CN107680831A - 一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法 - Google Patents
一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 48
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 17
- 240000008042 Zea mays Species 0.000 title claims abstract description 15
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 15
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 15
- 235000005822 corn Nutrition 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 42
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
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- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
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- 150000004706 metal oxides Chemical group 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- 239000010941 cobalt Substances 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- -1 cobalt nickel metal oxide Chemical class 0.000 abstract description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
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- 239000000463 material Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
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- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- BGORGFZEVHFAQU-UHFFFAOYSA-L cobalt(2+);sulfate;hydrate Chemical class O.[Co+2].[O-]S([O-])(=O)=O BGORGFZEVHFAQU-UHFFFAOYSA-L 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
本发明属于复合电极材料领域,公开了一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯复合材料的合成方法。将氧化石墨烯、Ni(NO3)2、Co(NO3)2溶解于乙二胺水溶液中,分散,微波反应,得Co3O4@NiCo2O4/氮掺杂石墨烯复合材料。采用一步法完成石墨烯的氮掺杂与金属氧化物的共沉积,操作简单,成本低廉,产率较高。乙二胺为石墨烯掺杂提供N,且水解产生氨水与Co2+、Ni2+结合产生钴镍金属氧化物。制得的介孔管状钴酸镍晶体表面生长有颗粒状Co3O4晶体与三维改性石墨烯包覆结合,双金属氧化物共生复合后晶体颗粒中金属离子表面电子云得到极大的活化,在充放电过程中电子转移加快,同时改性石墨烯所掺杂氮元素得邻近C活性位点与金属氧化物在充放电过程中的协同效益有效提高了复合材料的电容和循环稳定性。
Description
技术领域
本发明属于复合自支撑电极材料领域,涉及一种空心玉米棒状双金属协同效应
Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法。
技术背景
