CN103474254B - 含有MnCo2O4.5的超级电容器电极材料的制备方法 - Google Patents
含有MnCo2O4.5的超级电容器电极材料的制备方法 Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 19
- 239000003990 capacitor Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 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
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Abstract
本发明提供的是一种含有MnCo2O4.5的超级电容器电极材料的制备方法。将3.5-4.5mmolCo(NO3)2·6H2O、9-11mmol?CO(NH2)2、4.0-4.5mL?Mn(NO3)2溶液溶解在30mL蒸馏水中,搅拌使其形成均匀溶液,将2cm×3cm的泡沫镍置于所述均匀溶液中,在87-92℃反应10-12h,自然冷却至室温,取出泡沫镍基体,用蒸馏水洗涤干净,60-70℃干燥12-14h,之后在280-320℃煅烧3-4h,得到泡沫镍载MnCo2O4.5纳米线电极材料。本发明的方法得到的MnCo2O4.5作为超级电容器的电极材料,不但原料储量丰富易得,价格低廉,而且超级电容性能高,大倍率性能号,循环性能稳定。
Description
技术领域
本发明涉及的是一种超级电容器的电极材料的制备方法。
背景技术
超级电容器是利用电极/溶液表面的电化学过程储存电荷的一种储能元件,也叫电化学电容器。根据储能机理不同可将超级电容器分为双电层电容器、法拉第准电容器和混合电容器。超级电容器正向高比功率和高比能量发展,以过渡金属氧化物和多孔炭分别为正负极的混合超级电容器是今后的重要发展方向。充放电时电化学反应能量转化过程和双电层能量贮存过程分别在两极同时等量进行。双电层电容允许大电流快速充放电,而法拉第准电容可通过快速可逆的法拉第反应来实现大能量存储,两者结合起来,综合了超级电容器和电池两种储能机理,有望实现两种储能方式性能互补,获得高能量密度、高功率密度、长循环寿命、高工作电压等性能。
影响超级电容器发展的关键因素有电极材料、与电极材料匹配的电解液和电极的制备技术等,其中电极材料是制约超级电容器的关键。人们对电极材料的研究主要集中在多孔碳材料、导电聚合物材料及金属氧化物材料三大类。金属氧化物电极材料是通过在电极表面或体相中的二维或准二维空间,发生高度可逆的氧化还原反应,产生与电极充电电位有关的电容量,不仅可以像碳材料一样依靠双电层电容储能,还可以通过法拉第反应储能。目前的研究主要为Ru、Mn、Co和Ni等过渡金属氧化物,其中以RuO2的性能最好,但价格昂贵,限制了它的应用。具体可参见文献KotzR,CarlenM.Principlesandapplicationsofelectrochemicalcapacitors.ElectrochimActa,2000,45:2483-2498.以及GaoYinyi,ChenShuli,CaoDianxue,WangGuiling,YinJinling.ElectrochemicalcapacitanceofCo3O4nanowirearrayssupportedonnickelfoam.JournalofPowerSources,2010,195:1757–1760。
发明内容
本发明的目的在于提供一种价格低廉,能量密度高的含有MnCo2O4.5的超级电容器电极材料的制备方法。
本发明的目的是这样实现的:将3.5-4.5mmolCo(NO3)2·6H2O、9-11mmolCO(NH2)2、4.0-4.5mLMn(NO3)2溶液溶解在30mL蒸馏水中,搅拌使其形成均匀溶液,将2cm×3cm的泡沫镍置于所述均匀溶液中,在87-92℃反应10-12h,自然冷却至室温,取出泡沫镍基体,用蒸馏水洗涤干净,60-70℃干燥12-14h,之后在280-320℃煅烧3-4h,得到泡沫镍载MnCo2O4.5纳米线电极材料。
以本发明得到的泡沫镍载MnCo2O4.5为工作电极,对电极为铂电极,采用饱和甘汞电极(SCE)作为参比电极,以3~6mol·L-1的KOH为电解液,组装泡沫镍载MnCo2O4.5纳米线电极体系,在0~0.5V电压范围内进行充放电,即可获得超级电化学电容容量。
本发明的实质是采用氧化物超级电容器的电极结构,以MnCo2O4.5取代炭和RuO2等作为超级电容器的电极材料,在碱性电解液中进行充放电,构成超级电容器的电极,获得超级电化学电容容量。
本发明的优点在于这种三维立体结构的泡沫镍载MnCo2O4.5纳米阵列基体机械力学性能强,不使用粘结剂和导电剂;可以使活性物质充分与电解液接触,有效地增加了电荷的转移速度的传递。MnCo2O4.5比常见MnCo2O4的多0.5个O原子,即产生许多空位,导电性好,克服了其它过度金属氧化物导电性差的缺点。MnCo2O4.5为锰和钴的复合氧化物,即保持了锰氧化物的循环稳定性,有兼有钴氧化物的高比容量特性。利用MnCo2O4.5作为超级电容器的电极材料,不但原料储量丰富易得,价格低廉,而且超级电容性能高,大倍率性能号,循环性能稳定。
具体实施方式
下面举例对本发明做更详细的描述。
将4mmolCo(NO3)2·6H2O、10mmolCO(NH2)2、4mLMn(NO3)2溶液溶解在30mL蒸馏水中,搅拌使其形成均匀溶液,将其转移至40mL的反应釜中。剪取2cm×3cm的泡沫镍,将其斜靠在反应釜内部。将反应釜在90℃反应10h,取出反应釜,自然冷却至室温。取出泡沫镍基体,用蒸馏水洗涤干净,60℃干燥12h,之后将其在马弗炉中300℃煅烧4h,得到泡沫镍载MnCo2O4.5纳米线电极材料。
为了更好地说明本发明的效果,下面以应用实例加以说明。
应用实施例1
直接以泡沫镍载MnCo2O4.5为工作电极,对电极为铂电极,采用饱和甘汞电极(SCE)作为参比电极,以6mol·L-1的KOH为电解液,组装泡沫镍载MnCo2O4.5纳米线电极体系,在0~0.5V电压范围内进行充放电,在0~0.5V电压范围内,以1A·g-1的电流密度获得785F·g-1的容量。
应用实施例2
利用水热法制备MnCo2O4.5粉末,以MnCo2O4.5粉末作为超级电容器的电极材料、炭为导电极、聚四氟乙烯作为粘结剂、泡沫镍作为基体制备电极;以6mol·L-1的KOH作为电解液,铂片为对电级,采用饱和甘汞电极(SCE)作为参比电极,在0~0.5V电压范围内,以1A·g-1的电流密度获得527F·g-1的容量。
Claims (1)
1.一种含有MnCo2O4.5的超级电容器电极材料的制备方法,其特征是:将3.5-4.5mmolCo(NO3)2·6H2O、9-11mmolCO(NH2)2、4.0-4.5mLMn(NO3)2溶液溶解在30mL蒸馏水中,搅拌使其形成均匀溶液,将2cm×3cm的泡沫镍基体置于所述均匀溶液中,在87-92℃反应10-12h,自然冷却至室温,取出泡沫镍基体,用蒸馏水洗涤干净,60-70℃干燥12-14h,之后在280-320℃煅烧3-4h,得到泡沫镍载MnCo2O4.5纳米线电极材料。
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CN109119251B (zh) * | 2018-08-30 | 2020-04-24 | 中北大学 | 一种多孔MnCo2O4.5电极材料的制备方法 |
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CN112233912B (zh) * | 2020-09-21 | 2022-05-27 | 郑州大学 | 一种泡沫镍载MnCo2O4.5/MXene复合纳米材料的制备方法及应用 |
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