CN109338470A - 一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 - Google Patents
一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 Download PDFInfo
- Publication number
- CN109338470A CN109338470A CN201810280842.5A CN201810280842A CN109338470A CN 109338470 A CN109338470 A CN 109338470A CN 201810280842 A CN201810280842 A CN 201810280842A CN 109338470 A CN109338470 A CN 109338470A
- Authority
- CN
- China
- Prior art keywords
- crystalline material
- cumno
- crednerite
- control method
- umno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002178 crystalline material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000000877 morphologic effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002070 nanowire Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 230000003213 activating effect Effects 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 7
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WWSNLNXXISONLQ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Cl(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Cl(C)(C)C WWSNLNXXISONLQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明公开了一种锰铜矿结构CuMnO2晶体材料的形貌调控方法,在碱性条件下,将金属前驱体和表面活性剂加入到溶剂中,搅拌均匀后置于反应釜中进行不同温度下的溶剂热反应,一段时间后得到不同形貌的CuMnO2材料,形貌包括三角片、纳米线、六棱柱和八面体。这些CuMnO2晶体材料具有良好的电化学储能特性,其中纳米线形貌的CuMnO2电化学活性位点最为丰富,展现出最优异稳定的储能性能,在准固态超级电容器领域具有广阔的应用前景;本发明具有操作简单,反应条件易于控制,可实现规模化生产等优点。
Description
技术领域
本发明涉及超级电容器材料合成领域,尤其涉及一种锰铜矿结构CuMnO2晶体材料的形貌调控方法。
背景技术
随着混合动力车和可再生能源的快速发展,发展先进的高容量储能器件成为了世界关注的焦点。超级电容器作为一种可快速充放电的储能器件,与电池相比拥有超高的功率密度和循环稳定性,被认为是最有潜力的能量转化与储存器件。但是仍受限于低能量密度,因此赝电容材料被广泛研究。目前,RuO2赝电容材料由于高电导率和化学稳定性而被商业广泛使用。但超高的成本又限制了它的普及,因此,发展既拥有高能量密度又价格低廉的过渡金属氧化物赝电容材料极为迫切。CuMnO2作为一种典型双过渡金属氧化物,在一些重要领域已开展研究。
目前报道的传统高温固相法合成的CuMnO2材料尺寸较大且形貌不均一,十分不利于电解液传输,使得与材料的晶体形貌、尺寸相关的电化学性质的纳米效应未能得到充分体现。所以急需开展纳米级ABO2结构CuMnO2材料的形貌调控工艺研究,全面实现可控化电化学储能,进一步应用于各种超级电容器器件中。
发明内容
本发明的目的就在于为了解决上述问题而提供一种锰铜矿结构CuMnO2晶体材料的形貌调控方法。
本发明通过以下技术方案来实现上述目的:
根据本发明的一个方面,提供了不同种形貌的CuMnO2晶体材料(三角片、纳米线、六棱柱和八面体),这些材料用于超级电容器中具有良好的电化学储能特性。
所述CuMnO2晶体材料,形貌包括三角片、纳米线、六棱柱和八面体。
所述三角片状CuMnO2晶体材料等边长为250nm~300nm;纳米线状CuMnO2晶体材料横截面上相距最远两点的距离为5nm~10nm;六棱柱状CuMnO2晶体材料粒径为5μm~10μm;八面体状CuMnO2晶体材料粒径为30nm~100nm。
本发明的另一个方面,提供了所述的CuMnO2晶体材料的形貌调控方法,至少包括以下步骤:
将含有阳离子表面活性剂和铜、锰的前驱体在碱性条件下加入到溶剂中,搅拌均匀后置于反应釜中,分别在130~150℃、150~170℃、170~190℃、190~210℃温度区间得到三角片状、纳米线状、六棱柱状、八面体状CuMnO2晶体材料。
所述铜、锰的前驱体的摩尔比为1:1;且浓度均为0.1mol/L。优选地,调
控所述CuMnO2晶体材料的方法,至少包括以下步骤:在溶剂中溶解阳离子表面活性剂,然后依次加入碱液、锰前驱体、铜前驱体;搅拌均匀后转移入反应釜,进行130~210℃温度下的溶剂热反应。
优选地,所述铜前驱体选自乙酸铜、硝酸铜、氯化铜、硫酸铜中的至少一种;锰前驱体选自乙酸锰、硝酸锰、氯化锰、硫酸锰中的至少一种。
优选地,所述阳离子表面活性剂选自十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十二烷基苯磺酸钠中的至少一种。
优选地,所述溶剂为体积比为1:1的乙醇和去离子水的混合溶液。
优选地,所述溶剂热反应温度控制在130~150℃之间,反应时间为24h,得到三角片状CuMnO2晶体材料。
优选地,所述溶剂热反应温度控制在150~170℃之间,反应时间为24h,得到纳米线状CuMnO2晶体材料。
优选地,所述溶剂热反应温度控制在170~190℃之间,反应时间为24h,得到六棱柱状CuMnO2晶体材料。
优选地,所述溶剂热反应温度控制在190~210℃之间,反应时间为24h,得到八面体状CuMnO2晶体材料。
本发明的又一方面,提供了一种超级电容器电极材料,所述电极材料包含所述的不同形貌CuMnO2晶体材料或/和所述形貌调控方法得到的CuMnO2晶体材料。即,所述CuMnO2晶体材料作为超级电容器电极材料的应用。
优选地,所述电极材料用于三电极下的赝电容储能。从而促进高容量储能器件的发展。
本发明的有益效果在于:
本发明是一种锰铜矿结构CuMnO2晶体材料的形貌调控方法,与现有技术相比,本发明以Cu(NO3)2为铜前驱体,Mn(CH3COO)2为锰前驱体,阳离子表面活性剂做修饰;采用溶剂热反应的方法,通过调控反应温度控制合成了不同形貌的CuMnO2材料,形貌包括三角片、纳米线、六棱柱和八面体。本发明所提供的不同形貌CuMnO2晶体材料,其作为电极材料用于超级电容器具有高良好的电化学储能特性,其中纳米线状CuMnO2电化学活性位点最为丰富,展现出最优异稳定的储能性能,优于商业用RuO2;该方法操作简单,反应条件易于控制,可实现规模化生产且对环境友好。该方法所用原料来源广泛且价格低廉,相较于商业用RuO2电极材料成本很低。
附图说明
图1为实施例1、2、3、4所制备产物的X射线衍射谱图。
图2为实施例1中样品1#的TEM图。
图3为实施例2中样品2#的TEM图。
图4为实施例3中样品3#的TEM图。
图5为实施例4中样品4#的TEM图。
图6为实施例1、2、3、4所制备产物在碱性条件下,超级电容器电极的线性扫描伏安曲线图。
图7为实施例1、2、3、4所制备产物在碱性条件下,超级电容器电极的恒电流充放电曲线图。
具体实施方式
下面结合附图对本发明作进一步说明:
本发明利用日本Rigaku公司的miniflex600粉末X射线衍射仪进行结构分析;荷兰FEI公司的Tecnai G2S-Twin F20透射电子显微镜进行TEM形貌分析。
实施例1制备三角片状CuMnO2晶体材料
将0.15g的十六烷基三甲基溴化铵溶于25ML水和25ML乙醇的混合溶液中,然后加入5ML NaOH溶液(浓度2mol/L),随后依次加入2.5ML Mn(CH3COO)2·4H2O溶液(浓度0.1mol/L)和2.5ML Cu(NO3)2·3H2O溶液(浓度0.1mol/L)。充分搅拌2h至混合均匀,转移至100ML反应釜,在130~150℃的条件下反应24小时。反应结束后待其自然冷却,取出样品分别用水和乙醇洗涤,重复此步骤三次,置于70℃烘箱干燥6h,得到三角片状CuMnO2晶体材料,记为1#。
实施例2制备纳米线状CuMnO2晶体材料
将0.15g的十六烷基三甲基溴化铵溶于25ML水和25ML乙醇的混合溶液中,然后加入5ML NaOH溶液(浓度2mol/L),随后依次加入2.5ML Mn(CH3COO)2·4H2O溶液(浓度0.1mol/L)和2.5ML Cu(NO3)2·3H2O溶液(浓度0.1mol/L)。充分搅拌2h至混合均匀,转移至100ML反应釜,在150~170℃的条件下反应24小时。反应结束后待其自然冷却,取出样品分别用水和乙醇洗涤,重复此步骤三次,置于70℃烘箱干燥6h,得到纳米线状CuMnO2晶体材料,记为2#。
实施例3制备六棱柱状CuMnO2晶体材料
将0.15g的十六烷基三甲基溴化铵溶于25ML水和25ML乙醇的混合溶液中,然后加入5ML NaOH溶液(浓度2mol/L),随后依次加入2.5ML Mn(CH3COO)2·4H2O溶液(浓度0.1mol/L)和2.5ML Cu(NO3)2·3H2O溶液(浓度0.1mol/L)。充分搅拌2h至混合均匀,转移至100ML反应釜,在170~190℃的条件下反应24小时。反应结束后待其自然冷却,取出样品分别用水和乙醇洗涤,重复此步骤三次,置于70℃烘箱干燥6h,得到六棱柱状CuMnO2晶体材料,记为3#。
实施例4制备八面体状CuMnO2晶体材料