石墨烯凭借其独特的蜂窝网状二维空间结构,展现出超大的比表面积、良好的电子迁移率、超高的稳定性等优异性能。因此作为基体材料在超级电容器领域有着极佳的应用潜力。然而已有的文献表明,石墨烯电极材料的实际容量远小于理论容量,且衰减较快,这需要进行氮元素的掺杂调节石墨烯的电子结构。在石墨烯片层间引入N、B等杂原子可以有效的将石墨烯从零带隙的半金属转变成半导体,形成n-型或p-型掺杂的石墨烯。(ZhangC H,Fu L等,Adv.Mater.2011,23,1020–1024;Huang C J,Chen C等,J.Mater.Chem.A,2013,1,12192-12197)氮元素的引入增加石墨烯导电能力的同时在石墨烯表面造成平面结构的改变,有利于减小石墨烯相互间的堆叠。
钴系金属氧化物性能稳定,廉价易得绿色环保是一种理想的超级电容器电极材料。其中Co3O4具有优异的氧化还原性和较高的理论电容值(3560F·g-1),但较差的循环稳定性及较低的倍率性能限制了其在超级电容器方面的应用。钴酸镍是一种典型的尖晶石型混合价态金属复合氧化物,在其晶体结构中,镍离子占据八面体位置,钴离子既占有八面体位置又占据四面体位置。固态氧化还原对Co2+/Co3+和Ni2+/Ni3+在结构中的出现为赝电容的产生提供了两个活性中心。混合过渡金属氧化物(Co3O4/NiCo2O4)由于阳离子的多种价态和不同的性能使得电子转移有较低的活化能,比电容性能提高是非常理想的超级电容器电极材料。将NiCo2O4与Co3O4双金属共结晶能够在钴酸镍纳米管表面生成颗粒状的四氧化三钴纳米晶(如玉米棒上生长玉米粒),金属氧化物与三维氮掺杂石墨烯基材料进行复合使纳米棒包覆在石墨烯片层间,有效的避免石墨烯间重新堆叠,使NiCo2O4的高电容与石墨烯材料的大比表面积优势相互结合,极大的改良了复合和材料的性能。(Wu H Y,Wang H W,物理化学学报,2013,29(7),1501-1506)一般地,双金属氧化物纳米管状结构易损导致导电性变差,为了保证电极的柔性和导电性符合要求,可以将具有高长径比的双金属氧化物的纳米线或纳米棒与碳纳米管(石墨烯)复合成柔性电极。这种氧化物纳米线或纳米管与石墨烯相互穿插的结构之间存在着相互连通的孔道,有利于电解液的填充而使氧化还原反应充分进行,具有较高的能量密度和功率密度。(Tai Z,Yan X,Lang J,Xue Q,J.PowerSources.2012,199:373-378)。
发明内容
本发明的目的是提供一种操作简单、具有空心玉米棒状结构的Co3O4@NiCo2O4/氮掺杂石墨烯复合纳米材料的制备方法,制备自支撑柔性复合材料的比电容可达2324.6F·g-1。
本发明以乙二胺为氮源,氧化石墨烯,六水合硫酸钴和六水合硝酸镍为原料,在微波加热的过程中钴镍离子催化乙二胺分解产生氨,小分子氨中的氮原子取代氧化石墨烯中的部分碳原子,并修复氧化石墨烯的部分缺陷结构,形成氮掺杂石墨烯。乙二胺分解同时产生氨水,溶液呈现碱性,无需外加碱源;微波加热生成的四氧化三钴负载在钴酸镍空心纳米棒上,并均匀分散在氮掺杂石墨烯表面,制备出电化学性能良好的特殊形貌Co3O4@NiCo2O4/氮掺杂石墨烯制成了具有高柔软性和高比电容的电极材料。
本发明通过以下步骤实现:
将氧化石墨烯、Ni(NO3)2·6H2O、Co(NO3)2·6H2O分散在乙二胺的水溶液中,分散均匀后,得到混合溶液,然后将混合溶液转移到微波反应器中,微波反应结束后,产物分别用去离子水和乙醇洗涤,得到空心玉米棒状的Co3O4@NiCo2O4/氮掺杂石墨烯复合电极材料。
所述乙二胺为氮源和碱源。
所述混合溶液中Ni(NO3)2·6H2O、Co(NO3)2·6H2O和乙二胺的摩尔比为1:(2.5~10):(0.1~10),其中,镍离子在所述混合溶液中的摩尔浓度为0.071mol/L。
所述乙二胺水溶液中,乙二胺和去离子水的比例为(1~10):(69~60)。
所述微波反应的温度为300~450℃,反应时间为10~30min,微波功率是850W。
利用X射线衍射仪(XRD)、透射电子显微镜(TEM)、电化学工作站来表征其材料及电容活性。
用此方法制备的Co3O4@NiCo2O4/NG复合物,纳米管尺寸可控,纳米管直径为40-60nm,长度为2-5um,纳米晶Co3O4颗粒均匀,直径为3.5-4nm。
将本发明制备的空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料用于制备柔性超级电容器电极,不需要外加粘接剂、导电材料。
本发明的有益效果为:
(1)本方法具有反应条件温和、反应易于控制、成本低、工艺和流程简便的优点。
(2)微波合成纳米氧化物过程氮原子能同步掺杂到石墨烯中。
附图说明
图1为所制备Co3O4@NiCo2O4/NG,Co3O4/NG及其NiCo2O4/NG的XRD衍射谱图,图中衍射峰均为四氧化三钴、钴酸镍和石墨烯的特征衍射峰。
图2为双金属玉米棒状Co3O4@NiCo2O4的透射电镜照片。
图3为Co3O4@NiCo2O4/NG的XPS谱图。
图4为NiCo2O4/NG,Co3O4@NiCo2O4/GO,Co3O4@NiCo2O4/NG在1A·g-1条件下的恒电流充放电曲线图。
图5为Co3O4@NiCo2O4/NG在不同电流密度下的恒电流充放电曲线图。
具体实施方式
下面结合具体实施实例对本发明做进一步说明。
实施例1
将7.28g Co(NO3)2·6H2O(0.025mol)、1.45g Ni(NO3)2·6H2O(0.005mol)、0.15g氧化石墨烯超声分散在70ml乙二胺溶液中(V乙二胺:V去离子水=1:6),将溶液转移到微波反应器中,于850W功率、350℃下微波加热15min后将得到的产物分别用去离子水和乙醇洗涤三遍,得到Co3O4@NiCo2O4/NG复合物。
如图1,样品在2θ为18.9°、31.1°、36.7°、38.4°、44.5°、55.3°、59.2°和65.0°均出现了X射线的衍射峰,分别可以与NiCo2O4晶体(JCPDS No.73-1702)的(111)、(220)、(311)、(222)、(400)、(422)、(511)、(440)晶面对应。在19.0°、31.2°、36.9°、44.9°和65.3°的衍射峰分别与Co3O4晶体(JCPDS No.42-1467)在(111)、(220)、(311)、(400)、(440)晶面的标准谱图相一致。三维氮掺杂石墨烯具有较大的比表面积,氮元素的掺杂活化了与其相邻的碳原子,增加了改性石墨烯表面活性位点的数量,有利于金属氧化物与改性石墨烯表面之间的电子转移。而中空介孔的NiCo2O4晶体晶格与Co3O4晶体晶格结构一致,有利于小粒径Co3O4的负载,如图2。Co3O4@NiCo2O4/NG复合材料经X射线光电子能谱分析(XPS)表明镍元素、钴元素是以Ni2+、Co2+、Co3+的价态存在,氮元素以碳氮键、吡啶氮、吡咯氮形式存在,如图3。
实施例2
将7.28g Co(NO3)2·6H2O(0.025mol)、1.45g Ni(NO3)2·6H2O(0.005mol)、0.15g氧化石墨烯超声分散在70ml乙二胺溶液中(V乙二胺:V去离子水=1:69),将溶液转移到微波反应器中,于850W功率、450℃下微波加热15min后将得到的产物分别用去离子水和乙醇洗涤三遍,得到Co3O4@NiCo2O4/NG复合物。
三维氮掺杂石墨烯具有较大的比表面积,氮元素的掺杂活化了与其相邻的碳原子,增加了改性石墨烯表面活性位点的数量,有利于金属氧化物与改性石墨烯表面之间的电子转移。而中空介孔的NiCo2O4晶体晶格与Co3O4晶体晶格结构一致,有利于小粒径Co3O4的负载,将上述制备的复合材料进行充放电测试,当电流密度为1A·g-1时,比容量达到2157.3F·g-1;经过2000次循环充放电测试之后比容量仍保持在89%以上。
实施例3
将4.00g Co(NO3)2·6H2O(0.014mol)、1.45g Ni(NO3)2·6H2O(0.005mol)、0.15g氧化石墨烯超声分散在70ml乙二胺溶液中(V乙二胺:V去离子水=1:34),将溶液转移到微波反应器中,于850W功率、350℃下微波加热15min后将得到的产物分别用去离子水和乙醇洗涤三遍,得到Co3O4@NiCo2O4/NG复合物。
三维氮掺杂石墨烯具有较大的比表面积,氮元素的掺杂活化了与其相邻的碳原子,增加了改性石墨烯表面活性位点的数量,有利于金属氧化物与改性石墨烯表面之间的电子转移。而中空介孔的NiCo2O4晶体晶格与Co3O4晶体晶格结构一致,有利于小粒径Co3O4的负载,将上述制备的复合材料进行充放电测试,电流密度为1A·g-1时,比容量达到了2198.7F·g-1,如图4,比电容值大于NiCo2O4/NG(1874.3F·g-1)和Co3O4@NiCo2O4/GO(2005.6F·g-1);经过2000次循环充放电测试之后比容量仍保持在88.2%以上。
实施例4
将11.64g Co(NO3)2·6H2O(0.040mol)、1.45g Ni(NO3)2·6H2O(0.005mol)、0.15g氧化石墨烯超声分散在70ml乙二胺溶液中(V乙二胺:V去离子水=1:34),将溶液转移到微波反应器中,于850W功率、450℃下微波加热15min后将得到的产物分别用去离子水和乙醇洗涤三遍,得到Co3O4@NiCo2O4/NG复合物。
三维氮掺杂石墨烯具有较大的比表面积,氮元素的掺杂活化了与其相邻的碳原子,增加了改性石墨烯表面活性位点的数量,有利于金属氧化物与改性石墨烯表面之间的电子转移。而中空介孔的NiCo2O4晶体晶格与Co3O4晶体晶格结构一致,有利于小粒径Co3O4的负载,将上述制备的复合材料进行充放电测试,当电流密度为1A·g-1时,比容量达到了2003.6F·g-1;经过2000次循环充放电测试之后比容量仍保持在91.6%以上。
实施例5
将7.28g Co(NO3)2·6H2O(0.025mol)、1.45g Ni(NO3)2·6H2O(0.005mol)、0.15g氧化石墨烯超声分散在70ml乙二胺溶液中(V乙二胺:V去离子水=1:34),将溶液转移到微波反应器中,于850W功率、350℃下微波加热15min后将得到的产物分别用去离子水和乙醇洗涤三遍,得到Co3O4@NiCo2O4/NG复合物。
三维氮掺杂石墨烯具有较大的比表面积,氮元素的掺杂活化了与其相邻的碳原子,增加了改性石墨烯表面活性位点的数量,有利于金属氧化物与改性石墨烯表面之间的电子转移。而中空介孔的NiCo2O4晶体晶格与Co3O4晶体晶格结构一致,有利于小粒径Co3O4的负载,将上述制备的复合材料进行充放电测试,当电流密度为1A·g-1时,比容量达到了2324.6F·g-1;经过2000次循环充放电测试之后比容量仍保持在92.4%以上。如图5,当电流密度为1A·g-1、2A·g-1、5A·g-1、10A·g-1和20A·g-1时,所得比电容值分别为2324.6F·g-1、2293.3F·g-1、2146.6F·g-1、2024.6F·g-1和1824.6F·g-1。当电流密度从1A·g-1增加到20·A g-1时其放电比电容值可保持初始值的78.5%。其优异的电容性能主要是结合了钴酸镍的大比电容性能及四氧化三钴的高稳定性能,同时发挥了同类型双金属氧化物晶体间的协同效应。
最后应说明的是: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,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。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 (7)
1.一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,其特征在于:具体步骤为:
将氧化石墨烯、Ni(NO3)2·6H2O、Co(NO3)2·6H2O分散在乙二胺的水溶液中,分散均匀后,得到混合溶液,然后将混合溶液转移到微波反应器中,微波反应结束后,产物分别用去离子水和乙醇洗涤,得到空心玉米棒状的Co3O4@NiCo2O4/氮掺杂石墨烯复合电极材料。
2.如权利要求1所述的一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,其特征在于:乙二胺为氮源和碱源。
3.如权利要求1所述的一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,其特征在于:所述混合溶液中Ni(NO3)2·6H2O、Co(NO3)2·6H2O和乙二胺的摩尔比为1:(2.5~10):(0.1~10),其中,镍离子在所述混合溶液中的摩尔浓度为0.071mol/L。
4.如权利要求1所述的一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,其特征在于:所述乙二胺水溶液中,乙二胺和去离子水的体积例为(1~10):(69~60)。
5.如权利要求1所述的一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,其特征在于:所述微波反应的温度为300~450℃,反应时间为10~30min,微波功率是850W。
6.一种空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料的制备方法,是通过权利要求1~5任一项所述制备方法制得的,为自支撑电极材料,纳米管直径为40-60nm,长度为2-5um,纳米晶Co3O4颗粒均匀,直径为3.5-4nm;比电容达2324.6F·g-1,形貌为空心玉米棒状。
7.将权利要求6所述的空心玉米状Co3O4@NiCo2O4/氮掺杂石墨烯柔性电极材料用于制备柔性超级电容器电极。
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