CN106920696A - Nano hybridization aeroge electrode material for super capacitor and its preparation method and application - Google Patents
Nano hybridization aeroge electrode material for super capacitor and its preparation method and application Download PDFInfo
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- CN106920696A CN106920696A CN201710254725.7A CN201710254725A CN106920696A CN 106920696 A CN106920696 A CN 106920696A CN 201710254725 A CN201710254725 A CN 201710254725A CN 106920696 A CN106920696 A CN 106920696A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of nano hybridization aeroge electrode material for super capacitor and its preparation method and application.The nano hybridization aeroge electrode material for super capacitor that the present invention is provided includes cellulose nano-fibrous, molybdenum bisuphide, redox graphene.The present invention is used as base material using the NCF prepared by TEMPO catalytic oxidations, effectively prevents the irreversible from accumulation and MoS of graphene nano lamella2Reunite；Macroscopic electrode material is improved to invade the performance of profit by electrolyte, improve the utilization rate of macroscopic electrode material intermediary hole, cellulose nano-fibrous after adsorbing electrolyte can be seen as a nano level electrolyte storage place of 1D, can significantly reduce the diffusion length of electrolyte ion；Aerogel products have tough and tensile skeleton structure and relatively low density, specific surface area it is big, beneficial to the transport of electrolyte ion and electric charge；Product has excellent chemical property, is had a good application prospect in energy field.
Description
Technical field
The invention belongs to electrochemical energy field of material technology, and in particular to a kind of cellulose nano-fibrous base nano hybridization
Aeroge electrode material for super capacitor and its preparation method and application.
Background technology
Aeroge (English name Aerogel, be also called xerogel) is that gel sloughs most of solvent, makes liquid in gel
Content is gas than the medium being full of in solids content much less, or the space net structure of gel, and appearance is in solid-like.Airsetting
The features such as glue has high porosity, huge specific surface area, low-density, excellent heat insulation, its application prospect is quite varied.
In electrochemical energy storage field, Graphene and MoS2(molybdenum bisuphide) has specific surface area higher and general because of it
Electronic structure, and become the study hotspot in the field.Graphene, as a kind of unique carbon nanomaterial, with larger
Theoretical specific surface area (about 2600m2g-1), electric conductivity higher, remarkable mechanical flexibility and good chemical stability
Deng premium properties, this causes that graphene carbon material has good application potential, but graphite on electrode material for super capacitor
The capacitance of olefinic carbon material is relatively low；Stratiform MoS2Can be electric double layer electricity due to the layer structure with class graphene film
Lotus storage provides big specific surface area, it is possible to which used as the electrode material of capacitor, but it is separately as energy storage material
Apply and nevertheless suffer from considerable restraint in ultracapacitor, therefore, can be by MoS2Nanometer sheet carries out compound preparation with Graphene
Composite.
But in the prior art, interacted due to there is strong π-π between graphene nano lamella, MoS2And pole
Easily reunite, this causes that the difficulty that the diffusion of electrolyte ion becomes in the macroscopic electrode material for preparing even may.
The content of the invention
For defect of the prior art, it is super that the present invention provides a kind of nano hybridization aeroge of electrochemical performance
Capacitor electrode material and its preparation method and application.
To achieve the above object, the technical solution adopted by the present invention is：
The nano hybridization aeroge electrode material for super capacitor that the present invention is provided includes following component：Cellulose Nanowire
Dimension, molybdenum bisuphide, redox graphene.That is, the present invention provide aeroge be include it is cellulose nano-fibrous
(NCF), molybdenum bisuphide (MoS2), redox graphene (RGO) these three components, each component is equally distributed.Described
NCF and RGO forms the 3D porous network structures of stabilization, MoS2Then it is evenly dispersed in these network structures and airsetting film layers
On.The NCF/MoS that the present invention is provided2The aperture of/RGO nano hybridization aeroges concentrates on the mesoporous interval in the range of 2-50nm,
Its BET specific surface area is 197m2/g。
It is further preferred that in above-mentioned nano hybridization aeroge electrode material for super capacitor, the cellulose Nanowire
Dimension, the solid masses ratio of molybdenum bisuphide are 7：3, the solid of described cellulose nano-fibrous and molybdenum bisuphide total amount and Graphene
Mass ratio is (7-27)：3.