将0.15g的十六烷基三甲基溴化铵溶于25ML水和25ML乙醇的混合溶液中,然后加入5ML NaOH溶液(浓度2mol/L),随后依次加入2.5ML Mn(CH3COO)2·4H2O溶液(浓度0.1mol/L)和2.5ML Cu(NO3)2·3H2O溶液(浓度0.1mol/L)。充分搅拌2h至混合均匀,转移至100ML反应釜,在190~210℃的条件下反应24小时。反应结束后待其自然冷却,取出样品分别用水和乙醇洗涤,重复此步骤三次,置于70℃烘箱干燥6h,得到八面体状CuMnO2晶体材料,记为4#。
实施例5样品的结构、形貌表征
采用粉末X射线对样品1#~样品4#进行结构分析如图1所示,结果表明,所合成的样品均为锰铜矿结构的CuMnO2。通过透射电子显微镜对样品1#~样品4#进行形貌分析,分别如图2至图5所示,样品1#为三角片状,样品2#为纳米线状,样品3#为六棱柱状,样品4#为八面体状。
实施例6电化学储能测试
采用三电极系统测试材料的电化学储能特性,选取6mol/L KOH溶液作为电解液。测试电极是由CuMnO2晶体材料、乙炔黑、聚四氟乙烯按照8:1:1的比例配制研磨,并均匀涂1cm2于镍网上,压片烘干后得到的。Pt作为对电极,饱和甘汞电极作参比。电化学工作站选择上海晨华Chi760e。工作模式选择线性扫描伏安法;电势范围选择0~0.4V(vs SCE)。
将样片1#~样品4#按照上述电化学测试条件得到的线性扫描伏安曲线如图6所示,恒电流充放电曲线如图7所示。由图7计算出在2A/g电流密度下,三角片状样品1#的比电容为122F/g;纳米线状样品的比电容为691F/g;六棱柱状样品的比电容为177F/g;八面体状样品的比电容为127F/g。
以上显示和描述了本发明的基本原理和主要特征及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
1.一种锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于:通过控制不同温度下的溶剂热反应调控晶体形貌;具体为:在碱性条件下,控制加料顺序和速率先将阳离子表面活性剂和0.1mol/L铜、锰的前驱体加入到乙醇和去离子水体积比为1:1的混合溶剂中,搅拌均匀后置于反应釜中,在130~210℃温度下进行24h溶剂热反应,将产物经洗涤离心烘干后,即得到三角片、纳米线、六棱柱和八面体形貌的CuMnO2材料。
2.根据权利要求1所述的锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于,所述阳离子表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十二烷基苯磺酸钠中的一种或多种组合。
3.根据权利要求1所述的锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于,所述铜前驱体选自乙酸铜、硝酸铜、氯化铜、硫酸铜中的一种或多种组合;锰前驱体选自乙酸锰、硝酸锰、氯化锰、硫酸锰中的一种或多种组合;摩尔比为1:1,且浓度均为0.1mol/L。
4.根据权利要求1所述的锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于,所述溶剂为乙醇和去离子水的混合溶液,体积比为1:1。
5.根据权利要求1所述的锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于,控制反应温度为130~210℃之间来调控形貌,反应时间为24h。
6.根据权利要求1所述的锰铜矿结构CuMnO2晶体材料的形貌调控方法,其特征在于,所得CuMnO2形貌包括三角片、纳米线、六棱柱和八面体。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810280842.5A CN109338470B (zh) | 2018-04-02 | 2018-04-02 | 一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810280842.5A CN109338470B (zh) | 2018-04-02 | 2018-04-02 | 一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109338470A true CN109338470A (zh) | 2019-02-15 |
CN109338470B CN109338470B (zh) | 2021-04-27 |
Family
ID=65291341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810280842.5A Active CN109338470B (zh) | 2018-04-02 | 2018-04-02 | 一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109338470B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110683583A (zh) * | 2019-10-23 | 2020-01-14 | 山东大学 | 一种氧化锰铜超级电容器电极材料的制备方法 |
