CN110734094B - Mn3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material and preparation method and application thereof - Google Patents
Mn3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides Mn3O4The functional N/P co-doped carbon sheet embedded 3D carbon foam composite material and the preparation method and application thereof are disclosed, wherein the preparation method comprises the following steps: step 1, completely dipping melamine foam in biomass proton salt (Chit)][H2PO4]And Mn (NO)3)2In the mixed solution of (1); in the mixed solution, the molar ratio [ Chit][H2PO4]:Mn(NO3)25-20: 1; step 2, drying the soaked melamine foam, then placing the melamine foam in a tubular furnace, heating the melamine foam to 700-1000 ℃ at a certain heating rate, carrying out pyrolysis for a period of time, then naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for a period of time to obtain the 3D carbon foam compositeA material. The method has the advantages of simple process, wide applicability, high efficiency and the like, and can be used for preparing the composite material with abundant 3D porous structures, high specific surface area, high specific capacitance and excellent mechanical properties.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to Mn3O4A 3D carbon foam composite material embedded with a functionalized N/P co-doped carbon sheet, and a preparation method and application of the composite material.
Technical Field
Doping with a dopant material/transition metal oxide (CO)3O4、MnO2、Mn3O4NiO and RuO2) The composite material has been widely used in the field of supercapacitors due to the excellent characteristics of abundant pore structure, excellent stability, large surface area, high specific capacitance, etc. Hetero atoms (N, S, O, B and P) replace carbon atoms in the carbon material skeleton, can adjust the properties of electrons and provide more active sites, and have important influence on the conductivity, wettability and pseudocapacitance of the electrode material of the supercapacitor. It was found that the multiple-dopant doping has a better synergistic effect on the electrochemical properties of the carbon material than the single-dopant doping. However, many of the chemical and physical methods currently used to prepare heteroatom-doped carbon materials, such as ammonia treatment, chemical vapor deposition, and the like, still suffer from several drawbacks, mainly: the equipment is complex, the synthesis process is long, the prepared carbon material has poor mechanical property, and a large number of common gap holes are not beneficial to the transportation of ions and electrons. In recent years, heteroatom-doped carbon foams have been the focus of research due to the 3D interconnect network structure and excellent flexibility characteristics. At present, the 3D interconnection network structure of the heteroatom-doped carbon foam obtained by directly pyrolyzing cheap commercial melamine foam is beneficial to rapid ion transport and the growth of active inorganic components, has the advantages of a preparation process and has great potential in the field of flexible energy storage electrode materials.
The metal oxide and the heteroatom doped carbon material can be compounded to generate a rapid and reversible Faraday redox reaction so as to provide high specific capacitance. Mn3O4The material has great potential in pseudo-capacitance electrode materials due to good environmental compatibility, low cost, abundant natural resources and larger specific capacitance. However, due to Mn3O4Poor conductivity (10)-5～10-6s cm-1) The stability is relatively low, the wetting area is small, and the application of the composite material in a high-performance super capacitor is hindered. Therefore, the microstructure of the excellent electrode is designed to increase Mn3O4The maintenance of high electrolyte permeation/diffusion rates to improve its electrochemical performance is a very critical strategy.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide Mn3O4The functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material and the preparation method and application thereof have the advantages of simple process, wide applicability, high efficiency and the like, and can be used for preparing the impurity-doped carbon foam/transition metal oxide composite material with rich 3D porous structure, high specific surface area, high specific capacitance and excellent mechanical property.
In order to achieve the purpose, the invention adopts the following scheme:
< preparation method >
The invention provides Mn3O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps: step 1, completely dipping melamine foam in biomass proton salt (Chit)][H2PO4]And Mn (NO)3)2In the mixed solution of (1); in the mixed solution, the molar ratio [ Chit][H2PO4]:Mn(NO3)25-20: 1; step 2, drying the soaked melamine foam, then placing the melamine foam in a tubular furnace, heating the melamine foam to 700-1000 ℃ at a certain heating rate, carrying out pyrolysis for a period of time, then naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for a period of time to obtain Mn3O4And (3D) the carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet.
