WO2015169104A1 - Sandwich-like manganese dioxide/polyaniline composite material and preparation method therefor - Google Patents
Sandwich-like manganese dioxide/polyaniline composite material and preparation method therefor Download PDFInfo
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- WO2015169104A1 WO2015169104A1 PCT/CN2015/070020 CN2015070020W WO2015169104A1 WO 2015169104 A1 WO2015169104 A1 WO 2015169104A1 CN 2015070020 W CN2015070020 W CN 2015070020W WO 2015169104 A1 WO2015169104 A1 WO 2015169104A1
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- manganese dioxide
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- potassium permanganate
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000008367 deionised water Substances 0.000 abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
- 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
-
- 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
Definitions
- the invention belongs to the field of new energy materials, and particularly relates to a sandwich-type manganese dioxide/polyaniline composite material and a preparation method thereof.
- supercapacitor As a new type of energy storage component, supercapacitor has many advantages such as high charge and discharge efficiency, long cycle life and no pollution in green. It has broad application prospects in mobile communication, electric vehicles, aerospace and other fields. Since it was proposed, it has received world attention. Supercapacitors are divided into electric double layer capacitors and Faraday tantalum capacitors according to the energy storage mechanism.
- the main electrode materials are carbon materials, transition metals and their oxides, conductive polymers and composite materials.
- Manganese dioxide is an ideal material for supercapacitor electrodes because of its high theoretical specific capacitance and energy density, and its abundant reserves in nature.
- problems to be solved in manganese dioxide (1) the easy agglomeration of manganese dioxide particles leads to a much smaller actual capacity than the theoretical capacity; (2) the electronic conductivity of manganese dioxide is lower than that of the other two materials, resulting in The internal resistance of the capacitor is too large, it is easy to generate heat, and the capacitance decays too fast. Therefore, it is a hot spot to prepare composite materials with high specific surface and high conductivity by compounding with other materials. Under acidic conditions, doped polymerized polyaniline has a high electrical conductivity and is the best choice for manganese dioxide composite.
- the object of the present invention is to provide a high-performance sandwich manganese dioxide/polyaniline composite material and a preparation method thereof, and the manganese dioxide sheet and the polyaniline are alternately stacked to form a sandwich manganese dioxide/polyaniline composite material.
- the polyaniline formed by doping polymerization greatly improves the electrical conductivity of the composite.
- the polyaniline layer effectively inhibits the agglomeration of the manganese dioxide sheet and fully exerts the high specific capacitance of manganese dioxide.
- the present invention adopts the following technical solutions:
- a method for preparing a sandwich-type manganese dioxide/polyaniline composite material wherein an organic solution of aniline is used as an organic phase, and an acidic aqueous solution of potassium permanganate is used as an inorganic phase, and an organic-inorganic interface reaction is used to react at a low temperature for a period of time.
- An alternate layer of manganese dioxide/polyaniline composite was prepared by suction filtration, washing and drying.
- a method for preparing a sandwich-type manganese dioxide/polyaniline composite material comprises dissolving aniline in an organic solvent to obtain an aniline organic solution, and dissolving potassium permanganate in deionized water to obtain an aqueous potassium permanganate solution,
- the solution is pretreated at a low temperature, and the pH of the potassium permanganate aqueous solution is adjusted to 1 to 4; the potassium permanganate aqueous solution is introduced to the surface of the aniline organic solution to form a two-phase interface, and the reaction is carried out at 0-4 ° C. 48 hours; the product was filtered, washed and dried to obtain a sandwich manganese dioxide/polyaniline composite.
- the organic solvent is one or more of carbon tetrachloride, toluene, and dichlorotoluene.
- the volume ratio of aniline to organic solvent in the organic solution of aniline is 1-10:100.
- the concentration of the potassium permanganate aqueous solution is 0.001 to 0.01 mg/mL.
- the low temperature pretreatment is to seal the solution and place it at 0 to 5 ° C for 30 to 50 minutes.
- sandwich-type manganese dioxide/polyaniline composite material prepared by the preparation method as described above is specifically used as an electrode material of a supercapacitor.
- the polyaniline formed by doping polymerization has good electrical conductivity
- the interlayer-type manganese dioxide/polyaniline composite material is prepared by the organic-inorganic interfacial reaction, which effectively inhibits the circulation of manganese dioxide. Agglomeration during charging and discharging;
- the composite material Due to the synergistic effect between the layers of manganese dioxide and polyaniline, the composite material has high electrical conductivity and high specific capacitance, which lays a foundation for its application in supercapacitor electrode materials.
- Example 1 is a TEM image of a sandwich-type manganese dioxide/polyaniline composite material obtained in Example 1;
- Example 2 is an FT-IR diagram of the sandwiched manganese dioxide/polyaniline composite material obtained in Example 1;
- Example 3 is a charge-discharge diagram of the sandwich-type manganese dioxide/polyaniline composite material obtained in Example 1.
- a method for preparing a sandwich-type manganese dioxide/polyaniline composite material the specific steps are as follows:
- aniline is extracted (purified by two distillations), dissolved in 100 mL of an organic solvent, and formulated into an organic solution of a corresponding concentration;
- Example 1 The sandwiched manganese dioxide/polyaniline composite prepared in Example 1 was characterized by transmission electron microscopy scanning, Fourier-infrared spectroscopy and charge-discharge characterization.
- Figure 1 shows that the amorphous polyaniline molecular chain is along the dioxide. manganese layer growth, and thus build a structural sandwich in;
- FIG. 1 shows that the amorphous polyaniline molecular chain is along the dioxide.
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Abstract
The present invention relaters to a sandwich-like manganese dioxide/polyaniline composite material and a preparation method therefor, belonging to the field of novel energy materials. Aniline is dissolved in an organic solvent to obtain an aniline organic solution; potassium permanganate is dissolved in deionized water to obtain an aqueous potassium permanganate solution, and the pH value of the aqueous potassium permanganate solution is controlled; a low-temperature pretreatment is performed on the two solutions respectively; the aqueous potassium permanganate solution is introduced to the surface of the aniline organic solution, forming a two-phase interface and is reacted for 12-48 hours under conditions of 0-4°C; and the product is filtered, washed and dried to obtain the sandwich-like manganese dioxide/polyaniline composite material. Under acidic conditions, oxidized and polymerized polyaniline has a very high conductivity, and at the same time, the polyaniline is positioned between manganese dioxide slice layers, so that the agglomeration thereof is effectively prevented, and the performances, such as the high specific capacitance, are greatly developed, laying the foundation for applications thereof in electrode materials for super-capacitors.
Description
本发明属于新型能源材料领域，具体涉及一种夹层状二氧化锰/聚苯胺复合材料及其制备方法。The invention belongs to the field of new energy materials, and particularly relates to a sandwich-type manganese dioxide/polyaniline composite material and a preparation method thereof.
超级电容器作为一种新型的能源存储元件，具有充放电效率高、循环使用寿命长、绿色无污染等众多优点，在移动通讯、电动汽车、航空航天等领域具有广阔的应用前景。自从其被提出来，就受到世界的关注。超级电容器按照储能机理分为双电层电容器和法拉第赝电容器，主要的电极材料有碳材料、过渡金属及其氧化物、导电聚合物以及复合材料。As a new type of energy storage component, supercapacitor has many advantages such as high charge and discharge efficiency, long cycle life and no pollution in green. It has broad application prospects in mobile communication, electric vehicles, aerospace and other fields. Since it was proposed, it has received world attention. Supercapacitors are divided into electric double layer capacitors and Faraday tantalum capacitors according to the energy storage mechanism. The main electrode materials are carbon materials, transition metals and their oxides, conductive polymers and composite materials.
二氧化锰因具有高理论比电容和能量密度，同时在自然界具有丰富的储量，是用作超级电容器电极的理想材料。然而，二氧化锰存在许多待解决的问题：(1)二氧化锰颗粒易团聚导致实际容量远小于理论容量；(2)相对于其他两种材料，二氧化锰的电子电导率较低，导致电容器内阻过大，容易发热，同时电容衰减过快。因此，通过与其他材复合料制备高比表面、高电导率的复合材料是当今的热点。在酸性条件下，掺杂聚合的聚苯胺具有很高电导率，是二氧化锰复合的最佳选择。Manganese dioxide is an ideal material for supercapacitor electrodes because of its high theoretical specific capacitance and energy density, and its abundant reserves in nature. However, there are many problems to be solved in manganese dioxide: (1) the easy agglomeration of manganese dioxide particles leads to a much smaller actual capacity than the theoretical capacity; (2) the electronic conductivity of manganese dioxide is lower than that of the other two materials, resulting in The internal resistance of the capacitor is too large, it is easy to generate heat, and the capacitance decays too fast. Therefore, it is a hot spot to prepare composite materials with high specific surface and high conductivity by compounding with other materials. Under acidic conditions, doped polymerized polyaniline has a high electrical conductivity and is the best choice for manganese dioxide composite.
发明内容Summary of the invention
本发明的目的在于提供一种高性能的夹层状二氧化锰/聚苯胺复合材料及其制备方法，将二氧化锰片层与聚苯胺交替叠加制成夹层状二氧化锰/聚苯胺复合材料，在酸性条件下，掺杂聚合生成的聚苯胺大大提高了复合材料的导电性，同时聚苯胺层有效的抑制了二氧化锰片层的团聚，充分发挥了二氧化锰的高比电容等性能。The object of the present invention is to provide a high-performance sandwich manganese dioxide/polyaniline composite material and a preparation method thereof, and the manganese dioxide sheet and the polyaniline are alternately stacked to form a sandwich manganese dioxide/polyaniline composite material. Under acidic conditions, the polyaniline formed by doping polymerization greatly improves the electrical conductivity of the composite. At the same time, the polyaniline layer effectively inhibits the agglomeration of the manganese dioxide sheet and fully exerts the high specific capacitance of manganese dioxide.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种夹层状二氧化锰/聚苯胺复合材料的制备方法，以苯胺有机溶液作为有机相，高锰酸钾酸性水溶液作为无机相，采用有机-无机界面反应，在低温条件下反应一段时间，最后抽滤、洗涤、干燥制备了层层交替的二氧化锰/聚苯胺复合材料。A method for preparing a sandwich-type manganese dioxide/polyaniline composite material, wherein an organic solution of aniline is used as an organic phase, and an acidic aqueous solution of potassium permanganate is used as an inorganic phase, and an organic-inorganic interface reaction is used to react at a low temperature for a period of time. An alternate layer of manganese dioxide/polyaniline composite was prepared by suction filtration, washing and drying.
具体地，一种夹层状二氧化锰/聚苯胺复合材料的制备方法，将苯胺溶解在有机溶剂中得到苯胺有机溶液，将高锰酸钾溶解在去离子水中得到高锰酸钾水溶液，对两种溶液分别进行低温预处理，并调节高锰酸钾水溶液的pH值为1～4；将高锰酸钾水溶液引入至苯胺有机溶液表面，形成两相界面，0-4℃条件下反应12-48小时；产物经过滤、洗涤、干燥制得夹层状二氧化锰/聚苯胺复合材料。
Specifically, a method for preparing a sandwich-type manganese dioxide/polyaniline composite material comprises dissolving aniline in an organic solvent to obtain an aniline organic solution, and dissolving potassium permanganate in deionized water to obtain an aqueous potassium permanganate solution, The solution is pretreated at a low temperature, and the pH of the potassium permanganate aqueous solution is adjusted to 1 to 4; the potassium permanganate aqueous solution is introduced to the surface of the aniline organic solution to form a two-phase interface, and the reaction is carried out at 0-4 ° C. 48 hours; the product was filtered, washed and dried to obtain a sandwich manganese dioxide/polyaniline composite.
所述的有机溶剂为四氯化碳、甲苯、二氯甲苯中的一种或多种。The organic solvent is one or more of carbon tetrachloride, toluene, and dichlorotoluene.
苯胺有机溶液中苯胺与有机溶剂的体积比为：1-10:100。The volume ratio of aniline to organic solvent in the organic solution of aniline is 1-10:100.
高锰酸钾水溶液的浓度为0.001～0.01mg/mL。The concentration of the potassium permanganate aqueous solution is 0.001 to 0.01 mg/mL.
所述的低温预处理为将溶液密封、放置于0～5℃低温处理30～50min。The low temperature pretreatment is to seal the solution and place it at 0 to 5 ° C for 30 to 50 minutes.
如上所述的制备方法制得的夹层状二氧化锰/聚苯胺复合材料的应用，具体为用作超级电容器的电极材料。The use of the sandwich-type manganese dioxide/polyaniline composite material prepared by the preparation method as described above is specifically used as an electrode material of a supercapacitor.
本发明的有益效果在于：The beneficial effects of the invention are:
(1)在酸性条件下，掺杂聚合生成的聚苯胺具有良好的电导率，同时利用有机-无机界面反应，制备夹层状的二氧化锰/聚苯胺复合材料，有效抑制了二氧化锰在循环充放电过程中的团聚现象；(1) Under acidic conditions, the polyaniline formed by doping polymerization has good electrical conductivity, and the interlayer-type manganese dioxide/polyaniline composite material is prepared by the organic-inorganic interfacial reaction, which effectively inhibits the circulation of manganese dioxide. Agglomeration during charging and discharging;
(2)由于二氧化锰和聚苯胺层层之间的协同作用，复合材料具有高电导率、高比电容等性能，为其在超级电容器电极材料的应用奠定了基础。(2) Due to the synergistic effect between the layers of manganese dioxide and polyaniline, the composite material has high electrical conductivity and high specific capacitance, which lays a foundation for its application in supercapacitor electrode materials.
图1为实例1制得的夹层状的二氧化锰/聚苯胺复合材料的TEM图；1 is a TEM image of a sandwich-type manganese dioxide/polyaniline composite material obtained in Example 1;
图2为实例1制得的夹层状的二氧化锰/聚苯胺复合材料的FT-IR图；2 is an FT-IR diagram of the sandwiched manganese dioxide/polyaniline composite material obtained in Example 1;
图3为实例1制得的夹层状的二氧化锰/聚苯胺复合材料的充-放电图。3 is a charge-discharge diagram of the sandwich-type manganese dioxide/polyaniline composite material obtained in Example 1.
本发明用下列实施例来进一步说明本发明，但本发明的保护范围并不限于下列实施例。The invention is further illustrated by the following examples, but the scope of the invention is not limited to the following examples.
一种夹层状二氧化锰/聚苯胺复合材料的制备方法，具体步骤为：A method for preparing a sandwich-type manganese dioxide/polyaniline composite material, the specific steps are as follows:
(1)量取苯胺(经过2次蒸馏提纯)，溶于100mL有机溶剂中，配制成相应浓度的有机溶液；(1) aniline is extracted (purified by two distillations), dissolved in 100 mL of an organic solvent, and formulated into an organic solution of a corresponding concentration;
(2)称量高锰酸钾固体，溶于100mL去离子水中，并用硫酸调节pH，配制成相应浓度的水溶液；(2) Weighing potassium permanganate solid, dissolving in 100 mL of deionized water, and adjusting the pH with sulfuric acid to prepare an aqueous solution of corresponding concentration;
(3)将上述配制好的溶液放置于低温条件下(0～5℃)预处理30～50min，然后将高锰酸钾溶液缓慢引入至苯胺有机溶液中，形成稳定的有机-无机溶液后，置于0-4℃条件下，反应12-48h；(3) pre-treating the prepared solution under low temperature conditions (0 to 5 ° C) for 30 to 50 minutes, and then slowly introducing the potassium permanganate solution into the organic solution of aniline to form a stable organic-inorganic solution. Set at 0-4 ° C, the reaction is 12-48h;
(4)将上述溶液抽滤、洗涤、干燥，得到最终产物。(4) The above solution was suction filtered, washed, and dried to obtain a final product.
实施例1Example 1
(1)量取1mL苯胺单体，溶于100mL的四氯化碳有机溶剂中，得到苯胺有机溶液；(1) Measure 1 mL of aniline monomer, dissolved in 100 mL of carbon tetrachloride organic solvent to obtain an aniline organic solution;
(2)称量0.1mg高锰酸钾固体，溶于100mL的去离子水中，得到0.001mg/mL的高锰
酸钾水溶液，用浓硫酸调节pH值为3；(2) Weigh 0.1 mg of potassium permanganate solid and dissolve it in 100 mL of deionized water to obtain 0.001 mg/mL of high manganese.
An aqueous potassium acid solution, adjusted to a pH of 3 with concentrated sulfuric acid;
(3)将上述溶液置于0～5℃条件下预处理30min，然后将高锰酸钾水溶液引入至苯胺有机溶液表面，形成有机-无机溶液；再置于0℃条件下，反应24h；(3) The above solution is pretreated at 0 to 5 ° C for 30 min, then the potassium permanganate aqueous solution is introduced to the surface of the aniline organic solution to form an organic-inorganic solution; and then placed at 0 ° C for 24 h;
(4)将上述得到的溶液抽滤、洗涤、干燥，得到最终产物，即为夹层状二氧化锰/聚苯胺复合材料。(4) The solution obtained above is suction filtered, washed, and dried to obtain a final product, which is a sandwich-type manganese dioxide/polyaniline composite material.
