CN112133567A - 一种高度规则排列Mn掺杂Ni-MOF超薄纳米片阵列超级电容器电极材料的制备方法 - Google Patents
一种高度规则排列Mn掺杂Ni-MOF超薄纳米片阵列超级电容器电极材料的制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 28
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- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000006260 foam Substances 0.000 claims abstract description 7
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims abstract description 7
- 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 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 239000011737 fluorine Substances 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 10
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 claims description 10
- 238000012512 characterization method Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000011565 manganese chloride Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 230000001351 cycling effect Effects 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001069 Raman spectroscopy Methods 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
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- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 2
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种高度规则排列Mn掺杂Ni‑MOF超薄纳米片阵列超级电容器电极材料(Mn0.1‑Ni‑MOF/NF)的制备方法。以六水合硝酸镍为镍源,四水合氯化锰为锰源,采用氟化铵为氟源并和尿素共同调控前驱体溶液的pH值,泡沫镍为导电基底,采用水热法制备MnNi‑LDH/NF前驱,通过溶剂热法处理MnNi‑LDH/NF制备Mn0.1‑Ni‑MOF/NF,将其用于超级电容器自支撑电极材料,在6 M KOH电解质中电流密度为2 mA cm‑2表现出极高的面积比电容(16.2 F cm‑2),该性能远高于未掺杂的Ni‑MOF纳米片阵列材料。本发明充分利用了纳米阵列结构的高比表面积和多种金属间的协同作用,构建了一种面积比电容高、循环寿命长、成本低的新型储能材料。
Description
技术领域
本发明涉及金属掺杂和三维高度规则排列纳米阵列结构的材料制备和应用于超级电容器电极材料的方法,特别是涉及在泡沫镍(NF)上原位生长超薄纳米片阵列结构的MnNi-LDH/NF前驱,再通过溶剂热法处理制备Mn0.1-Ni-MOF/NF,以及该材料在电化学储能领域中的应用。仅采用简单,可控,经济的合成方法便可制备高性能超级电容器电极材料。
背景技术