Preferably, the Mn provided by the invention3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material can also have the following characteristics: biomass proton salt [ Chit ] in step 1][H2PO4]The preparation method of the solution comprises the following steps: dissolving chitosan in volume percentageStirring in 1-5% acetic acid solution in ice water bath until the solution is clear, then slowly dripping phosphoric acid in inert atmosphere, and continuously stirring for 0.5-2 h; the preferable molar ratio of chitosan to phosphoric acid is 1: 2-3: 1, and the optimal molar ratio is 1: 1.
Preferably, the Mn provided by the invention3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material can also have the following characteristics: in step 1, the preparation method of the mixed solution comprises the following steps: mn (NO) with the concentration of 0.05 mol/L-0.2 mol/L3)2Slowly dripping the aqueous solution into biomass proton salt [ Chit ]][H2PO4]Continuously stirring the solution for 0.5 to 2 hours; and, [ Chit][H2PO4]And Mn (NO)3)2The molar ratio of (a) to (b) is preferably 5 to 20:1, and the most preferable molar ratio is 10: 1.
Preferably, the Mn provided by the invention3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material can also have the following characteristics: in step 1, the immersion time is 1 to 24 hours in step 1.
Preferably, the Mn provided by the invention3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material can also have the following characteristics: in the step 2, the heating rate is 1-10 ℃/min, and the pyrolysis time is 0.5-2 h.
Preferably, the Mn provided by the invention3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material can also have the following characteristics: in the step 2, the cooling time is 0.5 h-2 h, and the cooling is carried out to 200-320 ℃ and then the cooling is maintained for 0.5 h-2 h in the air atmosphere.
<3D carbon foam composite >
Further, the invention also provides Mn3O43D carbon foam composite of functionalization N/P codope carbon piece embedding, its characterized in that: adopt the above<Preparation method>By the process described in (1).
< application >
Furthermore, the inventionAlso provides Mn3O4Application of the 3D carbon foam composite material embedded in the functionalized N/P co-doped carbon sheet is characterized in that: the 3D carbon foam composite material is used as an electrode material in a flexible supercapacitor.
The invention has the following functions and effects:
(1) mn prepared by the invention3O4The 3D carbon foam composite material embedded in the functionalized N/P co-doped carbon sheet has rich pore structures, large specific surface area and high N/P atom content; wherein, P, N and Mn content can be respectively as high as 5.64 at.%, 6.82 at.% and 9.87 at.%;
(2) the 3D carbon foam composite material prepared by the invention is applied to a super capacitor, has high capacitance performance and circulation stability, and has the current density of 0.2A g-1When the specific capacitance reaches 583F g-1Increasing the current density to 20A g-1The specific capacitance can still be maintained at 154F g-1And the capacitance can still remain 96% after 5000 cycles;
(3) the supercapacitor device assembled by the 3D carbon foam composite material has excellent temperature resistance and flexibility, and the capacitance performance is almost kept unchanged at the temperature of minus 20 ℃ and 80 ℃ and in different bending states (the bending diameter is 3-20 mm).
(4) The method has the advantages of simple and green treatment process flow, easy operation, low cost and wide application prospect in the field of composite material preparation.