实施例2Example 2
(1)量取2mL苯胺单体，溶于100mL的四氯化碳有机溶剂中，得到苯胺有机溶液；(1) Quantitatively taking 2 mL of aniline monomer, and dissolving in 100 mL of an organic solvent of carbon tetrachloride to obtain an organic solution of aniline;
(2)称量1mg高锰酸钾固体，溶于100mL的去离子水中，得到0.01mg/mL的高锰酸钾水溶液，用浓硫酸调节pH值为3；(2) Weigh 1mg potassium permanganate solid, dissolved in 100mL of deionized water to obtain 0.01mg / mL potassium permanganate aqueous solution, adjusted to pH 3 with concentrated sulfuric acid;
(3)将上述溶液都置于0～5℃条件下预处理40min，然后将高锰酸钾水溶液引入苯胺有机溶液表面，形成有机-无机溶液；再置于4℃条件下，反应48h；(3) The above solution was pretreated at 0 to 5 ° C for 40 min, then the potassium permanganate aqueous solution was introduced into the surface of the aniline organic solution to form an organic-inorganic solution; and then placed at 4 ° C for 48 h;
(4)将上述得到的溶液抽滤、洗涤、干燥，得到最终产物，即为夹层状二氧化锰/聚苯胺复合材料。(4) The solution obtained above is suction filtered, washed, and dried to obtain a final product, which is a sandwich-type manganese dioxide/polyaniline composite material.
实施例3Example 3
(1)量取10mL苯胺单体，溶于100mL的四氯化碳有机溶剂中，得到苯胺有机溶液；(1) Measure 10 mL of aniline monomer, dissolved in 100 mL of carbon tetrachloride organic solvent to obtain an aniline organic solution;
(2)称量0.2mg高锰酸钾固体估计，溶解于100mL的去离子水中，得到0.002mg/mL的高锰酸钾水溶液，用浓硫酸调节pH值为3；(2) Weighing 0.2 mg of potassium permanganate solid, estimated to dissolve in 100 mL of deionized water to obtain 0.002 mg / mL potassium permanganate aqueous solution, adjusted to pH 3 with concentrated sulfuric acid;
(3)将上述溶液都置于0～5℃条件下预处理30min，然后将高锰酸钾水溶液引入苯胺有机溶液表面，形成有机-无机溶液；再置于2℃条件下，反应12h；(3) The above solution was pretreated at 0 to 5 ° C for 30 min, then the potassium permanganate aqueous solution was introduced into the surface of the aniline organic solution to form an organic-inorganic solution; and then placed at 2 ° C for 12 h;
(4)将上述得到的溶液抽滤、洗涤、干燥，得到最终产物，即为夹层状二氧化锰/聚苯胺复合材料。(4) The solution obtained above is suction filtered, washed, and dried to obtain a final product, which is a sandwich-type manganese dioxide/polyaniline composite material.
实施例4Example 4
(1)量取1mL苯胺单体，溶于100mL的四氯化碳有机溶剂中，得到苯胺有机溶液；(1) Measure 1 mL of aniline monomer, dissolved in 100 mL of carbon tetrachloride organic solvent to obtain an aniline organic solution;
(2)称量0.5mg高锰酸钾固体，溶于100mL的去离子水中，得到0.005mg/mL的高锰酸钾水溶液，用浓硫酸调节pH值为1；(2) Weigh 0.5mg potassium permanganate solid, dissolved in 100mL of deionized water, to obtain 0.005mg / mL potassium permanganate aqueous solution, adjust the pH value with concentrated sulfuric acid 1;
(3)将上述溶液都置于0～5℃条件下预处理30min，然后将高锰酸钾水溶液引入苯胺有机溶液表面，形成有机-无机溶液；再置于0℃条件下，反应24h；(3) The above solution is pretreated at 0 to 5 ° C for 30 min, then the potassium permanganate aqueous solution is introduced into the surface of the aniline organic solution to form an organic-inorganic solution; and then placed at 0 ° C for 24 h;
(4)将上述得到的溶液抽滤、洗涤、干燥，得到最终产物，即为夹层状二氧化锰/聚苯胺复合材料。(4) The solution obtained above is suction filtered, washed, and dried to obtain a final product, which is a sandwich-type manganese dioxide/polyaniline composite material.