即将到来的化石燃料枯竭和日益严重的环境问题推动了对高能量输出的绿色和可再生能源的探索(Chem. Soc. Rev.,2015, 44, 5148–5180)。然而,典型的清洁能源,例如太阳能,风能和潮汐能,实际上是断断续续的,需要高效的能量存储/转换系统才能进一步扩大规模(Nano Energy, 2018, 45, 420-431)。超级电容器(SC)储存的能量密度比传统的介电电容器高几个数量级并且具有长循环寿命,和工业二次电池相比可实现数十倍的功率密度(Science, 2014, 343, 1210-1211)。能量密度是另一个关键指标,对于用于规模化应用的现有SC来说,能量密度相对较低,需要制备高性能电极材料来实现该目标(ACS Nano, 2015, 9, 5310-5317; Energy Environ. Sci., 2016, 9, 1299-1307)。然而,提高超级电容器的能量密度需要设计满足优异的电化学性能,高的电导率和大的可与电解质接触的比表面积条件的超级电容器。因此,为了满足超级电容器的要求,设计和发展高电容,高化学稳定性的新型电极材料是迫切需求的。
金属有机框架(MOF)是一类新兴的有机-无机杂化超分子材料,具有独特的周期性多孔结构,为容纳电解质离子提供了丰富的开孔和通道,并为氧化还原反应提供了统一的金属中心,是具有发展前景的材料(Nat. Mater., 2017, 16, 220-224; Chem. Commun.,2018, 54, 10499-10502)。然而低电导率,随机取向和缺乏化学稳定性是将大多数MOF直接进行电化学应用的三个障碍(Chem, 2017, 2, 791–802; J. Mater. Chem. A, 2019, 7,3815-3827; Adv. Energy Mater., 2018, 8, 1702294)。将MOF作为前驱体来制备所需目标产品和多孔模板似乎是一种理想的解决方案,在之前已经有科研工作者进行了广泛的研究(Chem. Soc. Rev., 2017, 46, 2660-2677)。然而将MOF作为前驱体制备材料通常需要耗费大量能量,而且可能损害MOF周期性的多孔结构(J. Mater. Chem. A, 2019, 7,8771-8776)。2018年,Zheng的研究小组首先报道了用Co(OH)2纳米阵列制备垂直取向的CoNi-MOF,然后用作不对称超级电容器电极材料,测试其性能得到CoNi-MOF在2 A g-1处实现了1044 F g-1的高比电容(Adv. Energy Mater., 2018, 8, 1702294)。牺牲具有独特纳米结构的目标材料可能是探索MOF材料用于超级电容器的另一个更好的选择。层状双金属氢氧化物(LDHs)作为一种经典的金属氢氧化物,可以与可交换的正离子和层间电荷平衡阴离子分层和重新堆叠(J. Am. Chem. Soc., 2013, 135, 8452-8455; J. Mater. Chem. A, 2016, 4, 167-172)。将LDHs作为模板转变成MOF,保留LDHs的层状结构,从而获得具有高能量密度的卓越超级电容器性能的电极材料,但迄今为止尚未得到证明。因此,我们期望在导电基底上设计一个三维高度规则排列Mn掺杂的Ni-MOF纳米阵列结构作为高性能的赝电容器电极。
本发明的目的是提供一种三维高度规则排列Mn掺杂Ni-MOF纳米片阵列结构的简单,可控,经济的合成方法,并将其用作高性能的超级电容器电极材料。
本发明的基本构思是:以四水合氯化锰为锰源,六水合硝酸镍为镍源,采用氟化铵为氟源并和尿素共同调控前驱体溶液的pH值,泡沫镍为导电基底,采用水热法制备MnNi-LDH/NF前驱,再以四水合氯化锰和六水合硝酸镍为辅助络合剂,对苯二甲酸为有机配体,氮,氮二甲基甲酰胺(DMF)为有机溶剂,无水乙醇和去离子水分别作为弱配位体溶剂和强配位体溶剂调控金属中心和有机配体的配位形式,采用溶剂热法以MnNi-LDH/NF为前驱和模板制备三维高度规则排列Mn掺杂Ni-MOF纳米阵列结构,并将其用作超级电容器电极材料。
发明内容
本发明提出一种简单易控的水热法和溶剂热法以原位制备三维高度规则排列Mn掺杂Ni-MOF纳米片阵列结构,并将其作为高性能的超级电容器电极材料。
本发明主要解决的技术问题是克服一般电极材料所带来较大的接触电阻,繁琐的制备电极过程,小的可与电解质接触的比表面积,低的循环稳定性等缺陷,并且避免一般MOFs基材料由于取向度和导电性较差而导致的活性位点利用率不高和催化活性降低的缺点,将Mn掺杂Ni-MOF材料直接原位生长在导电基底上以制备三维高度规则排列纳米阵列结构的电极材料,利用其超薄纳米片结构和多种金属间的协同效应,作为超级电容器电极材料,显示出极高的电化学储能性质。具体来讲,本发明是以四水合氯化锰为锰源,六水合硝酸镍为镍源,锰镍摩尔比为1:9,采用氟化铵为氟源并和尿素共同调控前驱体溶液的pH值,泡沫镍为导电基底,采用水热法制备MnNi-LDH/NF前驱,再以四水合氯化锰和六水合硝酸镍为辅助络合剂,对苯二甲酸为有机配体,氮,氮二甲基甲酰胺(DMF)为有机溶剂,无水乙醇和去离子水分别作为弱配位体溶剂和强配位体溶剂调控金属中心和有机配体的配位形式,采用溶剂热法以MnNi-LDH/NF为前驱和模板制备三维纳米片阵列结构的Mn0.1-Ni-MOF/NF超级电容器电极材料,展现出高的面积比电容和优异的循环稳定性。
本发明具体工序步骤如下:
(1)备料:MnCl2 4H2O(0.45 mmol),Ni(NO3)2 6H2O(4.05 mmol),CO(NH2)2(20 mmol)和NH4F(8 mmol),溶解于80 mL超纯水中,搅拌均匀,取一片尺寸为4×6 cm2的泡沫镍(NF),用无水乙醇,5%稀盐酸和去离子水分别超声10 min对其进行预处理;
(2)水热反应:将步骤(1)中的溶液和处理好的NF移至100 mL聚四氟乙烯衬里不锈高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应6 h;
(3)洗涤干燥:待步骤(2)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70℃下干燥3 h,制得MnNi-LDH/NF前驱;
(4)备料:C8H4O4(3.5 mmol),Ni(NO3)2 6H2O(4.725 mmol),MnCl2 4H2O(0.525 mmol),溶解于70 mL DMF后,搅拌中滴加5 mL C2H5OH和5 mL H2O,一片步骤(3)所获得的MnNi-LDH/NF前驱;
(5)溶剂热反应:将步骤(4)中的溶液和步骤(3)所制备的MnNi-LDH/NF前驱移至100 mL聚四氟乙烯高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应12~13 h;
(6)洗涤干燥:待步骤(5)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,即可得到Mn0.1-Ni-MOF/NF;
(7)表征及测量:采用XRD,FT-IR,Raman Scattering,SEM,TEM和XPS等测试方法表征Mn0.1-Ni-MOF/NF材料的结构和微观形貌,并使用DH7000电化学工作站,表征Mn0.1-Ni-MOF/NF的面积比电容,倍率性能以及循环稳定性,评价结果见表一。
附图说明
本发明所需的制备装置简单,仅需聚四氟乙烯高压反应釜,烘箱即可;所涉及的原料来源广泛,价格低廉;操作步骤简单,制备周期短,直接通过水热反应和模板法转换即可得到所需的电极材料(图1,图2,图3,图4分别是Mn0.1-Ni-MOF/NF的XRD谱图,FT-IR谱图,Raman谱图,XPS谱图),如此设计的Mn-Ni-MOF具有超薄纳米片的三维阵列结构(图5和图6分别是Mn0.1-Ni-MOF/NF的SEM和TEM图),将其用作超级电容器自支撑电极材料,在6 M KOH电解质中表现出极高的面积比电容(16.2 F cm-2,图7和图8分别是Mn0.1-Ni-MOF/NF的循环伏安曲线和恒电流充放电曲线)和优异的循环稳定性(图9是Mn0.1-Ni-MOF/NF的循环稳定性曲线)。
本发明与现有技术及合成路线相比,具有如下的优点和有益效果:
1.Mn0.1-Ni-MOF/NF制备过程简单可控,反应条件温和,反应周期短;
2.原位合成的Mn-Ni-MOF纳米阵列表现出高度规则排列超薄纳米片结构,可避免引入其他额外添加剂,有效减小其接触电阻,简化工作电极的制备过程,以及具有大的可与电解质接触的比表面积,更强的缓和体积改变能力和更多的电活性位点等优点;
3.三维高度规则排列超薄纳米片结构的Mn0.1-Ni-MOF/NF超级电容器电极材料表现出极好的电化学储能性质,拥有高的面积比电容(16.2 F cm-2)和优异的循环稳定性。
具体实施方式
实例一
(1)备料:MnCl2 4H2O(0.45 mmol),Ni(NO3)2 6H2O(4.05 mmol),CO(NH2)2(20 mmol)和NH4F(8 mmol),溶解于80 mL超纯水中,搅拌均匀,取一片尺寸为4×6 cm2的泡沫镍(NF),用无水乙醇,5%稀盐酸和去离子水分别超声10 min对其进行预处理;
(2)水热反应:将步骤(1)中的溶液和处理好的NF移至100 mL聚四氟乙烯衬里不锈高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应6 h;
(3)洗涤干燥:待步骤(2)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,制得MnNi-LDH/NF前驱;
(4)备料:C8H4O4(3.5 mmol),Ni(NO3)2 6H2O(4.725 mmol),MnCl2 4H2O(0.525 mmol),溶解于70 mL DMF后,搅拌中滴加5 mL C2H5OH和5 mL H2O,一片步骤(3)所获得的MnNi-LDH/NF前驱;
(5)溶剂热反应:将步骤(4)中的溶液和步骤(3)所制备的MnNi-LDH/NF前驱移至100 mL聚四氟乙烯高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应12 h;
(6)洗涤干燥:待步骤(5)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,即可得到Mn0.1-Ni-MOF/NF;
(7)表征及测量:采用XRD,FT-IR,Raman Scattering,SEM,TEM和XPS等测试方法表征Mn0.1-Ni-MOF/NF材料的结构和微观形貌,并使用DH7000电化学工作站,表征Mn0.1-Ni-MOF/NF的面积比电容,倍率性能以及循环稳定性,评价结果见表一。
实例二
(1)备料:MnCl2 4H2O(0.225 mmol),Ni(NO3)2 6H2O(2.025 mmol),CO(NH2)2(10 mmol)和NH4F(4 mmol),溶解于40 mL超纯水中,搅拌均匀,取一片尺寸为2×3 cm2的泡沫镍(NF),用无水乙醇,5%稀盐酸和去离子水分别超声10 min对其进行预处理;
(2)水热反应:将步骤(1)中的溶液和处理好的NF移至50 mL聚四氟乙烯衬里不锈高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应6 h;
(3)洗涤干燥:待步骤(2)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,制得MnNi-LDH/NF前驱;
(4)备料:C8H4O4(1.75 mmol),Ni(NO3)2 6H2O(2.3625 mmol),MnCl2 4H2O(0.2625mmol),溶解于35 mL DMF后,搅拌中滴加2.5 mL C2H5OH和2.5 mL H2O,一片步骤(3)所获得的MnNi-LDH/NF前驱;
(5)溶剂热反应:将步骤(4)中的溶液和步骤(3)所制备的MnNi-LDH/NF前驱移至100 mL聚四氟乙烯高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应12 h;
(6)洗涤干燥:待步骤(5)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,即可得到Mn0.1-Ni-MOF/NF;
(7)表征及测量:采用XRD,FT-IR,Raman Scattering,SEM,TEM和XPS等测试方法表征Mn0.1-Ni-MOF/NF材料的结构和微观形貌,并使用DH7000电化学工作站,表征Mn0.1-Ni-MOF/NF的面积比电容,倍率性能以及循环稳定性,评价结果见表一。
实例三
(1)备料:MnCl2 4H2O(0.45 mmol),Ni(NO3)2 6H2O(4.05 mmol),CO(NH2)2(20 mmol)和NH4F(8 mmol),溶解于80 mL超纯水中,搅拌均匀,取一片尺寸为4×6 cm2的泡沫镍(NF),用无水乙醇,5%稀盐酸和去离子水分别超声10 min对其进行预处理;
(2)水热反应:将步骤(1)中的溶液和处理好的NF移至100 mL聚四氟乙烯衬里不锈高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应6 h;
(3)洗涤干燥:待步骤(2)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,制得MnNi-LDH/NF前驱;