Drawings
FIG. 1 shows Mn prepared in the first embodiment of the present invention3O4Scanning electron microscope images of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material;
FIG. 2 shows Mn prepared in the first embodiment of the present invention3O4A transmission electron microscope image of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet;
FIG. 3 shows Mn prepared in the first embodiment of the present invention3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite (NPCF/Mn)3O4) An X-ray photoelectron spectrum of (a);
FIG. 4 shows the present inventionMn prepared in example one3O4The method comprises the steps of functionalizing cyclic voltammetry curve maps of different scanning speeds of a 3D carbon foam composite material embedded with an N/P co-doped carbon sheet;
FIG. 5 shows Mn prepared in the first embodiment of the present invention3O4The cycle stability map of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet;
FIG. 6 shows Mn prepared in the first embodiment of the present invention3O4The temperature resistance test map of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet;
FIG. 7 shows Mn prepared in the first embodiment of the present invention3O4A flexible performance test map of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet;
FIG. 8 shows Mn prepared in example one3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite (NPCF/Mn)3O4) N/P codoped carbon sheet-embedded 3D carbon foam composite (NPCF) prepared in comparative example one, and 3D carbon foam/Mn prepared in comparative example two3O4Composite material (CF/Mn)3O4) Comparative graph of nitrogen adsorption/desorption curves of the 3D Carbon Foam (CF) prepared in comparative example three;
FIG. 9 is the NPCF/Mn prepared in example one3O4NPCF prepared in comparative example one, CF/Mn prepared in comparative example two3O4Comparative example c and comparative example c.
Detailed Description
Mn related to the present invention is described below with reference to the accompanying drawings3O4The 3D carbon foam composite material embedded by the functionalized N/P co-doped carbon sheet and the preparation method and the application thereof are explained in detail.
< example one >
Mn3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material comprises the following steps: 1.61 g of chitosan was dissolved in 50mL of 3% acetic acid by volume and stirred for 30 minutes to completely dissolve the chitosan. Under the protection of nitrogen and iceIn a water bath, 6mL of diluted phosphoric acid with a concentration of 1.5mol/L was slowly added dropwise to the completely dissolved solution. After stirring for 2 hours, [ Chit ] is obtained][H2PO4]。
Subsequently, 10ml of Mn (NO) was added at a concentration of 0.1mol/L3)2The solution was slowly added dropwise [ Chit][H2PO4]The stirring was continued for 1h, the melamine foam was impregnated therein for 12h and then freeze-dried at-50 ℃ for 72 h. Placing the sample obtained by freeze drying in a tube furnace under argon atmosphere, heating at 5 deg.C per minute, heating to 800 deg.C, pyrolyzing for 1h, naturally cooling to 320 deg.C in ambient atmosphere, and maintaining for 30min to obtain Mn3O4And (3D) the carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet.
Mn prepared in the first example3O4And carrying out scanning electron microscope, transmission electron microscope and X-ray photoelectron spectroscopy experiments on the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet.
Further, Mn prepared in the first example was added3O4The 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is applied to a supercapacitor as an electrode material, cyclic voltammetry curves and cyclic stability tests are carried out at different scanning speeds, and Mn prepared by the embodiment is used3O4The 3D carbon foam composite material embedded in the functionalized N/P co-doped carbon sheet is applied to the test of the temperature resistance and the flexibility of the supercapacitor.
Experimental results and effects thereof:
FIG. 1 shows Mn prepared in example one3O4Scanning electron microscope image of 3D carbon foam composite material embedded with functionalized N/P co-doped carbon sheet, namely Mn3O4The 3D carbon foam embedded by the functionalized N/P co-doped carbon sheet shows a remarkable 3D porous interconnection structure.
FIG. 2 shows Mn prepared in example one3O4Transmission electron microscopy of functionalized N/P co-doped carbon sheet embedded 3D carbon foam, the Mn3O4Transmission electron microscope image of 3D carbon foam embedded with functionalized N/P co-doped carbon sheet shows Mn3O4Particles are embedded in carbon sheets and high power transmission electron microscopy shows Mn3O4The particles are surrounded by a disordered carbon layer with vermicular channels.
FIG. 3 shows Mn prepared in example one3O4X-ray photoelectron spectrum of 3D carbon foam embedded with functionalized N/P co-doped carbon sheet, the Mn3O4X-ray photoelectron spectroscopy of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam showed Mn 3P, Mn3s, P2P, C1 s, N1 s, O1 s and Mn 2P peaks indicating the presence of P, C, N, O and Mn elements, P, N and Mn contents as high as 5.64 at.%, 6.82 at.% and 9.87 at.%, respectively.
FIG. 4 shows Mn prepared in example one3O4The 3D carbon foam embedded by the functionalized N/P co-doped carbon sheet is applied to a super capacitor as an electrode material, the cyclic voltammetry curves of the super capacitor at different scanning speeds all show oxidation-reduction peaks, and the shapes of the cyclic voltammetry curves do not change significantly with the increase of the scanning speed, which indicates that Mn is present3O4The good capacitance behavior of the 3D carbon foam embedded by the functionalized N/P co-doped carbon sheet.
FIG. 5 shows Mn prepared in example one3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam as electrode material applied to super capacitor and having scanning speed of 100mV & s-1When the circuit is continuously cycled for 5000 times, the capacitance of the circuit can still be kept 96%, which means excellent stability.
FIGS. 6 and 7 show Mn prepared in example one3O4The 3D carbon foam embedded by the functional N/P co-doped carbon sheet is used as an electrode material to be assembled into a super capacitor device, when the temperature is-20 ℃ and 80 ℃ and different bending states (the bending diameter is 0, 3, 7 and 10mm), the capacitance performance is slightly changed, and the super capacitor device has excellent temperature resistance and flexibility.
< comparative example A >
In the first comparative example, [ Chit][H2PO4]The preparation method of (1) is identical to that of the first example except that the melamine foam in the first example is removed and 10ml of Mn (NO) with a concentration of 0.1mol/L is added3)2The solution was slowly added dropwise [ Chit][H2PO4]After stirring for 1 hour, the mixture was lyophilized for 72 hours. Drying the frozen foodAnd (3) placing the obtained sample in a tubular furnace, heating to 5 ℃ per minute, heating to 800 ℃, then pyrolyzing for 1h, naturally cooling to 320 ℃ in an ambient atmosphere, and maintaining for 30min to obtain the N/P co-doped carbon sheet embedded 3D carbon foam composite material (NPCF).
< comparative example II >
In the second comparative example, the [ Chit ] of the first example][H2PO4]10ml of Mn (NO) with a concentration of 0.1mol/L was removed3)2The solution was slowly added dropwise to 50ml of water, stirred for 1 hour and then lyophilized for 72 hours. Placing the sample obtained by freeze drying in a tube furnace, heating to 5 deg.C per minute, heating to 800 deg.C, pyrolyzing for 1h, naturally cooling to 320 deg.C in ambient atmosphere, and maintaining for 30min to obtain 3D carbon foam/Mn3O4Composite material (CF/Mn)3O4)。
< comparative example III >
In the third comparative example, the melamine foam was directly placed in a tube furnace to be heated to 5 ℃ per minute, heated to 800 ℃ and pyrolyzed for 1 hour, and then naturally cooled to 320 ℃ in the ambient atmosphere and maintained for 30 minutes, so as to obtain the 3D Carbon Foam (CF).
The materials prepared in the first embodiment, the second embodiment and the third embodiment are characterized by nitrogen adsorption and desorption, and are used as electrode materials to be applied to supercapacitors for cyclic voltammetry curve test.
Experimental results and effects thereof: fig. 8 is a nitrogen adsorption and desorption curve of the materials prepared in the first, second and third comparative examples, wherein the nitrogen adsorption and desorption curve of the first example shows a type IV isotherm with a significant hysteresis loop of H4 and has a high adsorption capacity, which indicates that the nitrogen and sulfur co-doped carbon material prepared in the first example has a significant hierarchical porous characteristic and a large specific surface area, while the nitrogen adsorption and desorption curves of the first, second and third comparative examples respectively show an insignificant hierarchical porous characteristic and a insignificant microporous characteristic and have a low adsorption capacity and a small specific surface area.
The above embodiments are merely illustrative of the technical solutions of the present invention. Mn according to the invention3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foamThe composite material and the method and application of the same are not limited to the content described in the above embodiments, but are subject to the scope of protection defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.