Still more preferably, in above-mentioned nano hybridization aeroge electrode material for super capacitor, the cellulose nanometer
Fiber, molybdenum bisuphide, the mass ratio of redox graphene are 70:30:42.86.
Further, during the electro-chemical test of above-mentioned nano hybridization aeroge electrode material for super capacitor is characterized, than electricity
Capacitance：0.5mA/cm2Specific capacitance value is up to 657.7F/g under constant current charge-discharge；It is forthright again：Increase current strength to 10mA/
cm2, specific capacitance value is 71% initial specific capacitance value；Cyclical stability：5mA/cm25000 constant current cycle charge discharges of lower experience
Electric specific capacitance value retains 98% initial specific capacitance value.
The present invention also provides the preparation method of nano hybridization aeroge electrode material for super capacitor as described above, including
Step：
S1. NCF/MoS is prepared2Suspension：By nano flower-like molybdenum bisuphide powder ultrasonic disperse in cellulose nano-fibrous
NCF/MoS is obtained in suspension2Suspension；
S2. GO soliquids are prepared：Graphene oxide colloidal dispersions are obtained into GO soliquids in water；
S3. NCF/MoS is prepared2/ GO- (VC-Na) suspension：By the GO soliquids and the NCF/MoS2Suspend
Liquid is mixed, then ultrasonically treated to forming uniform NCF/MoS2/ GO suspension altogether, is subsequently adding VC-Na and stirs to complete
CL forms NCF/MoS2/GO- (VC-Na) suspension in common suspension；
S4. NCF/MoS is prepared2/ RGO nano hybridization aeroges：By the NCF/MoS2/ GO- (VC-Na) suspension is placed in
NCF/MoS is formed in hydrochloric acid atmosphere2/ GO- (VC-Na) nano hybridized hydrogel, then places a period of time shape in uniform temperature
Into NCF/MoS2/ RGO nano hybridized hydrogels, are then washed with water to neutrality, with absolute ethyl alcohol by the NCF/MoS2/ RGO receives
Rice hybridized hydrogel is replaced into NCF/MoS2/ RGO nano hybridization alcogel, using supercritical CO2Dry technology is by the NCF/
MoS2It is NCF/MoS that/RGO nano hybridizations alcogel is dried2/ RGO nano hybridization aeroges.Herein hydrochloric acid atmosphere be concentrated hydrochloric acid with
Concentration atmosphere during equilibrium relation is reached between air.
The NCF prepared by TEMPO catalytic oxidations not only has appropriate nanometer geometry, and (3-4nm is wide, micro-
Meter level is long), a good hydrophily (under drying regime cellulose nano-fibrous very readily can be moistened by electrolyte),
But also with some other premium properties：Relatively low density, cheap, bio-compatible and advantages of environment protection.Therefore, with
Nano particle, macromolecule etc. are compared, and the NCF of 1D nanostructureds (i.e. one-dimensional nano structure) is more suitable as preventing graphene nano
Lamella produces irreversible from accumulation and MoS2The nanometer barrier material of reunion.
Additionally, being that one kind has compared with high length-diameter ratio, surface presence using the NCF that TEMPO catalysed oxidation processes are prepared
The nano-scale fiber of a large amount of-COONa groups, this feature shows that NCF can be by the simple concentration for changing NCF suspension
Or the pH value of NCF suspension prepares NCF hydrogels, and then to dry be NCF aeroges.Its aeroge not only have it is cheap,
The advantages of environment-friendly and bio-compatible, but also with tough and tensile skeleton structure, Micro porosity structure-controllable and chemistry
The advantages of modified is strong.
Further, in the preparation method of above-mentioned nano hybridization aeroge electrode material for super capacitor, the step S1
In cellulose nano-fibrous suspension be prepared as follows：
It is raw material to use wet wood pulp, and oxycellulose is prepared using TEMPO methods, will using Ultrasonic cell smash
Obtained oxycellulose ultrasound, supernatant liquor is taken after gained mixture is centrifuged, that is, obtain NCF suspension.
Further, in the preparation method of above-mentioned nano hybridization aeroge electrode material for super capacitor, the step S1
Middle nano flower-like molybdenum bisuphide powder is prepared as follows：Using sodium molybdate (Na2MoO4) and Cys be raw material, water
Hot method prepares dispersed nano flower-like MoS2Powder.
Further, in the preparation method of above-mentioned nano hybridization aeroge electrode material for super capacitor, the step S2
Middle GO soliquids are prepared as follows：With graphite powder as raw material, graphene oxide is prepared using improved Hummers methods
Colloid, homogeneous scattered GO colloidal suspensions are obtained after carrying out ultrasonically treated, dispersion dialysis after then being diluted with deionized water to it
Liquid.
Further, in the preparation method of above-mentioned nano hybridization aeroge electrode material for super capacitor, the step S4
NCF/MoS obtained by middle preparation2/ GO- (VC-Na) nano hybridized hydrogel places 6-24h at a temperature of 60-95 DEG C and obtains NCF/
MoS2/ RGO nano hybridized hydrogels.
Further, in the preparation method of above-mentioned nano hybridization aeroge electrode material for super capacitor, the step S3
In the addition of VC-Na be excessive.
It is prepared by nano hybridization aeroge electrode material for super capacitor as described above or preparation method as described above
Nano hybridization aeroge electrode material for super capacitor, be used for prepare all-solid-state flexible ultracapacitor.
In sum, the present invention has the advantages that：
1. base material is used as using the NCF prepared by TEMPO catalytic oxidations, can effectively prevent graphene nano
Lamella produces irreversible from accumulation and MoS2Reunite；Simultaneously have excellent hydrophilic 1D it is cellulose nano-fibrous can be significantly
Improve macroscopic electrode material to invade the performance of profit by electrolyte, improve the utilization rate of macroscopic electrode material intermediary hole, absorption electrolysis
Cellulose nano-fibrous after matter can be seen as a nano level electrolyte storage place of 1D, and the presence in the place can show
The reduction electrolyte ion diffusion length of work.
2. the NCF/MoS for preparing2/ RGO nano hybridization aeroges have tough and tensile skeleton structure and relatively low density, while
Specific surface area is big, is conducive to the transport of electrolyte ion and electric charge.
3. the NCF/MoS for preparing2/ RGO nano hybridization aeroge combination electrode materials have excellent chemical property,
Energy field has a good application prospect.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the specific embodiment of the invention, specific embodiment will be retouched below
The accompanying drawing to be used needed for stating is briefly described.
Fig. 1 is the NCF/MoS of embodiment preparation in the present invention2The SEM figures of/RGO nano hybridization aerogel composites；
Fig. 2 is the NCF/MoS of embodiment preparation in the present invention2/ RGO nano hybridization aeroges hybrid supercapacitor electricity
Pole material is in 0.5mA/cm2Constant current charge-discharge figure；
Fig. 3 is the NCF/MoS of embodiment preparation in the present invention2/ RGO nano hybridization aeroges hybrid supercapacitor electricity
Specific capacitance value of the pole material under different current densities；
Fig. 4 is the NCF/MoS of embodiment preparation in the present invention2/ RGO nano hybridization aeroges hybrid supercapacitor electricity
Pole material is in 5mA/cm2Lower constant current charge-discharge circulates 5000 attenuations of specific capacitance；
Fig. 5 is the NCF/MoS of embodiment preparation in the present invention2/ RGO nano hybridization aeroge macro morphology figures.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.It should be noted that the reality described in the present invention
Example only the preferred embodiments of the present invention are applied, is not intended to limit the invention, for a person skilled in the art, this
Invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made, equivalent,
Improve etc., should be included within the scope of the present invention.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.Implement
The percentage is mass percent if without specified otherwise in example 1 to 3.
