CN109205596B - graphene/WSe 2 NiFe-LDH aerogel and preparation thereof - Google Patents
graphene/WSe 2 NiFe-LDH aerogel and preparation thereof Download PDFInfo
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Abstract
The invention relates to graphene/WSe 2 A/NiFe-LDH aerogel and a method for making the same, the method comprising: dispersing graphene oxide lamella and WSe 2 Mixing the nanosheet dispersion liquid, adding at least one of a reducing agent, a cross-linking agent and a pH regulator, uniformly mixing, and reacting to obtain graphene/WSe 2 Hydrogel, freezing and drying to obtain graphene/WSe 2 An aerogel; subjecting the graphene/WSe 2 Soaking aerogel in NiFe-LDH nanosheet dispersion liquid to prepare graphene/WSe 2 Freezing and drying the NiFe-LDH hydrogel to obtain the graphene/WSe 2 /NiFe-LDH aerogel. The N, S co-doped graphene/WSe prepared by the method 2 Preparation method of/NiFe-LDH (N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide) is simple in preparation and low in cost, and prepared N, S co-doped graphene/WSe 2 The NiFe-LDH has excellent electrochemical properties such as large specific capacitance, good cycle performance, small internal resistance and the like.
Description
Technical Field
The invention relates to an electrode material, in particular to graphene/WSe 2 A NiFe-LDH aerogel and a preparation method thereof.
Background
With the rapid development of economy and the increase of global population, the problems of continuous deterioration of environment and increasingly deficient energy sources cause wide attention of people in all the world, and the search for sustainable, clean and efficient renewable energy materials is undoubtedly a hot spot of attention of people. The super capacitor is a novel energy storage device, has the advantages of high power density, long cycle life, rapid charge and discharge process, low cost and the like, becomes a hotspot of research, and has good application prospect in various fields. The performance of the electrode material is mainly determined by the selection of the electrode material, so that the preparation of a proper electrode material is of great significance. Research shows that the electrochemical performance of the electrode material is mainly influenced by the following factors: the conductivity of the electrode material, the pore structure of the electrode material, the effective specific surface area of the electrode material, the specific capacity of the electrode material itself, and the like.
Due to the strong pi-pi interaction between Graphene (GO) sheets, the graphene is agglomerated again after reduction, and the graphene has the defects of poor dispersibility, inactive surface, difficulty in compounding with other materials and the like, so that the application of the graphene is subjected to bottleneck. Therefore, the two-dimensional graphene sheets are assembled into a three-dimensional structure, such as graphene aerogel, the high specific surface area of graphene can be fully utilized, the graphene is endowed with strong macroscopic mechanical properties, and the time application of graphene is realized. The graphene aerogel has a plurality of excellent properties of graphene and aerogel, such as low density, high porosity, huge specific surface area, good mechanical properties, excellent conductivity, controllable structure and the like, so that the graphene aerogel is considered as one of the best candidate electrode materials of the electric double layer supercapacitor. In addition, the doping of the graphene through the heteroatom can reduce the forbidden band broadband of the graphene, increase the conductivity of the graphene and improve the electrochemical performance of the doped graphene through a strong synergistic effect between the heteroatom and the defect of the graphene.
The layered transition metal dichalcogenide has a graphite-like structure composed of X-M-X layers (M ═ Mo, W; (X ═ S, Se, Te)) bonded by covalent bonds, by means of inter-layer van der waals forces. Tungsten diselenide, as a typical transition metal disulfide, has a narrower forbidden band width and higher conductivity compared with molybdenum disulfide, so that the tungsten diselenide has higher pseudocapacitance performance. The composite material is peeled into a two-dimensional ultrathin nanosheet layer structure by a liquid phase ultrasonic method, so that the specific surface area of the composite material can be maximized, the electrochemical active sites of the composite material can be exposed, and the performance of the composite material in the application of a super capacitor can be improved.
Layered Double Hydroxide (LDH) is a Layered material that has a large specific surface area and can be artificially synthesized according to specific functions. LDH has various unique physical and chemical properties including laminate electropositivity, host element variability, interlayer spacing adjustability and the like, and therefore has great application potential in the aspects of catalysis, energy sources, water treatment and the like. In recent years, with the continuous and deep research on the structure and performance of LDH, the materials are found to have capacitance with two properties of an electric double layer and a pseudocapacitance, and show attractive development prospects in the field of energy storage.
Although the above materials all exhibit certain supercapacitive properties when used as individual electrode materials, the properties are not ideal.
Disclosure of Invention
In view of the above, it is actually necessary to provide a graphene/WSe 2 Preparation method of/NiFe-LDH (N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide), preparation is simple, cost is low, and prepared graphene/WSe 2 The NiFe-LDH has excellent electrochemical properties such as large specific capacitance, good cycle performance, small internal resistance and the like.
The invention provides graphene/WSe in a first aspect 2 The preparation method of the NiFe-LDH aerogel is characterized by comprising the following steps: dispersing graphene oxide lamella and WSe 2 Mixing the nanosheet dispersion liquid, adding at least one of a reducing agent, a cross-linking agent and a pH regulator, uniformly mixing, and reacting to obtain graphene/WSe 2 Hydrogel, freezing and drying to obtain graphene/WSe 2 An aerogel; subjecting the graphene/WSe 2 Soaking aerogel in NiFe-LDH nanosheet dispersion liquid to prepare graphene/WSe 2 Freezing and drying the NiFe-LDH hydrogel to obtain the graphene/WSe 2 /NiFe-LDH aerogel.
Further, the reducing agent or the cross-linking agent contains N and S, preferably, the reducing agent or the cross-linking agent is L-cysteine, and the obtained graphene/WSe 2 the/NiFe-LDH aerogel is N, S co-doped graphene/WSe 2 NiFe-LDH aerogel。
Further, the graphene oxide lamellar dispersion liquid is prepared by ultrasonically dispersing graphite oxide in deionized water; the WSe 2 The nano-sheet dispersion liquid is prepared by a liquid phase stripping method; the NiFe-LDH nanosheet dispersion is prepared by a hydrothermal method.
Further, the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and stirring 3 Dissolving in concentrated sulfuric acid until NaNO 3 Completely dissolving;
s12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches 4 Removing the ice bath after the addition, and reacting until the liquid becomes viscous;
s13, adding deionized water, reacting, and adding deionized water again at the temperature lower than 120 ℃;
s14, adding H at room temperature 2 O 2 Water solution, after the reaction is finished, centrifuging to remove supernatant, and keeping precipitate;
and S15, washing the precipitate with HCl solution, and drying to obtain graphite oxide.
Further, the WSe 2 The nanosheet dispersion was prepared by the following method: dispersing tungsten diselenide in isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain WSe 2 A nanosheet dispersion.
Further, the NiFe-LDH nanosheet dispersion is prepared by the following method:
s31, mixing Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Dispersing O, urea and trisodium citrate in water, reacting at the temperature of 130-170 ℃, washing and drying after the reaction is finished to obtain a powdery substance;
s32, dispersing the powdery substance in the step S31 in formamide solution, and taking supernatant as NiFe-LDH nanosheet dispersion liquid.
Further, the graphene oxide sheets and the WSe 2 The weight ratio of the nano sheets is 4: 9-36: 1.
Further, the graphene/WSe 2 And said NiFe-LThe weight ratio of DH is 10: 1-1: 10.
Further, the reducing agent is L-cysteine, ascorbic acid, glucose or any mixture thereof.
Further, the cross-linking agent is L-cysteine and/or polypyrrole.
The invention provides a graphene/WSe prepared by the method in a second aspect 2 /NiFe-LDH aerogel.
Compared with the prior art, the invention adopts graphite oxide and WSe 2 And preparing the ternary N, S co-doped graphene/WSe by using NiFe-LDH 2 The NiFe-LDH aerogel has the following beneficial effects:
1) the aerogel of the invention is used for preparing the ultra-thin tungsten diselenide nanosheet dispersion by a liquid phase stripping method, and compared with the existing lithium intercalation method, the stripping is safer, and the cost is reduced.
2) According to the aerogel disclosed by the invention, L-cysteine is taken as a doping element source to carry out N and S co-doping on graphene, and in addition, the L-cysteine can be taken as a cross-linking agent in the process of forming the aerogel by the graphene, so that the doping and cross-linking of the graphene can be simultaneously carried out when the hydrothermal method is used for loading tungsten diselenide on a graphene sheet layer to form the aerogel.
3) The self-assembly effect of the N, S co-doped graphene/tungsten diselenide/nickel-iron double hydroxide with negative charges and the nickel-iron double hydroxide with positive charges is prepared into the ternary N, S co-doped graphene/tungsten diselenide/nickel-iron double hydroxide aerogel composite material through the electrostatic effect, good interface contact is formed, agglomeration is reduced, and the method is simple and is easy for large-scale production.
4) The ternary N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide composite aerogel prepared by the method has excellent electrochemical performance, has large specific capacitance, good cycle performance, small internal resistance and the like, and can be used as a stable and efficient supercapacitor electrode material.
5) The N, S co-doped graphene/WSe prepared by the method 2 Preparation method of/NiFe-LDH (N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide) is simple in preparation and low in cost, and prepared N, S co-doped graphene/WSe 2 The NiFe-LDH has excellent electrochemical properties such as large specific capacitance, good cycle performance, small internal resistance and the like.
Drawings
FIG. 1 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A schematic diagram of a preparation process of the NiFe-LDH aerogel;
FIG. 2 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A scanning electron micrograph of NiFe-LDH;
FIG. 3 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 Partial enlargement of the scanning electron microscope of/NiFe-LDH.
FIG. 4 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 X-ray photoelectron spectroscopy of the NiFe-LDH aerogel;
FIG. 5 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A Tafel slope curve diagram of hydrogen evolution of a NiFe-LDH aerogel electrode;
FIG. 6 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A constant current charge-discharge curve of the NiFe-LDH aerogel electrode under different current densities;
FIG. 7 shows an N and S co-doped graphene/WSe in accordance with an embodiment of the present invention 2 The specific capacity of the NiFe-LDH aerogel electrode changes along the curve in the process of 2000 charge-discharge cycles.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
As shown in fig. 1, the N, S co-doped graphene/WSe of the preferred embodiment of the present invention 2 A method for preparing NiFe-LDH, comprising:
s1, ultrasonically dispersing the graphite oxide in deionized water to prepare graphene oxide lamellar dispersion liquid. Preferably, the concentration of the prepared graphene oxide dispersion liquid is 0.5-3mgmL -1 More preferably 2mg mL -1 。
Specifically, the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and vigorous stirring 3 Dissolving in concentrated sulfuric acid until NaNO 3 And completely dissolving.
For example: adding 98% concentrated sulfuric acid (H) into a three-mouth reaction bottle 2 SO 4 ) And the reaction flask is placed in an ice-water bath and stirred at the rotating speed of 150rpm, and NaNO is added 3 And stirring under ice-water bath. Wherein, the concentrated sulfuric acid and NaNO 3 The weight ratio of: 60: 1-100: 1.
S12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches 4 After the addition, the ice bath was removed and the reaction was allowed to proceed until the liquid became viscous.
For example: adding natural graphite powder, maintaining ice-water bath constant, adding KMnO 4 Adding slowly in batches, keeping the reaction temperature below 10 deg.C (more preferably below 5 deg.C), and stirring in ice water bath until the temperature does not rise. The ice-water bath was then removed and the reaction flask was placed in a water bath at 25-45 deg.C (more preferably 35 deg.C) to react until the reaction solution had a viscous greenish black color. Wherein: NaNO 3 Graphite powder and KMnO 4 The weight ratio of: (0.5-1.5): (1-3): (4-8).
S13, adding a first weight of deionized water, reacting for a period of time, and adding a second weight of deionized water at a temperature below 120 ℃. Preferably, the first weight is 1.5-2.5 times of the volume of the concentrated sulfuric acid, and the second weight is 2-4 times of the volume of the reaction liquid.
For example: adding deionized water with the first weight, controlling the reaction temperature to be lower than 98 ℃, carrying out oil bath, reacting for 15min, and adding deionized water with the weight more than 1.5 times that of the reaction liquid at 98 ℃.
The reaction liquid is controlled to be in a micro-boiling state, so that the phenomenon that the system releases heat violently and splashes after deionized water is added into a concentrated sulfuric acid system can be avoided, and particularly the system is dangerous after amplification reaction, so that the micro-boiling of the reaction system is safely controlled, and the temperature is not easy to exceed 98 ℃.
S14, slowly adding H at room temperature 2 O 2 And (4) after the aqueous solution and the reaction are finished, centrifuging to remove supernatant, and keeping the precipitate.
For example: slowly add 30 wt% H at room temperature 2 O 2 Stirring the aqueous solution for reaction for 1h, centrifuging in a centrifuge, pouring out the supernatant, and keeping the precipitate.
And S15, washing the precipitate with HCl solution, and drying to obtain graphite oxide.
For example: washing the precipitate with 10 wt% HCl solution, centrifuging for several times, washing with deionized water until the pH of the supernatant is neutral, and drying the precipitate in an oven at 50-90 deg.C to obtain solid graphite oxide.
S2 preparation of ultra-thin WSe by liquid phase stripping method 2 A nanosheet dispersion.
For example: dispersing the block tungsten diselenide in isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain the ultrathin WSe 2 A nanosheet dispersion. In one embodiment, bulk tungsten diselenide is dispersed in isopropanol/water (V/V, 6/4) mixed solution and stripped into ultra-thin tungsten diselenide (WSe) by 300W ultrasonic oscillation for 2-4 hours 2 ) A nanosheet dispersion. Preferably, the WSe 2 The concentration of the nano-sheet dispersion liquid is 0.2-1.0mg mL -1 (ii) a More preferably 0.5mg mL -1 . Preferably, WSe 2 The thickness of the nano-sheet is 1.6nm-8 nm.
The embodiment of the invention adopts a liquid phase stripping method to prepare the ultrathin WSe 2 The nano-sheet dispersion liquid has low cost and safe operation.
S3, preparing a layered NiFe-LDH nanosheet dispersion liquid by a hydrothermal method; preferably, the concentration of the NiFe-LDH nanosheet dispersion is (0.5-2) mg.ml -1 (ii) a More preferably: 1mg.ml -1 。
In particular, the amount of the solvent to be used,
s31, mixing Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Dispersing O, urea and trisodium citrate in water, reacting at 130-170 ℃, and washing and drying the obtained product after the reaction. More specifically, the weight ratio is(7-12): (1-4): (2-6): 1 Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Dispersing O, urea and trisodium citrate in distilled water, performing ultrasonic treatment until the solution is clarified, sealing in a stainless steel hydrothermal reaction kettle containing a polytetrafluoroethylene substrate, reacting at the temperature of 130-170 ℃, filtering after the reaction, washing with water and ethanol for multiple times, and performing vacuum drying to obtain a powdery substance.
S32, dispersing the powdery substance in the step S31 in formamide solution, and taking supernatant as NiFe-LDH nanosheet dispersion liquid. Specifically, the powdery substance obtained in the step S31 is put into a degassed formamide solution for ultrasonic treatment to obtain a suspension, and the suspension is centrifuged to remove the un-peeled blocks, so that the supernatant is the NiFe-LDH nanosheet dispersion.
The above steps S1, S2 and S3 are not sequentially divided, and the sequence of the three steps can be changed at will.
S4, mixing the graphene oxide lamella dispersion liquid and WSe 2 Mixing the nanosheet dispersion liquid, adding a reducing agent, a cross-linking agent and a pH regulator, uniformly stirring, and reacting to obtain the N and S co-doped graphene/WSe 2 Hydrogel, and freeze drying.
Wherein the graphene oxide sheets and the WSe 2 The weight ratio of the nano sheets is 4: 9-36: 1. The reducing agent is L-cysteine, ascorbic acid, glucose or any mixture thereof. The cross-linking agent is L-cysteine and/or polypyrrole. The pH regulator is ammonia water, and the dosage of the pH regulator is 0.05-0.1 time of the volume of the graphene oxide dispersion liquid.
In the present embodiment, a pH adjusting agent is used to adjust the pH value of the solution, so as to affect the potential of the surface of the graphene oxide sheet layer, and the electrostatic repulsion between the graphene oxide sheet layers is used to affect the aggregation state of the reduced graphene oxide in the solution. And then the graphene with good reduction degree and dispersion degree can be prepared without a stabilizer.
In a specific embodiment, the reducing agent and the cross-linking agent are both L-cysteine, and the L-cysteine is used as the cross-linking agent to cross-link graphene sheets to form a 3D network structure, and can also be used as an N, S source for graphiteDoping of the alkene due to N, S to sp ratio 2 C has a greater electronegativity, which increases its conductivity.
S5, co-doping the N and S with graphene/WSe 2 Soaking the hydrogel in NiFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/WSe 2 Carrying out freeze drying on/NiFe-LDH hydrogel to obtain N, S co-doped graphene/WSe 2 A NiFe-LDH aerogel; wherein, N, S codoped graphene/WSe 2 The weight ratio of the NiFe-LDH to the NiFe-LDH is 10: 1-1: 10.
When the N and S are codoped with graphene/WSe after freeze drying 2 After the NiFe-LDH nano-sheet is added into the NiFe-LDH nano-sheet dispersion liquid, the NiFe-LDH nano-sheet with positive charges is adsorbed to the N and S co-doped graphene/WSe with negative charges due to electrostatic adsorption 2 Self-assembling to form N, S codoped graphene/WSe on the surface 2 And freeze-drying the/NiFe-LDH hydrogel composite material to obtain the N and S co-doped graphene/WSe 2/NiFe-LDH composite aerogel.
In the invention, N and S are codoped with graphene and WSe 2 And three materials of CoFe-LDH are compounded to prepare N, S codoped graphene/WSe 2 the/CoFe-LDH composite aerogel has excellent electrochemical properties, such as large specific capacitance, good cycle performance, small internal resistance and the like, and can be used as a stable and efficient supercapacitor electrode material. Meanwhile, the aerogel disclosed by the invention is used for preparing the ultrathin tungsten diselenide nanosheet dispersion by a liquid phase stripping method, and compared with the existing lithium intercalation method, the stripping is safer and the cost is reduced. According to the method, L-cysteine is used as a doping element source to co-dope N and S for graphene, and the L-cysteine is used as a cross-linking agent in the process of forming the aerogel by the graphene, so that the doping and cross-linking of the graphene to form the aerogel can be simultaneously carried out when the tungsten diselenide is loaded on a graphene sheet layer by a hydrothermal method. The self-assembly effect of the N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide with negative charges and the nickel iron double hydroxide with positive charges is prepared into the ternary N, S co-doped graphene/tungsten diselenide/nickel iron double hydroxide aerogel composite material through the electrostatic effect, good interface contact is formed, agglomeration is reduced, and the method is simple and easy for large-scale production.
The graphite oxide in the following specific examples was prepared by the following method:
to a three-neck reaction flask was added 46mL of concentrated sulfuric acid (98% H) 2 SO 4 ) And the reaction flask is placed in an ice-water bath to be stirred at the rotating speed of 150rpm, and then 1g of NaNO is weighed 3 Adding into a reaction bottle, stirring for 10min under ice water bath until NaNO 3 Dissolving completely, adding 2g of natural graphite powder, keeping ice-water bath constant, and weighing 6g of KMnO 4 Slowly adding in batches, keeping the reaction temperature below 5 ℃, and continuously stirring in an ice water bath for 30min after the addition is finished until the temperature does not rise any more. Then removing the ice water bath, placing the reaction bottle in a water bath with the temperature of 35 +/-3 ℃ for reacting for 1 hour, slowly adding 92mL of deionized water, raising the temperature of the reaction system, controlling the temperature not to exceed 98 ℃, reacting for 15 minutes under a 98 ℃ oil bath, adding 300mL of deionized water while the reaction system is hot, removing the oil bath, cooling the temperature of the reaction system to room temperature, adding 10mL of 30% H 2 O 2 (slowly adding), continuously stirring for 1 hour, and rotating at the speed of 5000r min -1 The centrifugal machine is used for centrifuging, the supernatant is poured off, the lower sediment is washed and centrifuged by 10 wt% HCl solution, the washing and centrifuging are repeated for 10 times, and finally the centrifugal machine is washed and centrifuged by deionized water until the pH value of the supernatant is neutral. The resulting precipitate was dried in an oven at 80 ℃ overnight to give solid graphite oxide.
Tungsten diselenide (WSe) used in the following examples 2 ) From Michelin, purity 99.8%, MDL number MFCD 00049703.
