CN114368787A - 一种高导电性、高稳定性的锰酸锂材料及其应用 - Google Patents
一种高导电性、高稳定性的锰酸锂材料及其应用 Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 238000004146 energy storage Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011232 storage material Substances 0.000 claims abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 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
- 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
- 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
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-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
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000000149 penetrating effect Effects 0.000 abstract description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B82—NANOTECHNOLOGY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
本发明公开了一种高导电性、高稳定性的锰酸锂材料及其制备方法与其在离子吸附、电池或电容器储能材料中的应用。制备方法为：将锰盐、碳纳米管、水合肼和聚乙烯吡咯烷酮分散到二甲基亚砜和无水乙醇中，得到碳纳米管穿插四氧化三锰材料；然后将碳纳米管穿插四氧化三锰材料分散到氢氧化锂溶液中进行水热反应，得到碳纳米管穿插锰酸锂材料。所述碳纳米管穿插锰酸锂材料为碳纳米管穿过八面体尖晶石锰酸锂颗粒并且将锰酸锂颗粒有效连接起来而形成的导电网形貌。本发明提供的方法简单，所制备的碳纳米管穿插锰酸锂材料具有高导电性、高容量和优异的循环稳定性，可广泛应用于离子吸附、电池和电容器储能等领域。
Description
技术领域
本发明涉及一种高导电性、高稳定性的锰酸锂材料及其制备方法与应用，本发明制备的材料可用于离子吸附和电池或电容器储能领域。
背景技术
随着全球对可持续，清洁能源的需求增加，锂离子电池在新能源领域所占市场份额逐年增加。据统计，在2019年，锂离子电池所消耗的锂源已占全球锂总消耗量的65％。这种持续快速的锂需求增长趋势将会引起锂供应不足的危机。据报道，全球约三分之二的锂源储存在盐湖卤水中，而这些盐湖卤水中同时包含大量的钠离子、钾离子、镁离子和钙离子等。尤其是在我国西部富锂盐湖(如西台吉乃尔盐湖)具有镁锂比高的特点，并且镁离子和锂离子具有相似的离子半径和物理化学性质给盐湖卤水选择性提锂工作带来了很大的挑战。因此，开发高效的液相选择性提锂材料具有重要的意义。
锰酸锂具有成本低、理论吸附容量高、选择性好，环境友好等优点使其成为卤水提锂的理想材料。但是，锰酸锂的导电性和循环稳定性较差，限制了其大规模的电化学提锂应用。通常，科研工作者通过将锰酸锂与导电剂(如石墨烯，碳纳米管，炭黑以及碳纳米纤维)进行复合来改善锰酸锂的电化学性能。其中，碳纳米管因其优异的导电性、良好的化学稳定性和较强的机械强度而成为最常用的添加剂之一。然而，传统的碳纳米管与锰酸锂的机械混合往往导致复合材料中锰酸锂颗粒与碳纳米管接触不够充分，相互作用较弱致使碳纳米管的导电性不能充分发挥。因此，亟需设计一种制备方法简单、电极导电性好、循环稳定性高的电极材料用于盐湖卤水选择性提锂。
