CN109205596A - A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation - Google Patents
A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation Download PDFInfo
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Abstract
The present invention relates to a kind of graphene/WSe2/ NiFe-LDH aeroge and preparation method thereof, which comprises by graphene oxide layer dispersion liquid and WSe2Nanometer sheet dispersion liquid mixing, is added at least one of reducing agent, crosslinking agent and pH adjusting agent, is uniformly mixed, and reacts and graphene/WSe is made2Hydrogel, freeze-drying, obtains graphene/WSe2Aeroge；By the graphene/WSe2Aeroge is immersed in NiFe-LDH nanometer sheet dispersion liquid, and graphene/WSe is made2/ NiFe-LDH hydrogel is freeze-dried to obtain graphene/WSe2/ NiFe-LDH aeroge.N produced by the present invention, S codope graphene/WSe2The preparation method of/NiFe-LDH (N, S codope graphene/bis- tungsten selenides/ferronickel double-hydroxide) prepares simple, at low cost, N obtained, S codope graphene/WSe2/ NiFe-LDH has the excellent chemical properties such as big specific capacitance, good cycle, internal resistance be small.
Description
Technical field
The present invention relates to a kind of electrode materials, and in particular to a kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation
Method.
Background technique
With the increase of economic fast development and population in the world, the continuous of environment deteriorates the problems such as increasingly deficient with the energy
The extensive concern for causing global people from all walks of life seeks sustainable, cleaning, efficient renewable energy source material undoubtedly becomes people
The hot spot of concern.Wherein, supercapacitor is a kind of novel energy storage apparatus, it have high power density, long circulation life, quickly
Charge and discharge process and the advantages such as low cost, have become a hot topic of research, and had a good application prospect in every field.And
The quality of its performance depends primarily on the selection of electrode material, therefore prepares suitable electrode material with very important meaning
Justice.Studies have shown that influencing electrode material chemical property mainly by there is following factor: the electric conductivity of electrode material, electrode
The specific capacity etc. that the pore structure of material, the effective ratio area of electrode material and electrode material itself have.
Due to the π-π interaction that graphene (GO) piece interlayer is strong, so that it is reunited again after reduction and arrive together, and
Graphene dispersion is poor, and surface torpescence is difficult the disadvantages of compound with other materials, and the application of graphene is caused to meet with bottle
Neck.Therefore two-dimensional graphene sheet layer is assembled into three-dimensional structure, such as graphene aerogel, graphene height can be made full use of
Specific surface area, assign its stronger macro-mechanical property, realize graphene time application.Graphene aerogel has both graphite
The multinomial excellent properties of alkene and aeroge, such as low-density, high porosity, huge specific surface area, good mechanical performance, superior
Electric conductivity and structure-controllable etc., thus graphene aerogel is considered as the optimal candidate electrode material of double electric layers supercapacitor
One of material.Graphene is doped additionally by hetero atom can reduce the forbidden band broadband of graphene, increase its electric conductivity with
And the strong synergistic effect between hetero atom and graphene defect can make the chemical property of doped graphene get a promotion.
Two chalkogenide of stratiform transition metal, be by be covalently keyed X-M-X layer (M=Mo, W,；X=S, Se, Te) it is logical
Cross the graphite-like structure of interlayer Van der Waals force composition.Two tungsten selenides compare curing as typical transition metal dichalcogenide
Molybdenum has narrower forbidden bandwidth and higher electric conductivity, makes it have higher fake capacitance performance.By liquid phase ultrasonic method by its
Two-dimensional ultrathin nano-lamellar structure is removed into, its specific surface area and its electro-chemical activity site of exposure can be maximized, be conducive to
Improve its performance in supercapacitor applications.