Embodiment 1
The first step：1) TEMPO of 0.05g is weighed, the NaBr of 0.5g is added sequentially in the deionized water of 400mL, 10 DEG C
Under, it is sufficiently stirred for said mixture using magnetic stirring apparatus；2) after TEMPO, NaBr are completely dissolved, added in reaction system
10g never dried wood pulp cellulose；3) it is stirred vigorously after wood pulp cellulose is uniformly dispersed, then to adding 70g in system
NaClO, the pH of reaction system is controlled 10 or so by the NaOH solution that 0.5mol/L is constantly added dropwise, until pH is protected substantially
When holding constant, reaction terminates；4) it is washed with deionized 3-5 times and obtains oxycellulose, then will be aoxidized using deionized water
Cellulose is configured to the slurry of 2mg/ml, and in ice-water bath, it is fiber that ultrasound 20min peels off oxycellulose under 300W power
Plain nanofiber, the cellulose nano-fibrous suspension that then will be prepared is under 10000r, and centrifugation 20min removals are unstripped
Oxycellulose, take supernatant liquor, that is, obtain NCF suspension.
Second step：1.2g Na2MoO4﹒ 2H2O is dissolved in 70ml deionized waters；2) in above-mentioned solution again plus the Guangs of 3g L- half
Propylhomoserin, is moved in polytetrafluoroethylene (PTFE) water heating kettle after being sufficiently stirred for, and 200 DEG C of hydro-thermal reaction 24h, last precipitation is washed through washing, alcohol
After be dried to obtain MoS2Powder.
3rd step：Take step 2) prepare nano flower-like MoS2Powder 42.85mg ultrasonic disperses are in step 1) prepare 50g
(NCF and MoS in NCF (solids content 0.2%) suspension2Mass ratio is 70:30).
4th step：1) the 25ml concentrated sulfuric acids, 5g potassium peroxydisulfates (K will be contained2S2O8) and 5g phosphorus pentoxides (P2O5) 100ml
Beaker is persistently stirred down and is heated to 80 DEG C；2) 80 DEG C of temperature, the beaker during 1) 5g graphite powders are slowly added under lasting stirring
In, after persistently stirring 4.5 hours, mixture is transferred in the beaker of 5L, the about deionized water of 1L is slowly added to, overnight；
3) will be dried at 60 DEG C after pretreated graphite filtration treatment；4) dried pretreating graphite powder is slowly added into and is contained
There is in the 1000ml beakers of the 230ml concentrated sulfuric acids (in ice-water bath), then again by 30g KMnO4It is slowly added into above-mentioned beaker,
Stir to KMnO4It is completely dissolved；5) after above-mentioned reaction system is reacted 2 hours at 35 DEG C, then 460ml deionized waters are slowly dripped
It is added in reaction system (holding temperature of reaction system is constant), after dripping, adds 1.4L deionized waters, continues at room temperature
Stirring 2 hours；6) under agitation toward the H of addition 25ml 30% in reaction system2O2Remove excessive KMnO4, at this moment mix
Closing liquid can become golden yellow；7) remove supernatant within static 12 hours, disposed the material of dissolving using 5% HCl solution, so
Graphene oxide is washed into neutrality with deionized water afterwards；8) it is oxidation that ultrasound 20min peels off graphite oxide under 800W power
Graphene suspension, the graphene oxide suspension centrifugation that then will be prepared removes unstripped graphite oxide；9) it is last
It is the inorganic ions in the bag filter removal graphene oxide suspension of 8000-14000 using molecular cut off, that is, obtains yellowish-brown
The homogeneous scattered mono-layer graphite oxide dilute suspension of color.
5th step：At room temperature, the graphene oxide suspension (solid content 0.5%) of 17.27mg is added to the 3rd step and obtains
NCF/MoS2(CNFs//MoS in suspension2It is 70 with GO mass ratioes:30), stirred and ultrasonically treated by lasting, until shape
Into uniform CNFs/MoS2, then be added to excessive VC-Na in above-mentioned suspension altogether by the common suspension of/GO, and 3min is straight for stirring
It is dissolved completely in common suspension to VC-Na.