CN113769757A (zh) * | 2021-09-09 | 2021-12-10 | 武汉理工大学 | 原位光致热制备尖晶石结构Cu1.5Mn1.5O4催化剂的方法及其应用 |
-
2018
- 2018-04-02 CN CN201810280842.5A patent/CN109338470B/zh active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110683583A (zh) * | 2019-10-23 | 2020-01-14 | 山东大学 | 一种氧化锰铜超级电容器电极材料的制备方法 |
CN110683583B (zh) * | 2019-10-23 | 2020-06-05 | 山东大学 | 一种氧化锰铜超级电容器电极材料的制备方法 |
CN113769757A (zh) * | 2021-09-09 | 2021-12-10 | 武汉理工大学 | 原位光致热制备尖晶石结构Cu1.5Mn1.5O4催化剂的方法及其应用 |
Also Published As
Publication number | Publication date |
---|---|
CN109338470B (zh) | 2021-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Influence of metallic oxide on the morphology and enhanced supercapacitive performance of NiMoO4 electrode material | |
CN105448543A (zh) | 一种泡沫镍为基底的CoMoO4纳米结构超级电容器电极材料的制备方法 | |
CN108470628B (zh) | 一种复合电极材料及其制备方法 | |
CN104409219B (zh) | 六边形二氧化锰纳米片材料的制备及其作为超级电容器电极材料的应用 | |
CN112830523B (zh) | 用于超级电容器的钼掺杂四氧化三钴及其制备方法 | |
CN112670096B (zh) | 一种碱式金属盐纳米材料及其制备方法与应用 | |
He et al. | Binder-free MgCo2O4@ Ni3S2 core-shell-like composites as advanced battery materials for asymmetric supercapacitors | |
CN109133199A (zh) | 一种高循环性能球状纳米钼酸镍电极材料的制备方法 | |
CN104157858A (zh) | 分级多孔四氧化三铁/石墨烯纳米线及其制备方法和应用 | |
CN110350184A (zh) | 一种用于电池正极材料的高容量NiMoO4储能材料的制备方法 | |
CN109741966A (zh) | 一种具有核壳结构特征的Ni6MnO8@碳纳米管复合材料及其制备方法和应用 | |
CN109830383A (zh) | 一种超级电容器复合材料及其制备方法与应用 | |
CN112490017A (zh) | 一种NiCo-LDH纳米材料的制备方法及其应用 | |
CN104867680B (zh) | 用作超级电容器电极的NiCo2O4@NiCo2O4纳米材料及其制备方法 | |
Luo et al. | Preparation of NiMoO4 nanoarrays electrodes with optimized morphology and internal crystal water for efficient supercapacitors and water splitting | |
CN109545573B (zh) | 金属1t相硫化铼中空纳米球超级电容器电极材料的制备方法 | |
CN109817475B (zh) | 硫化铋镍正极材料的制备方法及其应用 | |
CN107128981A (zh) | Ni‑M‑O‑H纳米晶及其可控式合成方法和在制备超级电容器中的应用 | |
CN109338470A (zh) | 一种锰铜矿结构CuMnO2晶体材料的形貌调控方法 | |
CN106683896A (zh) | 一种核壳结构钼酸镍/二氧化锰复合材料的制备方法及其应用 | |
CN110759389B (zh) | 一种Cu(Ni,Co)2S4电极材料及其制备方法 | |
CN112279308A (zh) | 一种大批量制备高储能镍钴氢氧化物电极材料的方法 | |
CN112467077A (zh) | 有效增强多种过渡金属氧化物储电性能的普适性电化学改性制备方法 | |
CN115763096A (zh) | 一种基于乌洛托品的Ni-MOF及其制备方法和应用 | |
CN114709086B (zh) | 镍基金属有机框架层状纳米片阵列材料及其制备和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |