CN109671575A - 一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法 - Google Patents
一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法 Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- FLOGAHIUJLPRMR-UHFFFAOYSA-L [Co](O)O.[Mg] Chemical compound [Co](O)O.[Mg] FLOGAHIUJLPRMR-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- DRNBZUBTWDQKQA-UHFFFAOYSA-N [C].[Mn].[Co]=O Chemical compound [C].[Mn].[Co]=O DRNBZUBTWDQKQA-UHFFFAOYSA-N 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
本发明属于功能化多孔纳米材料领域,具体涉及一种氧化钴锰纳米花‑碳海绵柔性复合材料的制备方法;具体步骤为:取商用三聚氰胺海绵,然后用蒸馏水和无水乙醇清洗,干燥,然后在氮气或氩气氛围下,通过程升温煅烧三聚氰胺海绵,冷却后得到碳海绵;配制含有锰盐和钴盐的混合溶液,将碳海绵浸入混合溶液中,进行水热反应,反应结束后取出碳海绵,用蒸馏水清洗并烘干,得到锰钴氢氧化物前驱体‑碳海绵复合材料;进一步在氩气气氛下进行退火反应,得到氧化钴锰纳米花‑碳海绵柔性复合材料;本发明以柔性、多孔、自支撑的碳海绵为生长模板,成功解决了纳米材料易团聚的难题;并且得到的复合材料具有大量暴露的活性位点、丰富的孔隙和良好的导电性能。
Description
技术领域
本发明属于功能化多孔纳米材料领域,具体涉及一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法。
背景技术
近年来,随着化石能源储量的日益降低和环境问题的不断突出,人们对绿色可再生能源的需求急剧增加。近二十年,人们不断开发和利用太阳能、风能和潮汐能等清洁能源且已取得可见成效。然而,这些能源具有间歇不连续等特点,因此还需要开发高效、经济的能源存储与转换装置将清洁能源进行存储和转化。其中,超级电容器、燃料电池、锂离子电池被认为是目前最具发展前景的三种电化学能源存储与转换系统。而为了促进这类新能源技术的产业化,寻找绿色、低成本的非贵金属基电极材料是研究者们重点关注的方向。
最近,一类新型的储能材料——过渡金属氧化物因为他们在能源存储与转换应用中表现出的超凡潜力,如优异的电化学活性、低成本、环境友好等优点,而成为全世界研究者关注的焦点。同时,由不同过渡金属元素组成的双金属氧化物能通过两种金属的不同氧化态之间的氧化还原反应以及金属元素之间的协同作用而获得更为理想的比电容。在众多双金属氧化物材料中,一种新型的氧化钴锰(MnCo2O4)因为它良好的导电性和丰富的氧化还原价态而具有相对其单金属氧化物更高的赝电容性能和催化活性。尽管过渡金属氧化物具有诸多优势,但其低电导率、低比表面积和充放电过程中较大的体积膨胀等缺点都限制了它的应用。
进而,通过合理构建低维单元组装结构框架能有效提高活性材料的可接触表面积、电荷离子扩散传输速率和结构韧性,从而获得优越均衡的电容性能。此外,将这类双金属氧化物直接生长在柔性基底表面能避免传统电极制作过程中绝缘粘结剂的使用,不仅能最大限度提高活性电极的表面利用率,而且能有效降低电子传输阻抗,从而获得最佳比容和倍率性能。
碳海绵因具有三维网络结构、导电性好、价廉质轻、耐腐蚀、机械强度高等优点非常适合用于柔性电极基底材料。进一步的在碳海绵多孔骨架上构筑具有电化学活性的纳米材料多级结构,可望制备出具有优异电化学性能和力学性能的碳海绵复合材料,这类复合多孔材料在能源存储领域具有广泛的应用价值。
发明内容
针对现有技术的不足,本发明旨在解决上述问题之一;本发明提供一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法。本发明利用高温煅烧法制备的碳海绵为导电、自支撑模板,通过溶剂热法及退火法合成氧化钴锰纳米花-碳海绵柔性复合材料。