Claims (8)
1.Mn3O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps:
step 1, completely dipping melamine foam in biomass proton salt (Chit)][H2PO4]And Mn (NO)3)2In the mixed solution of (1); in the mixed solution, the molar ratio [ Chit][H2PO4]:Mn(NO3)2＝5～20:1；
Step 2, drying the soaked melamine foam, then placing the melamine foam in a tubular furnace, heating the melamine foam to 700-1000 ℃ at a certain heating rate, carrying out pyrolysis for a period of time, then naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for a period of time to obtain Mn3O4And (3D) the carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet.
2. Mn according to claim 13O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps of:
wherein, in the step 1, the biomass proton salt [ Chit][H2PO4]The preparation method of the solution comprises the following steps: dissolving chitosan in 1-5 vol% acetic acid solution, stirring in ice-water bath until the solution is clear, then slowly dripping phosphoric acid in an inert atmosphere, and continuously stirring for 0.5-2 h; and the molar ratio of the chitosan to the phosphoric acid is 1: 2-3: 1.
3. Mn according to claim 13O4Preparation method of functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material, and preparation methodIs characterized in that:
in the step 1, the preparation method of the mixed solution comprises the following steps: mn (NO) with the concentration of 0.05 mol/L-0.2 mol/L3)2Slowly dripping the aqueous solution into biomass proton salt [ Chit ]][H2PO4]Continuously stirring the solution for 0.5 to 2 hours; and, [ Chit][H2PO4]And Mn (NO)3)2The molar ratio of (A) to (B) is 5-20: 1.
4. Mn according to claim 13O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps of:
wherein, in the step 1, the dipping time is 1-24 h.
5. Mn according to claim 13O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps of:
wherein in the step 2, the heating rate is 1-10 ℃/min, and the pyrolysis time is 0.5-2 h.
6. Mn according to claim 13O4The preparation method of the 3D carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet is characterized by comprising the following steps of:
wherein, in the step 2, the mixture is naturally cooled to 200-320 ℃ and then is maintained in the air atmosphere for 0.5-2 h.
7.Mn3O43D carbon foam composite of functionalization N/P codope carbon piece embedding, its characterized in that:
the preparation method of any one of claims 1 to 6.
8. An Mn as set forth in claim 73O4Application of the 3D carbon foam composite material embedded in the functionalized N/P co-doped carbon sheet is characterized in that:
wherein the 3D carbon foam composite material is used as an electrode material in a flexible supercapacitor.
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| CN105355874A (en) * | 2015-11-03 | 2016-02-24 | 湖北工程学院 | Nitrogen-doped porous carbon ball/manganic manganous oxide nanometer composite electrode material and preparation method thereof |
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2019
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355874A (en) * | 2015-11-03 | 2016-02-24 | 湖北工程学院 | Nitrogen-doped porous carbon ball/manganic manganous oxide nanometer composite electrode material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| High performance supercapacitors based on three-dimensional ultralight flexible manganese oxide nanosheets/carbon foam composites;Shuijian He等;《Journal of Power Sources》;20140413;391-400 * |
| Interconnected Phosphorus and Nitrogen Codoped Porous Exfoliated Carbon Nanosheets for High-Rate Supercapacitors;Jutao Jin等;《ACS Appl. Mater. Interfaces》;20170503;17317-17325 * |
| N/P Codoped Porous Carbon/One-Dimensional Hollow Tubular Carbon Heterojunction from Biomass Inherent Structure for Supercapacitors;Li Li等;《ACS Sustainable Chem. Eng.》;20181120;1337-1346 * |
| One-Step Construction of N,P-Codoped Porous Carbon Sheets/CoP Hybrids with Enhanced Lithium and Potassium Storage;Jing Bai等;《Adv. Mater.》;20180713;1802310 * |
| 锰氧化物/碳氮三维网络结构复合材料的制备及锂电性能;杨蓉等;《无机化学学报》;20170228;210-218 * |
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