(4)备料:C8H4O4(3.5 mmol),Ni(NO3)2 6H2O(4.725 mmol),MnCl2 4H2O(0.525 mmol),溶解于70 mL DMF后,搅拌中滴加5 mL C2H5OH和5 mL H2O,一片步骤(3)所获得的MnNi-LDH/NF前驱;
(5)溶剂热反应:将步骤(4)中的溶液和步骤(3)所制备的MnNi-LDH/NF前驱移至100 mL聚四氟乙烯高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应13 h;
(6)洗涤干燥:待步骤(5)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3h,即可得到Mn0.1-Ni-MOF/NF;
(7)表征及测量:采用XRD,FT-IR,Raman Scattering,SEM,TEM和XPS等测试方法表征Mn0.1-Ni-MOF/NF材料的结构和微观形貌,并使用DH7000电化学工作站,表征Mn0.1-Ni-MOF/NF的面积比电容,倍率性能以及循环稳定性,评价结果见表一。
表一 各实例Mn0.1-Ni-MOF/NF的储能性能评价
Claims (3)
1.一种基于在泡沫镍(NF)上原位合成高度规则排列Mn掺杂Ni-MOF超薄纳米片阵列的超级电容器电极材料的方法,其特征在于,以四水合氯化锰为锰源,六水合硝酸镍为镍源,锰镍摩尔比为1:9,氟化铵作为氟源并和尿素共同调控前驱体溶液的pH值,氟化铵和尿素的摩尔比为2:5,采用水热法合成MnNi-LDH/NF,再以四水合氯化锰和六水合硝酸镍为辅助络合剂,锰镍元素的摩尔比为1:9,对苯二甲酸为有机配体,氮,氮二甲基甲酰胺(DMF)为有机溶剂,无水乙醇和去离子水分别作为弱配位体溶剂和强配位体溶剂调控金属中心和有机配体的配位形式,无水乙醇和去离子水的摩尔比为1:1,采用溶剂热法以MnNi-LDH/NF为前驱和模板制备纳米片阵列结构的Mn0.1-Ni-MOF/NF超级电容器电极材料。
2.根据权利要求1所述Mn0.1-Ni-MOF/NF的制备方法,其特征在于包含以下工序和步骤:
(1) 备料:MnCl2 4H2O(0.45 mmol),Ni(NO3)2 6H2O(4.05 mmol),CO(NH2)2(20 mmol)和NH4F(8 mmol),溶解于80 mL超纯水中,搅拌均匀,取一片尺寸为4×6 cm2的泡沫镍(NF),用无水乙醇,5%稀盐酸和去离子水分别超声10 min对其进行预处理;
(2) 水热反应:将步骤(1)中的溶液和处理好的NF移至100 mL聚四氟乙烯衬里不锈高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应6 h;
(3) 洗涤干燥:待步骤(2)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3 h,制得MnNi-LDH/NF前驱;
(4) 备料:C8H4O4(3.5 mmol),Ni(NO3)2 6H2O(4.725 mmol),MnCl2 4H2O(0.525 mmol),溶解于70 mL DMF后,搅拌中滴加5 mL C2H5OH和5 mL H2O,一片步骤(3)所获得的MnNi-LDH/NF前驱;
(5) 溶剂热反应:将步骤(4)中的溶液和步骤(3)所制备的MnNi-LDH/NF前驱移至100mL聚四氟乙烯高压釜中,并密封高压釜,将其放置在烘箱中,于120 ℃下反应12~13 h;
(6) 洗涤干燥:待步骤(5)的反应完成后,放置聚四氟乙烯高压釜于空气中冷却至室温,取出被产物均匀覆盖的NF,用去离子水和乙醇多次洗涤后放置在烘箱中于70 ℃下干燥3 h,即可得到Mn0.1-Ni-MOF/NF;
(7) 表征及测量:采用XRD,FT-IR,Raman Scattering,SEM,TEM和XPS等测试方法表征Mn0.1-Ni-MOF/NF材料的结构和微观形貌,并使用DH7000电化学工作站,表征Mn0.1-Ni-MOF/NF的面积比电容,倍率性能以及循环稳定性。
3.根据权利要求2所述Mn0.1-Ni-MOF/NF电极材料的制备方法,其特征在于:电极材料具有高度规则排列超薄的纳米片阵列结构,且如此设计的三维纳米阵列结构用作超级电容器电极材料表现出在2 mA cm-2电流密度下16.2 F cm-2的面积比电容和优异的循环稳定性。
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