Stratiform transition metal double-hydroxide (Layered double hydroxide, LDH) is a kind of with larger ratio
Surface area can carry out a kind of artificial synthesized stratified material according to specific function.LDH has various unique physics, change
The properties such as property, including laminate electropositive, main element variability, interlamellar spacing adjustability are learned, therefore in catalysis, the energy, Shui Chu
Reason etc. has very big application potential.In recent years, it deepens continuously, finds to the research of LDH structure and performance with people
This kind of material has the capacitance of two kinds of property of electric double layer and fake capacitance simultaneously, before energy storage field shows and lures man-based development
Scape, but since in charge and discharge process, the metallic element in electrode material is constantly occurring redox reaction, cause activity
Mass volume is shunk and expansion, causes its cyclical stability bad.
Although all showing certain electrochemical capacitance performance when above-mentioned material is as individual electrode material, its performance is not
It is ideal.
Summary of the invention
In view of this, it is really necessary to provide a kind of graphene/WSe2/ NiFe-LDH (N, S codope graphene/bis- selenizings
Tungsten/ferronickel double-hydroxide) preparation method, prepare simple, at low cost, graphene/WSe obtained2/ NiFe-LDH has
The excellent chemical properties such as big specific capacitance, good cycle, internal resistance be small.
First aspect present invention provides a kind of graphene/WSe2The preparation method of/NiFe-LDH aeroge, feature exist
In, comprising the following steps: by graphene oxide layer dispersion liquid and WSe2Reducing agent, crosslinking is added in nanometer sheet dispersion liquid mixing
At least one of agent and pH adjusting agent are uniformly mixed, and react and graphene/WSe is made2Hydrogel, freeze-drying, obtains stone
Black alkene/WSe2Aeroge；By the graphene/WSe2Aeroge is immersed in NiFe-LDH nanometer sheet dispersion liquid, and graphite is made
Alkene/WSe2/ NiFe-LDH hydrogel is freeze-dried to obtain graphene/WSe2/ NiFe-LDH aeroge.
Further, the reducing agent or crosslinking agent contain N and S, it is preferable that the reducing agent or crosslinking agent is L-
Cysteine, resulting graphene/WSe2/ NiFe-LDH aeroge is graphene/WSe of N, S codope2/ NiFe-LDH airsetting
Glue.
Further, the graphene oxide layer dispersion liquid, by by graphite oxide in deionized water ultrasonic disperse
It is made；The WSe2Nanometer sheet dispersion liquid is made by liquid phase stripping method；The NiFe-LDH nanometer sheet dispersion liquid passes through hydro-thermal
Method is made.
Further, the graphite oxide is prepared by the following method:
S11, under ice bath, stirring, by NaNO3It is dissolved in the concentrated sulfuric acid, until NaNO3It is completely dissolved；
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath, reaction to liquid are removed after having added
It becomes viscous；
Deionized water is added in S13, and after reaction, deionized water is added again at lower than 120 DEG C；
H is added in S14, room temperature2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating；
S15, the precipitating are washed with HCl solution, dry to obtain graphite oxide.
Further, the WSe2Nanometer sheet dispersion liquid is prepared by the following method: by two tungsten selenides be dispersed in isopropanol/
In water mixed solution, WSe is made in ultrasonic oscillation2Nanometer sheet dispersion liquid.
Further, the NiFe-LDH nanometer sheet dispersion liquid is prepared by the following method:
S31, by Ni (NO3)2·6H2O、Fe(NO3)3·9H2O, urea and trisodium citrate are dispersed in water, in 130-
170 DEG C of reactions, washing, drying, obtain powdered substance after having reacted；
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is that NiFe-LDH receives
Rice piece dispersion liquid.
Further, the graphene oxide layer and the WSe2The weight ratio of nanometer sheet is 4:9~36:1.
Further, the graphene/WSe2Weight ratio with the NiFe-LDH is 10:1~1:10.
Further, the reducing agent is L-cysteine, ascorbic acid, glucose or their any mixing.
Further, the crosslinking agent is L-cysteine and/or polypyrrole.
Second aspect of the present invention provides graphene/WSe made from a kind of above method2/ NiFe-LDH aeroge.
Compared with prior art, the present invention uses graphite oxide, WSe2, NiFe-LDH be made ternary N, S codope graphite
Alkene/WSe2/ NiFe-LDH aeroge, has the following beneficial effects:
1) aeroge of the invention prepares ultra-thin two tungsten selenides nanometer sheet dispersion liquid with liquid phase stripping method, inserts compared to existing lithium
Layer method removing is safer, while reducing cost.
2) aeroge of the invention carries out the codope of N and S to graphene using L-cysteine as doped chemical source,
In addition, L-cysteine can be used as the crosslinking agent that graphene is formed in aerogel process, thus using hydro-thermal method by two selenizings
The doping of graphene may be implemented when on graphene sheet layer and be cross-linked to form aeroge while carrying out for tungsten load.
3) by electrostatic interaction by negatively charged N, S codope graphene/bis- tungsten selenides and positively charged ferronickel are double
The self assembly effect of hydroxide is prepared into ternary N, and S codope graphene/bis- tungsten selenides/ferronickel double-hydroxide aeroge is multiple
Condensation material forms good interfacial contact, while reducing reunion, and this method is simple, is easy to be mass produced.
4) ternary N produced by the present invention, S codope graphene/bis- tungsten selenides/ferronickel double-hydroxide composite aerogel tool
There is excellent chemical property, it is small etc. with big specific capacitance, good cycle, internal resistance, it can be used as stability and high efficiency super capacitor
Device electrode material.
5) N produced by the present invention, S codope graphene/WSe2/ NiFe-LDH (N, S codope graphene/bis- tungsten selenides/
Ferronickel double-hydroxide) preparation method, prepare simple, at low cost, N obtained, S codope graphene/WSe2/NiFe-
LDH has the excellent chemical properties such as big specific capacitance, good cycle, internal resistance be small.
Detailed description of the invention
Fig. 1 is the N of one embodiment of the invention, S codope graphene/WSe2The preparation process of/NiFe-LDH aeroge is shown
It is intended to；
Fig. 2 is the N of one embodiment of the invention, S codope graphene/WSe2The scanning electron microscope (SEM) photograph of/NiFe-LDH；
Fig. 3 is the N of one embodiment of the invention, S codope graphene/WSe2It puts the part of the scanning electron microscope of/NiFe-LDH
Big figure.
Fig. 4 is the N of one embodiment of the invention, S codope graphene/WSe2The x-ray photoelectron of/NiFe-LDH aeroge
Power spectrum；
Fig. 5 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode liberation of hydrogen Tafel
Slope curve figure；
Fig. 6 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode is in different electricity
Constant current charge-discharge curve under current density；
Fig. 7 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode is at 2000 times
The change curve of specific capacity during charge and discharge cycles.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
As shown in Figure 1, the N of present pre-ferred embodiments, S codope graphene/WSe2The preparation method of/NiFe-LDH,
Include:
S1, by graphite oxide in deionized water ultrasonic disperse, be made graphene oxide layer dispersion liquid.Preferably, it makes
The concentration of the graphene oxide dispersion obtained is 0.5-3mg mL-1, more preferably 2mg mL-1。
Specifically, the graphite oxide is prepared by the following method:
S11, in ice bath, be vigorously stirred under, by NaNO3It is dissolved in the concentrated sulfuric acid, until NaNO3It is completely dissolved.
Such as: the concentrated sulfuric acid (H that concentration is 98% is added into three mouthfuls of reaction flasks2SO4), and reaction flask is placed in ice-water bath
In with 150rpm revolving speed stirring, be added NaNO3, continue to stir under ice-water bath.Wherein, the concentrated sulfuric acid and NaNO3Weight ratio
Are as follows: 60:1~100:1.
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath, reaction to liquid are removed after having added
It becomes viscous.
Such as: natural graphite powder is added, maintains ice-water bath constant, by KMnO4It is slowly added in batches, keeps reaction temperature control
System continues to stir in ice-water bath no longer to rise to temperature at 10 DEG C or less (more preferably 5 DEG C or less) after addition.So
Deicing water-bath is moved back, it is in sticky ink that reaction flask is placed in reaction to reaction solution in the water-bath of 25-45 DEG C (more preferably 35 DEG C)
Green.Wherein: NaNO3, graphite powder, KMnO4Weight ratio are as follows: (0.5-1.5): (1-3): (4-8).