发明内容
本发明所要解决的技术问题是：锰酸锂导电性和循环稳定性差的技术问题。
为了解决上述问题，本发明提供了一种高导电性、高稳定性的锰酸锂材料的制备方法，其特征在于，包括以下步骤：
步骤1)：将锰盐、碳纳米管、水合肼和聚乙烯吡咯烷酮分散到二甲基亚砜和无水乙醇中，搅拌，回流，洗涤，干燥，得到碳纳米管穿插四氧化三锰材料；
步骤2)：将步骤1)制得的碳纳米管穿插四氧化三锰材料分散到氢氧化锂溶液中进行水热反应，得到碳纳米管穿插锰酸锂材料。
优选地，所述步骤1)中的锰盐为乙酸锰、硫酸锰、硝酸锰、氯化锰中的任意一种或几种。
优选地，所述步骤1)中锰盐、水合肼、聚乙烯吡咯烷酮、二甲基亚砜、无水乙醇的比例为：1～1.8g:3～7mL:1.5～2.5g:100～200mL:10～30mL。
优选地，所述步骤1)中碳纳米管的质量百分含量为0.05％～20％。
优选地，所述步骤1)中回流的时间为6～48h。
优选地，所述步骤2)中碳纳米管穿插四氧化三锰和氢氧化锂的摩尔比为0.5～1:1。
优选地，所述步骤2)中水热反应的温度为200～260℃，反应时间为6～48h。
本发明还提供了一种通过上述制备方法制备的高导电性、高稳定性的锰酸锂材料，其特征在于，所述材料为碳纳米管穿过锰酸锂颗粒并且将锰酸锂颗粒有效连接起来而形成的导电网形貌，具有高的导电性，容量和循环稳定性。
优选地，所述的锰酸锂颗粒为八面体状，颗粒范围在100～1000nm。
优选地，所述锰酸锂材料中碳纳米管的质量百分含量为0.05％～20％。
本发明还提供了上述高导电性、高稳定性的锰酸锂材料在离子吸附材料、电池或电容器储能材料中的应用。
与现有技术相比，本发明的有益效果在于：
(1)本发明通过回流～水热两步法制备了碳纳米管穿插锰酸锂材料。并且，研究发现，成功制备此碳纳米管穿插锰酸锂材料的关键是首先要制备出碳纳米管穿插四氧化三锰材料。该制备方法较为简单，可重复性强。
(2)本发明制备的碳纳米管穿插锰酸锂材料，呈现出碳纳米管穿插过八面体尖晶石锰酸锂颗粒并且将锰酸锂颗粒有效连接起来而形成的导电网形貌。这种结构可以使电子沿着碳纳米管一维导电通道快速地进行转移，缩短电子传输距离，提升导电性和倍率性能。
(3)本发明制备的这种特殊的穿插结构提高了锰酸锂的活性位点，缓解锂离子在多次嵌入/脱出过程中造成的锰酸锂结构形变，从而提升锰酸锂的容量和循环稳定性，使其在离子吸附和电池或电容器储能领域展现出优异的性能。
附图说明
图1为实施例1制备的碳纳米管穿插四氧化三锰材料和碳纳米管穿插锰酸锂材料的扫描电镜(SEM)图；
图2为对比例1制备的四氧化三锰和锰酸锂的扫描电镜(SEM)图；
图3为对比例2制备的碳纳米管/四氧化三锰混合物和碳纳米管/锰酸锂混合物的扫描电镜(SEM)图；
图4为实施例1制备的碳纳米管穿插锰酸锂材料和对比例1制备的锰酸锂材料的交流阻抗图；
图5为实施例1制备的碳纳米管穿插锰酸锂材料和活性炭组装成的电容器在10mMLiCl溶液中的电压和电导率变化曲线图；
图6为实施例1制备的碳纳米管穿插锰酸锂材料和对比例1制备的锰酸锂材料在10mM LiCl中进行100次吸脱附锂过程中的吸附容量和锰溶损率图。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。
实施例1
本实施例提供了一种碳纳米管穿插锰酸锂材料的制备方法，具体如下：
(1)将1.4g乙酸锰，2g聚乙烯吡咯烷酮和0.02g碳纳米管分散于150mL二甲基亚砜溶剂中，得到溶液1；将25mL体积比为1:4的水合肼～无水乙醇混合溶液逐滴滴加到溶液1中得到混合溶液，然后将此混合溶液进行回流24h。待其冷却至室温后，用乙醇和水反复洗剂多次，离心，干燥得到碳纳米管穿插四氧化三锰材料，记为CNT-s-Mn3O4，其扫描电镜(SEM)图如图1(A)所示，材料为碳纳米管穿过四氧化三锰颗粒并且将四氧化三锰颗粒有效连接起来而形成的导电网形貌，其中四氧化三锰颗粒呈块状形貌。
(2)将物质的量比为0.6:1的CNT-s-Mn3O4和氢氧化锂分散到水中，然后将此分散液置于240℃烘箱中水热反应24h，得到碳纳米管穿插锰酸锂材料，记为CNT-s-LMO，其SEM图如图1(B)所示，材料为碳纳米管穿过锰酸锂颗粒并且将锰酸锂颗粒有效连接起来而形成的导电网形貌，其中锰酸锂颗粒呈八面体状。
如图4所示，本实施例制备的碳纳米管穿插锰酸锂材料(CNT-s-LMO)展现出较小的电子传递电阻(仅有12Ω)，电极导电性很好，非常利于离子的吸附和储能。将CNT-s-LMO制成电容器的阳极，其中活性材料、导电剂和粘结剂质量比为8:1:1，阴极为活性炭(AC)电极，该电容器(CNT-s-LMO‖AC)在10mM LiCl中电压和电导率随时间的变化曲线展示在图5中。图6表明该材料在第一次吸脱附锂时其吸附容量为1.6mmol g-1，经过100次循环后，该材料依然可以保持90％的吸附容量，且仅有0.1％的锰溶损率，说明该碳纳米管穿插锰酸锂材料具有高的吸附容量和循环稳定性。
对比例1
本对比例提供了一种锰酸锂材料的制备方法，具体如下：
(1)将1.4g乙酸锰和2g聚乙烯吡咯烷酮溶解于150mL二甲基亚砜溶剂中，得到溶液1；然后将25mL体积比为1:4的水合肼～无水乙醇混合溶液逐滴滴加到溶液1中得到混合溶液，然后将此混合溶液进行回流24h。待其冷却至室温后，用乙醇和水反复洗剂多次，离心，干燥得到四氧化三锰材料，记为Mn3O4，其扫描电镜(SEM)图如图2(A)所示，材料呈块状形貌。
(2)将物质的量比为0.6:1的Mn3O4和氢氧化锂分散到水中，然后将此分散液置于240℃烘箱中水热反应24h，得到锰酸锂材料，记为LMO，其SEM图如图2(B)所示，材料为八面体状。
如图4所示，相比于实施例1制备的碳纳米管穿插锰酸锂材料(CNT-s-LMO)，此本对比例制备的锰酸锂(LMO)材料展现出较大的电子传递电阻(约49Ω)，不利于离子吸附和储能。将LMO材料制成电容器的阳极，其中活性材料、导电剂和粘结剂质量比为8:1:1，阴极为活性炭(AC)电极。如图6所示，相比于CNT-s-LMO，该材料具有较低的初始吸附容量(1.38mmol g-1)，经过100次循环后，该材料只有65％的吸附容量保持率并且锰溶损率高达3％，说明碳纳米管穿插锰酸锂结构提升了锰酸锂的导电性，容量和循环稳定性。
对比例2
本对比例提供了一种碳纳米管/锰酸锂混合材料的制备方法，具体如下：
(1)将1.4g乙酸锰和2g聚乙烯吡咯烷酮溶解于150mL二甲基亚砜溶剂中，得到溶液1；然后将25mL体积比为1:4的水合肼～无水乙醇混合溶液逐滴滴加到溶液1中得到混合溶液，然后将此混合溶液进行回流24h。待其冷却至室温后，用乙醇和水反复洗剂多次，离心，干燥得到四氧化三锰材料，记为Mn3O4。将此过程得到的四氧化三锰和碳纳米管进行研磨得到四氧化三锰和碳纳米管的混合物，记为Mn3O4/CNT-m，其扫描电镜(SEM)图如图3(A)所示，明显地，四氧化三锰和碳纳米管呈现出分离状态，四氧化三锰呈块状形貌。
(2)将物质的量比为0.6:1的Mn3O4/CNT-m和氢氧化锂分散到水中，然后将此分散液置于240℃烘箱中水热反应24h，得到锰酸锂与碳纳米管混合材料，记为LMO/CNT-m，其SEM图如图3(B)所示，明显地，碳纳米管和锰酸锂呈现为分离状态，锰酸锂为八面体状。与实施例1做对比结果说明，成功制备碳纳米管穿插锰酸锂材料的关键是首先要制备出碳纳米管穿插四氧化三锰材料。
Claims (9)
1.一种高导电性、高稳定性的锰酸锂材料的制备方法，其特征在于，包括以下步骤：
步骤1)：将锰盐、碳纳米管、水合肼和聚乙烯吡咯烷酮分散到二甲基亚砜和无水乙醇中，搅拌，回流，洗涤，干燥，得到碳纳米管穿插四氧化三锰材料；
步骤2)：将步骤1)制得的碳纳米管穿插四氧化三锰材料分散到氢氧化锂溶液中进行水热得到碳纳米管穿插锰酸锂材料。
2.如权利要求1所述的制备方法，其特征在于，所述步骤1)中的锰盐为乙酸锰、硫酸锰、硝酸锰、氯化锰中的任意一种或几种。
3.如权利要求1所述的制备方法，其特征在于，所述步骤1)中锰盐、水合肼、聚乙烯吡咯烷酮、二甲基亚砜、无水乙醇的比例为：1～1.8g:3～7mL:1.5～2.5g:100～200mL:10～30mL。