为了实现以上目的,本发明的具体步骤如下:
(1)取商用三聚氰胺海绵,然后用蒸馏水和无水乙醇清洗,干燥后备用;
(2)在氮气或氩气氛围下,通过程序升温煅烧步骤(1)得到的三聚氰胺海绵,进行碳化处理,冷却后得到碳海绵;
(3)配制一定浓度的锰盐和钴盐的混合溶液;将步骤(2)中得到的碳海绵浸入混合溶液中,进行水热反应,反应结束后取出碳海绵,用蒸馏水清洗并烘干,得到锰钴氢氧化物前驱体-碳海绵复合材料;在氩气气氛下进行退火反应,得到氧化钴锰纳米花-碳海绵柔性复合材料。
优选的,步骤(1)中所述三聚氰胺海绵的尺寸为5cm×2cm×0.5cm。
优选的,步骤(2)中所述程序升温煅烧的具体参数为:升温速率2~5℃/min,温度700~900℃,时间0.5~3h。
优选的,步骤(3)中所述的锰盐为乙酸锰(Mn(CH2COOH)2),所述的钴盐为乙酸钴(Co(CH2COOH)2),所述混合溶液的溶剂为乙二醇。
优选的,步骤(3)中所述混合溶液中铁盐摩尔浓度为10~60mM。
优选的,步骤(3)中所述混合溶液中钴盐的摩尔浓度20~120mM。
优选的,步骤(3)中所述水热反应的温度为140~200℃,反应时间为6~12h。
优选的,步骤(3)中所述所述退火处理的参数为:升温速率为1~5℃/min,温度为350~450℃,时间为1~3h。
本发明的有益效果:
(1)本发明制备过程简单,易于操作,安全环保,所用的试剂均不会对人体和环境造成不良影响。
(2)本发明设计思路巧妙,以柔性、多孔、自支撑的碳海绵为生长模板,成功解决了纳米材料易团聚的难题;并且本发明选择碳海绵基底还可以增强复合材料的导电性。
(3)本发明所制备的氧化钴锰纳米花-碳海绵柔性复合材料具有大量暴露的活性位点、丰富的孔隙和良好的导电性能,可作为电化学催化剂、超级电容器电极材料以及锂离子电池等新能源器件的电极材料。
附图说明
图1是实施例1制备的煅烧后碳海绵骨架的电镜图。
图2是实施例1制备的氧化钴锰-碳海绵柔性复合材料的电镜图;其中A为10μm的电镜图片;B为1μm的电镜图片。
图3是实施例2制备的氧化钴锰-碳海绵柔性复合材料的电镜图;其中A和B分别为不同位置拍摄的电镜图片。
具体实施方式
下面结合具体实例,进一步阐述本发明,应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。但是本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换;而一切不脱离本发明的精神和范围的技术方案及其改进,其均应涵盖在本发明的权利要求范围内。
实施例1:
(1)将商用三聚氰胺海绵分割成5cm×2cm×0.5cm的长条状,并用蒸馏水和无水乙醇清洗干净,随后干燥过夜;
(2)将干净的三聚氰胺海绵置于程序控温管式炉中,在氮气气氛下,以5℃/min的升温速率从25℃升温至500℃,并保持0.5h,自然冷却后得到碳海绵;
(3)以乙二醇为溶剂,加入乙酸锰和乙酸钴,得到混合溶液;其中混合溶液中乙酸锰浓度为10mM,乙酸钴浓度为20mM;加入碳海绵,转移至聚四氟乙烯内衬的反应釜中,在140℃条件下反应6h,经清洗、烘干,得到锰钴氧化物前驱体-碳海绵复合材料,放入管式炉中,在氩气气氛中,以1℃/min的升温速率升至350℃,并保持1h,最终得到低载量的氧化钴锰纳米花-碳海绵柔性复合材料。
实施例2:
(1)将商用三聚氰胺海绵分割成5cm×2cm×0.5cm的长条状,并用蒸馏水和无水乙醇清洗干净,随后干燥过夜;
(2)将干净的三聚氰胺海绵置于程序控温管式炉中,在氮气气氛下,以3℃/min的升温速率从25℃升温至800℃,并保持1.5h,自然冷却后得到碳海绵;
(3)以乙二醇为溶剂,加入乙酸锰和乙酸钴,得到混合溶液;其中混合溶液中乙酸锰浓度为40mM,乙酸钴浓度为60mM;加入碳海绵,转移至聚四氟乙烯内衬的反应釜中,在170℃条件下反应8h,经清洗、烘干,得到锰钴氧化物前驱体-碳海绵复合材料,放入管式炉中,在氩气气氛中,以3℃/min的升温速率升至400℃,并保持2h,最终得到中等载量的氧化钴锰纳米花-碳海绵柔性复合材料。