The deionized water of the first weight is added in S13, and after reacting a period of time, the second weight is added at lower than 120 DEG C
Deionized water.Preferably, first weight is 1.5-2.5 times of concentrated sulfuric acid volume, and second weight is reaction solution volume
2-4 times.
Such as: the deionized water of the first weight is added, control reaction temperature is lower than 98 DEG C, under oil bath, after reacting 15min,
The deionized water of 1.5 times of reaction solution or more weight is added at 98 DEG C.
The present embodiment controls reaction solution in slight boiling condition, after concentrated sulfuric acid system being added to avoid deionized water, body
It is that heat release is more violent, it is more dangerous after generation splash phenomena, especially iodine, so in order to ensure security control reaction
System is slightly boiled, and temperature is not easy more than 98 DEG C.
S14, room temperature are slowly added to H2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating.
Such as: at room temperature, it is slowly added to 30wt%H2O2Aqueous solution after being stirred to react 1h, is centrifuged in centrifuge, outwells
Supernatant liquor retains precipitating.
S15, the precipitating are washed with HCl solution, dry to obtain graphite oxide.
Such as: precipitating is washed into centrifugation several times with 10wt%HCl solution, then is washed with deionized to supernatant liquor
PH is most neutral, and sediment is dried to obtain solid oxidation graphite in 50-90 DEG C of baking oven.
S2 prepares ultra-thin WSe by liquid phase stripping method2Nanometer sheet dispersion liquid.
Such as: two tungsten selenide of block is dispersed in isopropanol/water mixed solution, ultra-thin WSe is made in ultrasonic oscillation2It receives
Rice piece dispersion liquid.In one embodiment, two tungsten selenide of block is dispersed in isopropanol/water (V/V, 6/4) mixed solution,
Ultra-thin two tungsten selenides (WSe was removed by 300W ultrasonic oscillation 2-4 hours2) nanometer sheet dispersion liquid.Preferably, described
WSe2Nanometer sheet dispersion liquid concentration is 0.2-1.0mg mL-1；More preferably 0.5mg mL-1.Preferably, WSe2The thickness of nanometer sheet
Degree is 1.6nm-8nm.
The embodiment of the present invention prepares ultra-thin WSe using liquid phase stripping method2Nanometer sheet dispersion liquid, at low cost, safe operation.
S3 prepares stratiform NiFe-LDH nanometer sheet dispersion liquid by hydro-thermal method；Preferably, NiFe-LDH nanometer sheet dispersion liquid
Concentration be (0.5-2) mg.ml-1；More preferably are as follows: 1mg.ml-1。
Specifically,
S31, by Ni (NO3)2·6H2O、Fe(NO3)3·9H2O, urea, trisodium citrate are dispersed in water, in 130-170
DEG C reaction, react after washing, dry powdered substance.More specifically, being (7-12): (1-4): (2-6): 1 by weight ratio
Ni (NO3)2·6H2O、Fe(NO3)3·9H2O, urea, trisodium citrate are scattered in distilled water, ultrasound until clarified solution, in
In stainless steel hydrothermal reaction kettle containing polytetrafluoroethylsubstrate substrate, sealing reacts at 130-170 DEG C, filters after having reacted, uses water
With ethanol washing repeatedly, be dried in vacuo be made powdered substance.
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is that NiFe-LDH receives
Rice piece dispersion liquid.Specifically, step S31 powdered substance is entered into the formamide solution of degassing to be ultrasonically treated and is hanged
Turbid, centrifugation, removes unstripped block, obtaining supernatant is NiFe-LDH nanometer sheet dispersion liquid.
Point of above step S1, S2, S3 out-of-order, three sequence of steps can be converted arbitrarily.
S4, by the graphene oxide layer dispersion liquid and WSe2Reducing agent, crosslinking is added in nanometer sheet dispersion liquid mixing
Agent, pH adjusting agent stir evenly, and react and N, S codope graphene/WSe is made2Hydrogel, freeze-drying.
Wherein, the graphene oxide layer and the WSe2The weight ratio of nanometer sheet is 4:9~36:1.The reducing agent
For L-cysteine, ascorbic acid, glucose or their any mixing.The crosslinking agent is L-cysteine and/or poly- pyrrole
It coughs up.The pH adjusting agent is ammonium hydroxide, and dosage is 0.05~0.1 times of graphene oxide dispersion volume.
In the present embodiment, the pH value of solution is adjusted using pH adjusting agent, to influence graphene oxide layer surface
Potential, the aggregation shape of redox graphene in the solution is influenced using the electrostatic repulsion between graphene oxide layer
State.And then it is not necessarily to stabilizer, it can also be made that reducing degree is preferable, the good graphene of dispersion degree.
In a specific embodiment, the reducing agent and crosslinking agent are L-cysteine, are made using L-cysteine
Make to be cross-linked with each other between graphene sheet layer to form 3D network structure for crosslinking agent, be alternatively arranged as the source N, S and graphene is doped,
Due to N, S ratio sp2C has bigger electronegativity, improves its electric conductivity.
S5, by the N, S codope graphene/WSe2Hydrogel is immersed in NiFe-LDH nanometer sheet dispersion liquid, is made
N, S codope graphene/WSe2/ NiFe-LDH hydrogel is freeze-dried to obtain N, S codope graphene/WSe2/ NiFe-LDH gas
Gel；Wherein, N, S codope graphene/WSe2Weight ratio with the NiFe-LDH is 10:1~1:10.
N after freeze-drying, S codope graphene/WSe2After being added in NiFe-LDH nanometer sheet dispersion liquid, due to
Electrostatic adsorption makes positively charged NiFe-LDH nanometer sheet be adsorbed on negatively charged N, S codope graphene/WSe2
Surface is self-assembly of N, S codope graphene/WSe2/ NiFe-LDH hydrogel composite material, obtains N after freeze-drying, S is total
Doped graphene/WSe2/NiFe-LDH composite aerogel.
The present invention is by N, S codope graphene, WSe2, tri- kinds of Material claddings of CoFe-LDH, N obtained, S codope graphite
Alkene/WSe2/ CoFe-LDH composite aerogel, with excellent chemical property, such as big specific capacitance, good cycle,
Internal resistance is small etc., can be used as stability and high efficiency electrode material for super capacitor.Meanwhile aeroge of the invention is with the preparation of liquid phase stripping method
Ultra-thin two tungsten selenides nanometer sheet dispersion liquid removes safer, cost reduction compared to existing lithium graft process.Method of the invention is with L-
Cysteine is doped chemical source, and the codope of N and S is carried out to graphene, and L-cysteine forms airsetting as graphene
Graphene may be implemented when so that two tungsten selenides being supported on graphene sheet layer using hydro-thermal method in crosslinking agent during glue
It adulterates and is cross-linked to form aeroge while carrying out.By electrostatic interaction by negatively charged N, S codope graphene/bis- tungsten selenides
Self assembly effect with positively charged ferronickel double-hydroxide is prepared into ternary N, S codope graphene/bis- tungsten selenides/ferronickel
Double-hydroxide aerogel composite forms good interfacial contact, while reducing reunion, and this method is simple, easy
In large-scale production.
