CN108376614A - 一种NiCo2O4/碳纳米管复合电极材料及其制备方法 - Google Patents
一种NiCo2O4/碳纳米管复合电极材料及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 38
- 229910005949 NiCo2O4 Inorganic materials 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009415 formwork Methods 0.000 claims abstract description 28
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002146 bilateral effect Effects 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- -1 carbon nano tube compound Chemical class 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 8
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- 239000011258 core-shell material Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical class [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- 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
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Abstract
一种NiCo2O4/碳纳米管复合电极材料及其制备方法,它涉及一种单体以碳纳米管为核,NiCo2O4纳米管为壳的核壳结构,整体为高度有序纳米管阵列的NiCo2O4/碳纳米管复合电极材料,其制备步骤包括:一、选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干;二、以处理好的多孔氧化铝为模板,在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列;三、利用化学气相沉积法在镍钴合金纳米管内沉积碳纳米管;四、用NaOH除去氧化铝模板,经过煅烧后得到NiCo2O4/碳纳米管复合材料。该方法获得的NiCo2O4/碳纳米管复合材料应用于超级电容器电极材料时具有较高的比电容值和良好的电化学性能稳定性。
Description
技术领域
本发明涉及一种NiCo2O4/碳纳米管复合电极材料及其制备方法,属于材料制备领域。
背景技术
近年来,超级电容器因其具有高功率密度、充电短时间和循环寿命长等诸多优点,广泛用于通信,航空航天,大型工业装备,微电子器件等诸多等要求瞬间释放超大电流的场合,尤其是在新能源汽车领域有着广阔的应用前景。电极材料是影响超级电容器性能的关键因素,以RuO2等贵金属氧化物因其赝电容原理有较大的比电容值,但昂贵的价格和毒性限制了其商业化应用。一些廉价金属氧化物代替贵金属作为超级电容器电极材料成为研究热点。NiCo2O4是一种典型的尖晶石结构复合金属氧化物,存在Co3+/Co2+及Ni3+/Ni2+氧化还原电对,可以获得较高的工作电压窗口和比电容值,同时因其廉价无毒表现为极具潜力的电极材料,因此不同结构、形态、尺寸的NiCo2O4的制备受到了众多研究人员的关注(如CN102259936B; CN102092797B; CN102745752A; CN103107025A; CN103594246A;CN103318978B; CN104003455B; CN104659358A)。然而与贵金属氧化物相比,NiCo2O4由于其导电性较差,导致比电容偏低,在大电流密度下充循环冲放电不够稳定。因此,人们考虑将NiCo2O4与碳材料或导电聚合物进行复合来提高材料的导电性,以达到增强其电化学性能的目的(如CN103117389B; CN104143450A)。
碳纳米管(CNTs)具有特殊的一维中空的纳米结构,它主要由呈六边形排列的碳原子构成的单层或数层的同轴圆管构成,具有优良的耐热、耐腐蚀、耐冲击性能,而且传热和导电性能好,使其有制备大容量超级电容器的潜在优势。但CNTs单独作为超级电容器电极材料比电容值过低,一般只有40F/g。鉴于过渡氧化物和碳纳米管之间的互补性,通常考虑将其复合,使该复合产物既具有赝电容特性,又具有双电层特性,从而制备出具有高比电容、高导电率、循环充放电稳定的超级电容器电极材料。Leela等(Asymmetric FlexibleSupercapacitor Stack, Nonoscale Research Letters, 2008)利用溶胶凝胶法制备金属氧化物/多壁碳纳米管复合电极材料,表现出优异的电化学性能,但溶胶凝胶法加入表面活性剂,容易引入杂质,而且成本较高;Kuan等(Electrodeposition of Nickel and CobaltMixed Oxide/Carbon Nanotube Thin Films and Their Charge Storage Properties,J. Electorchem. soc., 2006)、Fan等(Preparation and capacitive properties ofcobalt-nickel oxides/carbon nanotube coposites,Electrochim. Acta. 2007)和Wen等(A three dimensional vertically aligned multiwall carbon nanotube-NiCo2O4core-shell structure for novel high-performance supercapacitors, J. Mater.Chem. A, 2014)利用电化学沉积方法制备了钴镍氧化物/碳纳米管复合材料,该方法反应时间长,耗能高;中国专利(CN1315139C)提供了一种碳纳米管与过渡氧化物复合的途径,利用粘结剂把碳纳米管和过渡金属氧化物复合,粘结剂的加入会增加材料的内阻,不利于该复合材料作为超级电容器电极材料。
发明内容
本发明的目的在于提供一种NiCo2O4/碳纳米管复合电极材料,同时还提供一种采用方波脉冲电沉积法制备镍钴合金纳米管阵列,进而通过化学气相沉积法在镍钴合金纳米管内沉积碳纳米管,经过除去氧化铝模板和煅烧,获得NiCo2O4/碳纳米管复合电极材料的制备方法。
本发明的具体步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后进行方波脉冲电沉积,沉积完成后用蒸馏水清洗至中性;
所述的沉积液成分为:1份的NiSO4•6H2O,2份的CoSO4•7H2O,H3BO3和(NH4)2SO4;
所述的方波脉冲电沉积的条件为:在0 V持续30 s,然后瞬间加-2.5 V的电位持续5 s的方波脉冲电沉积一定时间;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至500~800℃,通入50ml/min的C2H2,反应10~60min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
本发明的优点:一、本发明获得的NiCo2O4/碳纳米管复合电极材料具有新颖独特的结构(单体以碳纳米管为核,NiCo2O4纳米管为壳的核壳结构,其整体为高度有序纳米管阵列);二、所获得的NiCo2O4/碳纳米管复合电极材料用于超级电容器电极时具有较高的比电容值和良好的电化学性能稳定性。
具体实施方式
下面是结合实施例对本发明进行详细描述,以便更好地理解本发明的目的、特点和优点。虽然本发明是结合该具体实施例进行描述,但并不意味着本发明局限于所描述具体实施例。相反,对可以包括在本发明权利要求内所限定的保护范围内的实施方式进行替代、改进和等同的实施方式,都属于本发明的保护范围。对于未特别标注的工艺参数可按常规技术进行。
本发明的具体步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后进行方波脉冲电沉积,沉积完成后用蒸馏水清洗至中性;
所述的沉积液成分为:1份的NiSO4•6H2O,2份的CoSO4•7H2O,H3BO3和(NH4)2SO4;
所述的方波脉冲电沉积的条件为:在0 V持续30 s,然后瞬间加-2.5 V的电位持续5 s的方波脉冲电沉积一定时间;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至500~800℃,通入50ml/min的C2H2,反应10~60min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
实施例1:
步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:准备沉积液,其配方为:262 g/L NiSO4•6H2O和562 g/L CoSO4•7H2O,40 g/L H3BO3和40 g/L (NH4)2SO4;以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后在方波为0 V持续30 s, -2.5 V持续5 s下进行脉冲电沉积50个循环,沉积完成后用蒸馏水清洗至中性;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至500℃,通入50ml/min的C2H2,反应10min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
对实施例1所制备的样品进行XRD和TEM表征,检测到了NiCo2O4和碳纳米管物相,NiCo2O4/碳纳米管复合材料是核壳纳米阵列结构;对NiCo2O4/碳纳米管复合电极材料进行恒流充放电测试,在电流密度为1A/g下的比电容值分别问1046.8F/g。
实施例2:
步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:准备沉积液,其配方为:262 g/L NiSO4•6H2O和562 g/L CoSO4•7H2O,40 g/L H3BO3和40 g/L (NH4)2SO4;以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后在方波为0 V持续30 s, -2.5 V持续5 s下进行脉冲电沉积100个循环,沉积完成后用蒸馏水清洗至中性;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至800℃,通入50ml/min的C2H2,反应10min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
对实施例2所制备的样品进行XRD和TEM表征,检测到了NiCo2O4和碳纳米管物相,NiCo2O4/碳纳米管复合材料是核壳纳米阵列结构;对NiCo2O4/碳纳米管复合电极材料进行恒流充放电测试,在电流密度为1A/g下的比电容值分别问1153.9F/g。
实施例3:
步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:准备沉积液,其配方为:262 g/L NiSO4•6H2O和562 g/L CoSO4•7H2O,40 g/L H3BO3和40 g/L (NH4)2SO4;以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后在方波为0 V持续30 s, -2.5 V持续5 s下进行脉冲电沉积100个循环,沉积完成后用蒸馏水清洗至中性;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至600℃,通入50ml/min的C2H2,反应60min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
对实施例3所制备的样品进行XRD和TEM表征,检测到了NiCo2O4和碳纳米管物相,NiCo2O4/碳纳米管复合材料是核壳纳米阵列结构;对NiCo2O4/碳纳米管复合电极材料进行恒流充放电测试,在电流密度为1A/g下的比电容值分别问977.8F/g。
实施例4:
步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:准备沉积液,其配方为:262 g/L NiSO4•6H2O和562 g/L CoSO4•7H2O,40 g/L H3BO3和40 g/L (NH4)2SO4;以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后在方波为0 V持续30 s, -2.5 V持续5 s下进行脉冲电沉积200个循环,沉积完成后用蒸馏水清洗至中性;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至700℃,通入50ml/min的C2H2,反应30min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
对实施例4所制备的样品进行XRD和TEM表征,检测到了NiCo2O4和碳纳米管物相,NiCo2O4/碳纳米管复合材料是核壳纳米阵列结构;对NiCo2O4/碳纳米管复合电极材料进行恒流充放电测试,在电流密度为1A/g下的比电容值分别问1334.2F/g。
Claims (2)
1.一种NiCo2O4/碳纳米管复合电极材料,其特征在于,NiCo2O4/碳纳米管复合电极材料的单体以碳纳米管为核,NiCo2O4纳米管为壳的核壳结构,其整体为高度有序纳米管阵列。
2.如权利要求1所述的一种NiCo2O4/碳纳米管复合电极材料,其特征在于制备步骤为:
第一步:多孔氧化铝模板准备
选取孔径为200nm双通的氧化铝模板,在其背面磁控溅射一层厚度为1μm的铜膜,依次经过三甲基氰硅烷、乙醇、蒸馏水超声清洗后烘干以备用;
第二步:镍钴合金纳米管阵列制备
在电解池中采用方波脉冲电沉积法制备镍钴合金纳米管阵列:以第一步准备好氧化铝模板作为工作电极,铂片为对电极,饱和甘汞电极为辅助电极,加入沉积液后进行方波脉冲电沉积,沉积完成后用蒸馏水清洗至中性;
所述的沉积液成分为:1份的NiSO4•6H2O,2份的CoSO4•7H2O,H3BO3和(NH4)2SO4;
所述的方波脉冲电沉积的条件为:在0 V持续30 s,然后瞬间加-2.5 V的电位持续5 s的方波脉冲电沉积一定时间;
第三步:镍钴/碳纳米管阵列制备
将镍钴合金纳米管阵列放入管式炉中,多次置换Ar后将管式炉内气压调至10KPa,然后升温至500~800℃,通入50ml/min的C2H2,反应10~60min后停止加热,继续通入Ar并冷却至室温;
第四步:NiCo2O4/碳纳米管阵列制备
将镍钴/碳纳米管阵列取出,用1M/L的NaOH浸泡一段时间去除氧化铝模板,然后用乙醇和蒸馏水清洗至中性,烘干后放置马弗炉中,以1℃/min的的升温速率升温至300℃保温2h,冷却后得到NiCo2O4/碳纳米管阵列。
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