Example 1
N, S co-doped graphene/WSe 2 A preparation method of NiFe-LDH is shown in figure 1 and comprises the following steps:
(1) preparation of Graphene Oxide (GO) dispersion: dispersing 100mg of the graphite oxide prepared in the step of preparing into 100mL of deionized water, and carrying out ultrasonic treatment for 1 hour to obtain a tan GO lamella dispersion liquid, wherein the GO concentration is 2mg mL -1 。
(2) Ultra-thin WSe 2 Preparation of nanosheet dispersion: 20mg of the mass was WSe 2 Adding into 4mL of 60% volume fraction Isopropanol (IPA)/water (V/V, 6/4) mixed solvent, and placing into a super-solventUltrasonic vibration treatment was carried out in a sonicator at a power of 200W and a frequency of 40kHz for 4 hours, and the temperature was kept at room temperature during the ultrasonic treatment by adding circulating cooling water. Subsequently, the sonicated solution was centrifuged at 4000rpm for 20 minutes to remove WSe, a bulk material having not peeled off from the bottom 2 Obtaining supernatant which is the two-dimensional WSe 2 Nanoplatelets tested at a concentration of about 0.5mg/mL, ready for use.
(3) Preparing a layered NiFe-LDH nanosheet dispersion liquid: 0.27g of Ni (NO) 3 ) 2 ·6H 2 O，0.09 g Fe(NO 3 ) 3 ·9H 2 O, 0.12g urea and 0.03g trisodium citrate were dispersed in 75mL distilled water and sonicated for about 30min until clear. The resulting solution was transferred to a stainless steel hydrothermal reaction vessel containing a polytetrafluoroethylene substrate, sealed, and heated at 150 ℃ for 20 hours. And cooling to room temperature, filtering and collecting a solid product, washing with distilled water and ethanol for multiple times respectively, performing vacuum drying at 60 ℃ for 8 hours to obtain a powdery substance, dispersing the powdery substance into degassed 50mL formamide solution with the weight concentration of 50% to perform ultrasonic treatment to obtain suspension, and then centrifuging at 4000rpm for 20 minutes to remove un-peeled block materials to obtain a supernatant, namely the layered NiFe-LDH nanosheet with the preparation concentration of 1 mg/mL.
(4) 5mL of GO (2.0mg mL) -1 ) Lamellar Dispersion and 5mL of WSe 2 (0.5mg mL -1 ) Mixing the nanosheet dispersion, 50mg L-cysteine and 300. mu.L NH 3 ·H 2 O (27 wt%) was added gradually to 5mL GO (2.0mg mL) -1 ) And 5mL of WSe 2 (0.5mg mL -1 ) Then the mixture is mixed evenly by ultrasonic. The resulting mixed solution was transferred to a stainless steel hydrothermal reaction vessel containing a polytetrafluoroethylene substrate, sealed, and heated at 180 ℃ for 3 hours. Naturally cooling to room temperature to obtain N, S co-doped graphene (N, S-rGO)/WSe 2 A hydrogel. Subsequently, N, S-rGO/WSe 2 Washing hydrogel with distilled water for several times, and then freeze-drying to obtain N, S co-doped graphene/WSe 2 Aerogel (N, S-rGO/WSe) 2 Aerogel).
(5) The obtained N, S co-doped graphene/WSe 2 Soaking the aerogel in a layered NiFe-LDH nanosheet dispersion liquid (1mg/mL) for 24h to enable the layered NiFe-LDH nanosheets to be adsorbed on N, S co-doped graphene/WSe through electrostatic self-assembly 2 The balance is achieved. After that, the obtained N, S codoped graphene/WSe 2 Washing the/layered NiFe-LDH composite hydrogel with distilled water for several times, and then freeze-drying to obtain the N, S co-doped graphene/WSe 2 Layered NiFe-LDH aerogels.
And (3) performance testing:
the prepared N, S co-doped graphene/WSe 2 the/NiFe-LDH aerogels were tested with a Scanning Electron Microscope (SEM). As can be seen from FIG. 2, the prepared N, S co-doped graphene/WSe 2 the/NiFe-LDH aerogel forms a 3D pore channel structure, and N and S co-doped graphene/WSe 2 the/NiFe-LDH aerogel, and as can be seen from FIG. 3, N, S codoped with graphene and WSe 2 And three elementary materials of NiFe-LDH are effectively compounded to form a stable ternary composite material.
FIG. 4 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 X-ray photoelectron spectroscopy of the NiFe-LDH aerogel; through the graph in fig. 4, it can be verified that the composite aerogel contains N, S, C, W, Se, Ni, Fe elements, which indicates that all three elementary materials exist in the aerogel.
FIG. 5 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A cyclic voltammetry curve of a NiFe-LDH aerogel electrode; as can be seen from FIG. 5, the composite aerogel electrode material scanned at a rate of 5mV s -1 To 100mV s -1 In the process, the scanning rate is changed, and the shape of the curve is unchanged, so that the composite electrode material has better rate performance.
FIG. 6 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 A constant current charge-discharge curve of the NiFe-LDH aerogel electrode under different current densities; as can be seen from fig. 6, the constant current charge and discharge curves of the composite aerogel electrode material at different current densities are substantially symmetrical and have charge and discharge plateaus, which indicates that the composite aerogel electrode material has pseudocapacitance characteristics.
FIG. 7 shows N, S co-doped graphene/WSe according to an embodiment of the present invention 2 The NiFe-LDH aerogel electrode is 2Change curve of specific capacity in the process of 000 times of charge and discharge cycles. As can be seen in FIG. 7, the composite aerogel electrode material is shown at 15A g -1 After the current density is cycled for 2000 times, the capacitance retention rate is 92.3 percent, and the excellent cycle performance is embodied.
Example 2
This example was conducted under substantially the same reaction and operating conditions as those of example 1 except that L-cysteine, the reducing agent in example 1, was replaced with ascorbic acid.
Prepared graphene/WSe 2 The layered NiFe-LDH aerogel is tested to obtain the graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 91.5 percent.
Example 3
This example was conducted under substantially the same reaction and operation conditions as those in example 1 except that the reducing agent L-cysteine was replaced with glucose in example 1.
Prepared graphene/WSe 2 The layered NiFe-LDH aerogel is tested to obtain the graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.7 percent.
Example 4
This example was conducted under substantially the same reaction and operation conditions as those in example 1 except that the crosslinking agent L-cysteine in example 1 was replaced with polypyrrole.
Prepared graphene/WSe 2 The layered NiFe-LDH aerogel is tested to obtain the graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 91.8 percent.
Example 5
This example is essentially the same reaction and operating conditions as example 1, except that the GO dispersion has a concentration of 3mg/mL and the WSe is 2 The concentration of the nanosheet dispersion was 1 mg/mL.
Prepared N, S co-doped graphene/WSe 2 Layered NiFe-LDH aerogelsThe obtained N, S co-doped graphene/WSe can be known through tests 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 91.5 percent.
Example 6
The reaction and operating conditions of this example were substantially the same as those of example 1, except that the concentration of the GO dispersion was 0.5mg/mL and the concentration of the layered NiFe-LDH nanosheet dispersion was 0.5 mg/mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.4 percent.
Example 7
This example is essentially the same as example 1 except that the GO dispersion (concentration 2.0mg/mL) is 1mL in volume and WSe is used 2 The volume of the nanoplatelet dispersion (0.5mg/mL) was 9 mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.2 percent.
Example 8
This example is essentially the same as example 1 except that the volume of GO (2.0 mg/mL) dispersion is 1mL and WSe is 2 The concentration of the nanosheet dispersion was 0.2mg/mL, and the volume was 6 mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.9 percent.
Example 9
This example is essentially the same as example 1 except for the presence of GO (2.0 mg/mL) dispersionVolume 1mL, WSe 2 The volume of the nanoplatelet dispersion (0.5mg/mL) was 3 mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.6 percent.
Example 10
This example is essentially the same as example 1 except that the volume of GO (2.0 mg/mL) dispersion is 3mL and WSe is 2 The volume of the nanoplatelet dispersion (0.5mg/mL) was 1 mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.1 percent.
Example 11
This example is essentially the same as example 1 except that the volume of GO (2.0 mg/mL) dispersion is 6mL and WSe is 2 The volume of the nanoplatelet dispersion (0.5mg/mL) was 1 mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristics, and the capacitance retention rate is as follows: 90.7 percent.
Example 12
This example is essentially the same as example 1 except that the GO (2.0 mg/mL) dispersion has a volume of 9mL and the WSe has a volume of 9mL 2 The volume of the nano-sheet dispersion (0.5mg/mL) was 1mL, and the concentration of the NiFe-LDH nano-sheet dispersion was 2 mg/mL.
Prepared N, S co-doped graphene/WSe 2 Tests on the/layered NiFe-LDH aerogel show that the prepared N, S co-doped graphene/WSe 2 The layered NiFe-LDH aerogel has good rate performance and good pseudocapacitance characteristicsThe capacitance retention ratio is: 90.2 percent.
The foregoing is only a partial embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. N, S co-doped graphene/WSe 2 The preparation method of the NiFe-LDH aerogel is characterized by comprising the following steps: dispersing graphene oxide lamella and WSe 2 Mixing the nanosheet dispersion liquid, adding at least one of a reducing agent, a cross-linking agent and a pH regulator, uniformly mixing, and reacting to obtain graphene/WSe 2 Hydrogel, freezing and drying to obtain graphene/WSe 2 An aerogel; subjecting the graphene/WSe 2 Soaking aerogel in NiFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/WSe 2 the/NiFe-LDH hydrogel is frozen and dried to obtain N, S codoped graphene/WSe 2 A NiFe-LDH aerogel;
the graphene oxide lamellar dispersion liquid is prepared by ultrasonically dispersing graphite oxide in deionized water; the WSe 2 The nano-sheet dispersion liquid is prepared by a liquid phase stripping method; the NiFe-LDH nanosheet dispersion is prepared by a hydrothermal method;
the graphene oxide sheets and the WSe 2 The weight ratio of the nano sheets is 4: 9-36: 1;
the graphene/WSe 2 The weight ratio of the NiFe-LDH to the NiFe-LDH is 10: 1-1: 10.
2. The N, S-codoped graphene/WSe of claim 1 2 The preparation method of the NiFe-LDH aerogel is characterized in that the reducing agent or the cross-linking agent contains N and S, and the obtained graphene/WSe is 2 the/NiFe-LDH aerogel is N, S co-doped graphene/WSe 2 /NiFe-LDH aerogel.
3. The N, S-codoped graphene/WSe of claim 1 2 NiFe-LDH gasThe preparation method of the gel is characterized in that the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and stirring 3 Dissolving in concentrated sulfuric acid until NaNO 3 Completely dissolving;
s12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches 4 After the addition, the ice bath is removed, and the reaction is carried out until the liquid becomes viscous;
s13, adding deionized water, reacting, and adding deionized water again at the temperature lower than 120 ℃;
s14, adding H at room temperature 2 O 2 Water solution, after the reaction is finished, centrifuging to remove supernatant, and keeping precipitate;
and S15, washing the precipitate with HCl solution, and drying to obtain graphite oxide.
4. The N, S-codoped graphene/WSe of claim 1 2 The preparation method of the NiFe-LDH aerogel is characterized in that the WSe is 2 The nanosheet dispersion was prepared by the following method: dispersing tungsten diselenide in isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain WSe 2 A nanosheet dispersion.
5. The N, S-codoped graphene/WSe of claim 1 2 A preparation method of a NiFe-LDH aerogel is characterized in that the NiFe-LDH nanosheet dispersion liquid is prepared by the following method:
s31, mixing Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Dispersing O, urea and trisodium citrate in water, reacting at the temperature of 130-170 ℃, washing and drying after the reaction is finished to obtain a powdery substance;
s32, dispersing the powdery substance in the step S31 in formamide solution, and taking supernatant as NiFe-LDH nanosheet dispersion liquid.
6. The N, S-codoped graphene/WSe of claim 1 2 The preparation method of the/NiFe-LDH aerogel is characterized in that the reducing agent is L-cysteineAcid, ascorbic acid, glucose or any mixture thereof; the cross-linking agent is L-cysteine and/or polypyrrole.
7. N, S-codoped graphene/WSe prepared by the preparation method of claims 1-6 2 /NiFe-LDH aerogel.
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