Graphite oxide in following specific embodiments is made by the following method:
The 46mL concentrated sulfuric acid (98%H is added into three mouthfuls of reaction flasks2SO4), and reaction flask is placed in ice-water bath with 150rpm
Revolving speed stirring, then weighs 1g NaNO3It is added in reaction flask, continues to stir 10min under ice-water bath, to NaNO3It is completely dissolved, then
The addition of 2g natural graphite powder is weighed, maintains ice-water bath constant, weighs 6g KMnO4It is slowly added in batches, keeps reaction temperature control
No longer rise hereinafter, continuing the stirring 30min in ice-water bath after addition to temperature at 5 DEG C.Then ice-water bath is removed, it will be anti-
It answers bottle to be placed in 35 ± 3 DEG C of water-bath to react 1 hour, reaction solution is slowly added to 92mL deionized water in sticky blackish green, reacts
System temperature increases, and control temperature does not exceed 98 DEG C, and 15min is reacted under 98 DEG C of oil baths, and 300mL deionization is added while hot
Water removes oil bath, drops to room temperature to reacting liquid temperature, 10mL 30%H is added2O2(being slowly added to), continues to react for stirring 1 hour
It is after the completion 5000r min with revolving speed-1Centrifuge centrifugation, outwell supernatant liquor, lower sediment is washed with 10wt%HCl solution again
Centrifugation is washed, centrifugation is finally washed with deionized in repeated washing centrifugation 10 times, until supernatant liquor pH value is neutrality.It will obtain
Sediment be dried overnight in 80 DEG C of baking oven, obtain solid oxidation graphite.
Two tungsten selenide (WSe used in following embodiment2) be purchased from Mike woods company, purity 99.8%, No. MDL:
MFCD00049703。
Embodiment 1
A kind of N, S codope graphene/WSe2The preparation method of/NiFe-LDH, as shown in Figure 1, comprising:
(1) preparation of graphene oxide (GO) dispersion liquid: 100mL is dispersed by 100mg graphite oxide obtained above
In ionized water, ultrasound obtains the GO lamella dispersion liquid of sepia for 1 hour, and GO concentration is 2mg mL-1。
(2) ultra-thin WSe2The preparation of nanometer sheet dispersion liquid: by 20mg block WSe2Be added 4mL volume fraction be 60% it is different
The in the mixed solvent of propyl alcohol (IPA)/water (V/V, 6/4), put it into Ultrasound Instrument with the frequency of the power of 200W and 40kHz into
Row ultrasonic vibration is handled 4 hours, keeps temperature in ultrasonic procedure to control in room temperature by the way that recirculated cooling water is added.Then, will surpass
Solution after sound is centrifuged 20 minutes with the speed of 4000rpm, the unstripped block WSe in removal bottom2, obtaining supernatant liquor is
Two-dimentional WSe2Nanometer sheet, testing its concentration is about 0.5mg/mL, spare.
(3) preparation of stratiform NiFe-LDH nanometer sheet dispersion liquid: by 0.27g Ni (NO3)2·6H2O, 0.09g Fe
(NO3)3·9H2O, 0.12g urea and 0.03g trisodium citrate are dispersed in 75mL distilled water, ultrasonic treatment about 30min until
Clarification.Obtained solution is transferred in the stainless steel hydrothermal reaction kettle containing polytetrafluoroethylsubstrate substrate, is sealed, and at 150 DEG C
Heating reaction 20 hours.After being cooled to room temperature, solid product is collected by filtration, it is multiple with distilled water and ethanol washing respectively, and
It is dried in vacuo 8 hours at 60 DEG C and obtains powdered substance, be scattered in the formamide that the 50mL weight concentration of degassing is 50%
It is ultrasonically treated to obtain suspension in solution, then, is centrifuged 20 minutes with the speed of 4000rpm to remove unstripped block
Material, obtaining supernatant is stratiform NiFe-LDH nanometer sheet, compound concentration 1mg/mL.
(4) by 5mL GO (2.0mg mL-1) lamella dispersion liquid and 5mL WSe2(0.5mg mL-1) nanometer sheet dispersion liquid is mixed
It closes, by 50mg L-cysteine and 300 μ L NH3·H2O (27wt%) is added gradually to 5mL GO (2.0mg mL-1) and 5mL
WSe2(0.5mg mL-1) mixed solution in, then ultrasonic mixing is uniform.Resulting mixed solution is transferred to containing polytetrafluoro
In the stainless steel hydrothermal reaction kettle of ethylene substrate, sealing, and heating reaction 3 hours at 180 DEG C.Cooled to room temperature obtains
To N, S codope graphene (N, S-rGO)/WSe2Hydrogel.Then, by N, S-rGO/WSe2Hydrogel is washed with distilled water number
Secondary, then freeze-drying obtains N, S codope graphene/WSe2Aeroge (N, S-rGO/WSe2Aeroge).
(5) N that will be obtained, S codope graphene/WSe2Aeroge is immersed in stratiform NiFe-LDH nanometer sheet dispersion liquid
In (1mg/mL), impregnate for 24 hours so that stratiform NiFe-LDH nanometer sheet is adsorbed on N by electrostatic self-assembled, S codope graphene/
WSe2On reach balance.Hereafter, by the N of acquisition, S codope graphene/WSe2The distillation of/stratiform NiFe-LDH composite hydrogel
Water washing for several times, is then freeze-dried, and obtains N, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge.
Performance test:
By N obtained, S codope graphene/WSe2/ NiFe-LDH aeroge is tested with scanning electron microscope (SEM).
As can be seen from Figure 2, N obtained, S codope graphene/WSe2/ NiFe-LDH aeroge forms 3D cellular structure, the duct N, S
Codope graphene/WSe2/ NiFe-LDH aeroge, and as can be seen from Figure 3, N, S codope graphene, WSe2And NiFe-LDH tri-
Kind elementary material is effectively compound, forms stable trielement composite material.
Fig. 4 is the N of one embodiment of the invention, S codope graphene/WSe2The x-ray photoelectron of/NiFe-LDH aeroge
Power spectrum；The composite aerogel can be verified by Fig. 4 and contains N, S, C, and W, Se, Ni, Fe element illustrates that three kinds of elementary materials are all deposited
It is in aeroge.
Fig. 5 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode cyclic voltammetric
Method curve；As can be seen from Figure 5, the nano tube composite aerogel electrode material is in sweep speed from 5mV s-1To 100mV s-1When, sweep speed
Change, the shape invariance of curve, illustrates that the combination electrode material has preferable high rate performance.
Fig. 6 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode is in different electricity
Constant current charge-discharge curve under current density；As can be seen from Figure 6, constant current of the nano tube composite aerogel electrode material under different current densities
Charging and discharging curve, curve almost symmetry, and have charge and discharge platform, illustrate with fake capacitance characteristic.
Fig. 7 is the N of one embodiment of the invention, S codope graphene/WSe2/ NiFe-LDH silica aerogel electrode is at 2000 times
The change curve of specific capacity during charge and discharge cycles.As can be seen from Figure 7, the nano tube composite aerogel electrode material is in 15A g-1Electric current is close
After lower circulation 2000 times of degree, capacitance conservation rate is 92.3%, embodies its excellent cycle performance.
Embodiment 2
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the reduction in embodiment 1
Agent L-cysteine changes ascorbic acid into.
Graphene/WSe obtained2/ stratiform NiFe-LDH aeroge is tested it is found that graphene/WSe obtained2/ layer
Shape NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance conservation rate are as follows: 91.5%.
Embodiment 3
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the reduction in embodiment 1
Agent L-cysteine changes glucose into.
Graphene/WSe obtained2/ stratiform NiFe-LDH aeroge is tested it is found that graphene/WSe obtained2/ layer
Shape NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance conservation rate are as follows: 90.7%.
Embodiment 4
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the crosslinking in embodiment 1
Agent L-cysteine changes polypyrrole into.
Graphene/WSe obtained2/ stratiform NiFe-LDH aeroge is tested it is found that graphene/WSe obtained2/ layer
Shape NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance conservation rate are as follows: 91.8%.
Embodiment 5
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the concentration of GO dispersion liquid
For 3mg/mL, WSe2The concentration of nanometer sheet dispersion liquid is 1mg/mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 91.5%.
Embodiment 6
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the concentration of GO dispersion liquid
For 0.5mg/mL, the concentration of stratiform NiFe-LDH nanometer sheet dispersion liquid is 0.5mg/mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.4%.
