的温度为100-150℃。
8.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:高温烧结的温度为680-720℃。
9.根据权利要求1所述的包覆型钠离子电池正极材料的制备方法,其特征在于:还包括将制备的包覆型钠离子电池正极材料进行辊破、研磨和过筛的步骤;
优选的,包覆型钠离子电池正极材料研磨后的粒径为300目。
10.一种包覆型钠离子电池正极材料,其特征在于:由权利要求1-9任一所述制备方法制备而成。
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