将得到的中等载量的氧化钴锰纳米花-碳海绵柔性复合材料直接作为超级电容器正极材料,以乙炔黑涂覆的泡沫镍作为负极材料,以5M浓度的KOH作为电解液,组装非对称超级电容器器件,并评估器件的电容性能。
实施例3:
(1)将商用三聚氰胺海绵分割成5cm×2cm×0.5cm的长条状,并用蒸馏水和无水乙醇清洗干净,随后干燥过夜;
(2)将干净的三聚氰胺海绵置于程序控温管式炉中,在氮气气氛下,以5℃/min的升温速率从25℃升温至900℃,并保持3h,自然冷却后得到碳海绵;
(3)以乙二醇为溶剂,加入乙酸锰和乙酸钴,得到混合溶液;其中混合溶液中乙酸锰浓度为60mM,乙酸钴浓度为120mM;加入碳海绵,转移至聚四氟乙烯内衬的反应釜中,在200℃条件下反应12h,经清洗、烘干,得到锰钴氧化物前驱体-碳海绵复合材料,放入管式炉中,在氩气气氛中,以5℃/min的升温速率升至450℃,并保持3h,最终得到高载量的氧化钴锰纳米花-碳海绵柔性复合材料。
使用场发射扫描电子显微镜(FESEM)来表征本发明所获得的氧化钴锰纳米花-碳海绵柔性复合材料的形貌,其结果如下;
图1是实施例1制备的煅烧后碳海绵骨架的电镜图;通过图1可以看出高温煅烧后的海绵,依然保持着原有的三维网络型骨架。
图2是实施例1制备的氧化钴锰-碳海绵柔性复合材料的电镜图;通过图2可以看出水热反应中锰盐的浓度为10mM时,氧化钴锰在碳海绵骨架上呈现出规整的花状形貌,并均匀分布在碳海绵三维骨架上。
图3是实施例2制备的氧化钴锰-碳海绵柔性复合材料的电镜图;通过图3可以看出随着水热反应中锰盐和钴盐的浓度逐渐增大时,氧化钴锰在碳海绵上的生长呈现出逐渐密集的趋势;当锰盐浓度为40mM时,氧化钴锰会出现团聚形态,但依旧保持着花状。
本发明所制备的氧化钴锰纳米花-碳海绵柔性复合材料具有大量暴露的活性位点、丰富的孔隙和良好的导电性能,可作为电化学催化剂、超级电容器电极材料以及锂离子电池等新能源器件的电极材料。
Claims (7)
1.一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于具体步骤如下:
(1)取商用三聚氰胺海绵,然后用蒸馏水和无水乙醇清洗,干燥后备用;
(2)在氮气或氩气氛围下,通过程序升温煅烧步骤(1)得到的三聚氰胺海绵,进行碳化处理,冷却后得到碳海绵;
(3)配制一定浓度的锰盐和钴盐的混合溶液;将步骤(2)中得到的碳海绵浸入混合溶液中,进行水热反应,反应结束后取出碳海绵,用蒸馏水清洗并烘干,得到锰钴氢氧化物前驱体-碳海绵复合材料;在氩气气氛下进行退火反应,得到氧化钴锰纳米花-碳海绵柔性复合材料。
2.根据权利要求1所述的一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于,步骤(2)中所述程序升温煅烧的具体参数为:升温速率2~5 ℃/min,温度700~900℃,时间0.5~3 h。
3.根据权利要求1所述的一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于,步骤(3)所述混合溶液中铁盐摩尔浓度为10~60 mM;所述混合溶液中钴盐的摩尔浓度20~120 mM。
4.根据权利要求1或3所述的一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于,所述的锰盐为乙酸锰;所述的钴盐为乙酸钴。
5.根据权利要求1所述的一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于,优选的,步骤(3)中所述水热反应的温度为140~200℃,反应时间为6~12 h。
6.根据权利要求1所述的一种氧化钴锰纳米花-碳海绵柔性复合材料的制备方法,其特征在于,步骤(3)中所述所述退火处理的参数为:升温速率为1~5℃/min,温度为350~450℃,时间为1~3 h。
7.根据权利要求1所述的制备方法制备的氧化钴锰纳米花-碳海绵柔性复合材料应用于超级电容器的电极材料。
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