Embodiment 7
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO dispersion liquid (concentration
Volume 2.0mg/mL) is 1mL, WSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 9mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.2%.
Embodiment 8
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 1mL, WSe2The concentration of nanometer sheet dispersion liquid is 0.2mg/mL, volume 6mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.9%.
Embodiment 9
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 1mL, WSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 3mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.6%.
Embodiment 10
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 3mL, WSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.1%.
Embodiment 11
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 6mL, WSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.7%.
Embodiment 12
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 9mL, WSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL, NiFe-LDH nanometer sheet dispersion liquid
Concentration is 2mg/mL.
N obtained, S codope graphene/WSe2/ stratiform NiFe-LDH aeroge is tested it is found that N obtained, S are total
Doped graphene/WSe2/ stratiform NiFe-LDH aeroge has good high rate performance, good fake capacitance characteristic, capacitance
Conservation rate are as follows: 90.2%.
The above is only some embodiments of the invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of N, S codope graphene/WSe2The preparation method of/NiFe-LDH aeroge, which is characterized in that including following step
It is rapid: by graphene oxide layer dispersion liquid and WSe2Nanometer sheet dispersion liquid mixing, is added reducing agent, crosslinking agent and pH adjusting agent
At least one of, it is uniformly mixed, reacts and graphene/WSe is made2Hydrogel, freeze-drying, obtains graphene/WSe2Airsetting
Glue；By the graphene/WSe2Aeroge is immersed in NiFe-LDH nanometer sheet dispersion liquid, and graphene/WSe is made2/NiFe-
LDH hydrogel is freeze-dried to obtain graphene/WSe2/ NiFe-LDH aeroge.
2. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that described
Reducing agent or crosslinking agent contain N and S, resulting graphene/WSe2/ NiFe-LDH aeroge be N, S codope graphene/
WSe2/ NiFe-LDH aeroge.
3. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that the oxygen
Graphite alkene lamella dispersion liquid, by the way that ultrasonic disperse is made in deionized water by graphite oxide；The WSe2Nanometer sheet dispersion
Liquid is made by liquid phase stripping method；The NiFe-LDH nanometer sheet dispersion liquid is made by hydro-thermal method.
4. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that the oxygen
Graphite is prepared by the following method:
S11, under ice bath, stirring, by NaNO3It is dissolved in the concentrated sulfuric acid, until NaNO3It is completely dissolved；
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath is removed after having added, reaction to liquid becomes sticky
It is thick；
Deionized water is added in S13, and after reaction, deionized water is added again at lower than 120 DEG C；
H is added in S14, room temperature2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating；
S15, the precipitating are washed with HCl solution, dry to obtain graphite oxide.
5. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that described
WSe2Nanometer sheet dispersion liquid is prepared by the following method: two tungsten selenides being dispersed in isopropanol/water mixed solution, ultrasonic wave shake
Swing obtained WSe2Nanometer sheet dispersion liquid.
6. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that described
NiFe-LDH nanometer sheet dispersion liquid is prepared by the following method:
S31, by Ni (NO3)2·6H2O、Fe(NO3)3·9H2O, urea and trisodium citrate are dispersed in water, in 130-170
DEG C reaction, react after washing, dry, obtain powdered substance；
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is NiFe-LDH nanometer sheet
Dispersion liquid.
7. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that the oxygen
Graphite alkene lamella and the WSe2The weight ratio of nanometer sheet is 4:9~36:1.
8. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that the stone
Black alkene/WSe2Weight ratio with the NiFe-LDH is 10:1~1:10.
9. graphene/WSe as described in claim 12The preparation method of/NiFe-LDH aeroge, which is characterized in that described to go back
Former agent is L-cysteine, ascorbic acid, glucose or their any mixing；The crosslinking agent be L-cysteine and/or
Polypyrrole.
10. graphene/WSe prepared by preparation method described in claim 1-92/ NiFe-LDH aeroge.
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