CN110734094A - 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 PDF

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CN110734094A
CN110734094A CN201910954671.4A CN201910954671A CN110734094A CN 110734094 A CN110734094 A CN 110734094A CN 201910954671 A CN201910954671 A CN 201910954671A CN 110734094 A CN110734094 A CN 110734094A
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CN110734094B (en
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潘春旭
孙立
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Wuhan University (WHU)
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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. subjecting the melamineThe amine foam is completely immersed in the solution containing 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)2And 2, drying the soaked melamine foam, placing the dried melamine foam in a tubular furnace, heating the melamine foam to 700-1000 ℃ for periods at a heating rate of , naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for periods to obtain the 3D carbon foam composite material.

Description

Mn3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to kinds of 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 research finds that the synergistic effect of doping multiple heteroatoms on the electrochemical properties of the carbon material is superior to that of doping a single heteroatom, however, many cheap chemical and physical methods currently used for preparing heteroatom-doped carbon materials, such as ammonia treatment, chemical vapor deposition and the like still have defects, mainly including complex equipment, long synthesis process, poor mechanical properties of the prepared carbon material, and large amount of common pores which are not beneficial to the transport of ions and electrons.
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. Mn3O4Due to good environmentCompatibility, low cost, abundant natural resources and larger specific capacitance have great potential in pseudo-capacitance electrode materials. 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 kinds of 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, high applicability of , 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)2 Step 2, drying the soaked melamine foam, putting the dried melamine foam into a tubular furnace, heating the melamine foam to 700-1000 ℃ at a heating rate of for pyrolysis for periods, naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for periods 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 invention3O4Functionalization of NThe preparation method of the 3D carbon foam composite material embedded by the/P co-doped carbon sheet 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 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; 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 >
step, the invention also provides Mn3O4Functionalized N/P co-doped carbon sheetAn embedded 3D carbon foam composite characterized by: adopt the above<Preparation method>By the process described in (1).
< application >
Further , the invention also 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 and low cost, and has wide application prospect in the field of composite material preparation.
Drawings
FIG. 1 shows Mn as prepared in example 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 as prepared in example 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 is a schematic representation of the practice of the present inventionMn prepared in example 3O4Functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite (NPCF/Mn)3O4) An X-ray photoelectron spectrum of (a);
FIG. 4 shows Mn as prepared in example of the present invention3O4The 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 as prepared in example 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 as prepared in example 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 as prepared in example 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 3O4Functionalized 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 , 3D carbon foam/Mn prepared in comparative example II3O4Composite 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 3O4NPCF prepared in comparative example , CF/Mn prepared in comparative example II3O4Comparative 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 >
Mn3O4The preparation method of the functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material comprises the following steps: 1.61g of chitosan was dissolved in 50mL of 3% acetic acid by volume and stirred for 30 minutes to completely dissolve the chitosan. In a nitrogen protection and ice-water bath, 6mL of diluted phosphoric acid with the concentration of 1.5mol/L is slowly dropped into 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][HSO4]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 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 Mn3O4And (3D) the carbon foam composite material embedded with the functionalized N/P co-doped carbon sheet.
Mn prepared in this example 3O4And 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.
step Mn prepared in this example 3O4The 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 3O4Scanning 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 3O4Transmission electricity of 3D carbon foam embedded by functionalized N/P co-doped carbon sheetMirror image of 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 were encapsulated by layers of disordered carbon layers accompanied by worm-like channels.
FIG. 3 shows Mn prepared in example 3O4X-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 3O4The 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 3O4Functional N/P co-doped carbon sheet embedded 3D carbon foam is applied to a super capacitor as an electrode material, and the scanning speed of the super capacitor is 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 are Mn prepared from example 3O4The 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 >
In comparative example , [ Chit][H2PO4]Was prepared in exactly the same manner as in example , except that in example The melamine foam was removed and 10ml of Mn (NO) was added at a concentration of 0.1mol/L3)2The solution was slowly added dropwise [ Chit][HSO4]After stirring for 1 hour, the mixture was lyophilized for 72 hours. And (3) placing the sample obtained by freeze drying in a tubular furnace, heating to 5 ℃ per minute, heating to 800 ℃, 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 term "Chit" in 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 example , comparative example , comparative example two and comparative example three were characterized by nitrogen adsorption and desorption, and were used as electrode materials in supercapacitors for cyclic voltammetry tests.
Fig. 8 shows nitrogen adsorption and desorption curves of materials prepared in example , comparative example , comparative example two and comparative example three, the nitrogen adsorption and desorption curve of example shows an IV isotherm with a significant hysteresis loop of H4 and has a high adsorption amount, which indicates that the nitrogen and sulfur co-doped carbon material prepared in example has a significant hierarchical porous characteristic and a large specific surface area, while the nitrogen adsorption and desorption curves of comparative example , comparative example two and comparative example three respectively show an insignificant hierarchical porous characteristic and a insignificant microporous characteristic and have a low adsorption amount and a small specific surface area.
The above embodiments are merely illustrative of the technical solutions of the present invention. Mn according to the invention3O4The functionalized N/P co-doped carbon sheet embedded 3D carbon foam composite material, the preparation method and the application thereof are not limited to the contents described in the above embodiments, but shall be subject to the protection scope 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, placing the dried melamine foam in a tubular furnace, heating the melamine foam to 700-1000 ℃ at a heating rate of for pyrolysis for periods of time, naturally cooling the melamine foam to 200-320 ℃, and maintaining the melamine foam in an air atmosphere for periods 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 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:
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 of claims 1-6.
8. The method of claim 7Mn of (2)3O4Application 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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