对实施例1制得的夹层状二氧化锰/聚苯胺复合材料进行透射电镜扫描表征、傅里叶-红
外光谱表征、充-放电表征；图1表明无定型的聚苯胺分子链沿着二氧化锰层生长，进而构筑了夹层中的结构；图2中524cm-1为二氧化锰中Mn-O-Mn吸收峰，1050cm-1为聚苯胺中的C-H伸缩振动吸收峰，1412cm-1和1635cm-1分别为苯环和醌型环的振动吸收峰，1635cm-1为聚苯胺中的C＝N振动吸收峰，3425cm-1则为N-H和水分子中的-OH的吸收峰共同构成的，表明生成了二氧化锰/聚苯胺复合物；从图3中可以看出，以夹层状二氧化锰/聚苯胺复合材料制备的电极具有良好的充放电性能，在0.1A/g的电流密度下，电容可达到192.8F/g。The sandwiched manganese dioxide/polyaniline composite prepared in Example 1 was characterized by transmission electron microscopy scanning, Fourier-infrared spectroscopy and charge-discharge characterization. Figure 1 shows that the amorphous polyaniline molecular chain is along the dioxide. manganese layer growth, and thus build a structural sandwich in; FIG. 2 524cm -1 manganese dioxide absorption peak Mn-O-Mn, 1050cm -1 polyaniline is CH stretching vibration absorption peaks, 1412cm -1 and 1635cm -1 is the vibration absorption peak of the benzene ring and the fluorene ring, respectively, 1635 cm -1 is the C=N vibration absorption peak in polyaniline, and 3425 cm -1 is composed of the absorption peak of NH and the -OH in the water molecule. It is indicated that a manganese dioxide/polyaniline composite is formed; as can be seen from Fig. 3, the electrode prepared by sandwiched manganese dioxide/polyaniline composite has good charge and discharge performance at a current density of 0.1 A/g. The capacitance can reach 192.8F/g.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should fall within the scope of the present invention.
Claims (5)
- 一种夹层状二氧化锰/聚苯胺复合材料的制备方法，其特征在于：先对苯胺有机溶液、高锰酸钾水溶液进行低温预处理，并调节高锰酸钾水溶液的pH值为1～4；然后将高锰酸钾水溶液引入至苯胺有机溶液表面，形成两相界面，0-4℃条件下反应12-48小时；产物经过滤、洗涤、干燥制得夹层状二氧化锰/聚苯胺复合材料。The invention discloses a method for preparing a sandwich-type manganese dioxide/polyaniline composite material, which is characterized in that the aniline organic solution and the potassium permanganate aqueous solution are pretreated at a low temperature, and the pH of the potassium permanganate aqueous solution is adjusted to be 1 to 4 Then, the potassium permanganate aqueous solution is introduced into the surface of the aniline organic solution to form a two-phase interface, and the reaction is carried out at 0-4 ° C for 12-48 hours; the product is filtered, washed and dried to obtain a sandwich-type manganese dioxide/polyaniline composite. material.
- 根据权利要求1所述的夹层状二氧化锰/聚苯胺复合材料的制备方法，其特征在于：苯胺有机溶液中苯胺与有机溶剂的体积比为：1-10:100。The method for preparing a sandwich type manganese dioxide/polyaniline composite material according to claim 1, wherein the volume ratio of aniline to the organic solvent in the aniline organic solution is 1-10:100.
- 根据权利要求1所述的夹层状二氧化锰/聚苯胺复合材料的制备方法，其特征在于：高锰酸钾水溶液的浓度为0.001～0.01mg/mL。The method for producing a sandwich type manganese dioxide/polyaniline composite material according to claim 1, wherein the concentration of the potassium permanganate aqueous solution is 0.001 to 0.01 mg/mL.
- 根据权利要求1所述的夹层状二氧化锰/聚苯胺复合材料的制备方法，其特征在于：所述的低温预处理为将溶液密封、放置于0～5℃处理30～50min。The method for preparing a sandwich type manganese dioxide/polyaniline composite material according to claim 1, wherein the low temperature pretreatment is to seal the solution and place it at 0 to 5 ° C for 30 to 50 minutes.
- 根据权利要求1所述的制备方法制得的夹层状二氧化锰/聚苯胺复合材料的应用，其特征在于：用作超级电容器的电极材料。 The use of a sandwich-type manganese dioxide/polyaniline composite material obtained by the production method according to claim 1, which is used as an electrode material of a supercapacitor.
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| CN105070514B (en) * | 2015-07-06 | 2017-10-20 | 常州大学 | Interface method prepares polyaniline/graphene/manganese dioxide composite material applied to ultracapacitor |
| US11565241B2 (en) * | 2016-09-12 | 2023-01-31 | Fuzhou University | Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material |
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