4.如权利要求1所述的制备方法，其特征在于，所述步骤1)中回流的时间为6～48h。
5.如权利要求1所述的制备方法，其特征在于，所述步骤2)中碳纳米管穿插四氧化三锰和氢氧化锂的摩尔比为0.5～1:1。
6.如权利要求1所述的制备方法，其特征在于，所述步骤2)中水热反应的温度为200～260℃，反应时间为6～48h。
7.一种权利要求1-6任一项所述的制备方法制备的锰酸锂材料为碳纳米管穿过锰酸锂颗粒并且将锰酸锂颗粒有效连接起来而形成的导电网形貌；其中，锰酸锂颗粒呈现为八面体状，颗粒范围在100～1000nm。
8.如权利要求7所述的锰酸锂材料，其特征在于，所述锰酸锂材料中碳纳米管的质量百分含量为0.05％～20％。
9.一种权利要求7-8所述的锰酸锂材料在离子吸附材料、电池或电容器储能材料中的应用。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593446A (zh) * | 2012-02-22 | 2012-07-18 | 清华大学 | 一种锂离子电池活性电极材料的制备方法 |
| CN105958029A (zh) * | 2016-06-24 | 2016-09-21 | 合肥国轩高科动力能源有限公司 | 一种锂离子电池负极复合材料钒酸锂/碳纳米管/碳的制备方法 |
| CN106602008A (zh) * | 2016-12-06 | 2017-04-26 | 广州汽车集团股份有限公司 | 磷酸锰锂正极材料的自组装制备方法以及磷酸锰锂正极材料 |
| CN108470901A (zh) * | 2018-05-29 | 2018-08-31 | 山东大学 | 一种碳纳米管锰酸锂纳米复合材料及制备方法与应用 |
| CN109659560A (zh) * | 2018-12-26 | 2019-04-19 | 赵宏伟 | 一种用于锂离子电池的磷酸钴锂正极材料及制备方法 |
| CN110299516A (zh) * | 2019-06-10 | 2019-10-01 | 天津大学 | 碳纳米管阵列负载钛酸锂柔性电极材料的制备方法 |
| CN113896244A (zh) * | 2021-09-09 | 2022-01-07 | 江苏大学 | 用于盐湖提锂的多孔圆片状锰酸锂电极、及其制备方法 |
-
2022
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593446A (zh) * | 2012-02-22 | 2012-07-18 | 清华大学 | 一种锂离子电池活性电极材料的制备方法 |
| CN105958029A (zh) * | 2016-06-24 | 2016-09-21 | 合肥国轩高科动力能源有限公司 | 一种锂离子电池负极复合材料钒酸锂/碳纳米管/碳的制备方法 |
| CN106602008A (zh) * | 2016-12-06 | 2017-04-26 | 广州汽车集团股份有限公司 | 磷酸锰锂正极材料的自组装制备方法以及磷酸锰锂正极材料 |
| CN108470901A (zh) * | 2018-05-29 | 2018-08-31 | 山东大学 | 一种碳纳米管锰酸锂纳米复合材料及制备方法与应用 |
| CN109659560A (zh) * | 2018-12-26 | 2019-04-19 | 赵宏伟 | 一种用于锂离子电池的磷酸钴锂正极材料及制备方法 |
| CN110299516A (zh) * | 2019-06-10 | 2019-10-01 | 天津大学 | 碳纳米管阵列负载钛酸锂柔性电极材料的制备方法 |
| CN113896244A (zh) * | 2021-09-09 | 2022-01-07 | 江苏大学 | 用于盐湖提锂的多孔圆片状锰酸锂电极、及其制备方法 |
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