6th step：1) by 10g NCF/MoS2/ GO- (VC-Na) suspension is poured into 20ml glass molds, then will be upper
State glass mold and be placed in 4-8h in hydrochloric acid atmosphere, in the presence of hydrogen bond, NCF/MoS2/ GO- (VC-Na) suspension gradually changes
It is NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel；2) by NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel is in 60-
Placed at 95 DEG C and prepare NCF/MoS in 6-24 hours2/ RGO nano hybridized hydrogels；3) NCF/ is washed using a large amount of deionized waters
MoS2/ RGO nano hybridized hydrogels, until NCF/MoS2/ RGO nano hybridized hydrogels pH is in neutrality；4) utilization absolute ethyl alcohol will
NCF/MoS2/ RGO nano hybridized hydrogels are replaced into NCF/MoS2/ RGO nano hybridization alcogel；5) supercritical CO is finally utilized2
Dry technology is by NCF/MoS2It is NCF/MoS that/RGO nano hybridizations alcogel is dried2/ RGO nano hybridization aeroges.
NCF/MoS obtained in the present embodiment2/ RGO nano hybridization aeroge hybrid supercapacitor electrode materials 0.5mA/
cm2Specific capacitance 657.7F/g under constant current charge-discharge.Fig. 1 is NCF/MoS manufactured in the present embodiment2/ RGO nano hybridization aeroges
SEM schemes, and NCF is formed with RGO lamellas and stablized 3D porous network structures, and MoS2Then uniformly it is embedded in these mesh-structured and aeroges
On lamella；Fig. 2 is NCF/MoS manufactured in the present embodiment2/ RGO nano hybridization aeroge hybrid supercapacitor electrode materials exist
0.5mA/cm2Constant current charge-discharge figure；Fig. 3 is NCF/MoS manufactured in the present embodiment2/ RGO nano hybridization aeroge compound supers
Specific capacitance value of the capacitor electrode material under different current densities, 0.5mA/cm2Lower 657.7F/g, 10mA/cm2Under still have
468F/g (retains 71.2%), illustrates forthright good again；Fig. 4 is NCF/MoS manufactured in the present embodiment2/ RGO nano hybridization aeroges
Hybrid supercapacitor electrode material is in 5mA/cm2(specific capacitance is 533F/g) constant current charge-discharge circulates 5000 specific capacitances
Attenuation, specific capacitance is 531F/g after first circulation, and specific capacitance still retains 525F/g and (retains after 5000 circulations
98.5%) good cycling stability, is illustrated；Fig. 5 is NCF/MoS manufactured in the present embodiment2The macroscopic view of/RGO nano hybridization aeroges
Pattern.
Embodiment 2
The first step：1) TEMPO of 0.05g is weighed, the NaBr of 0.5g is added sequentially in the deionized water of 400mL, 10 DEG C
Under, it is sufficiently stirred for said mixture using magnetic stirring apparatus；2) after TEMPO, NaBr are completely dissolved, added in reaction system
10g never dried wood pulp cellulose；3) it is stirred vigorously after wood pulp cellulose is uniformly dispersed, then to adding 70g in system
NaClO, the pH of reaction system is controlled 10 or so by the NaOH solution that 0.5mol/L is constantly added dropwise, until PH is protected substantially
When holding constant, reaction terminates；4) it is washed with deionized 3-5 times and obtains oxycellulose, then will be aoxidized using deionized water
Cellulose is configured to the slurry of 2mg/ml, and in ice-water bath, it is fiber that ultrasound 20min peels off oxycellulose under 300W power
Plain nanofiber, the cellulose nano-fibrous suspension that then will be prepared is under 10000r, and centrifugation 20min removals are unstripped
Oxycellulose, take supernatant liquor, that is, obtain NCF suspension.
Second step：1.2g Na2MoO4﹒ 2H2O is dissolved in 70ml deionized waters；2) in above-mentioned solution again plus the Guangs of 3g L- half
Propylhomoserin, is moved in polytetrafluoroethylene (PTFE) water heating kettle after being sufficiently stirred for, and 200 DEG C of hydro-thermal reaction 24h, last precipitation is washed through washing, alcohol
After be dried to obtain MoS2Powder.
3rd step：Take step 2) prepare nano flower-like MoS2Powder 42.85mg ultrasonic disperses are in step 1) prepare 50g
(NCF and MoS in NCF (solids content 0.2%) suspension2Mass ratio is 70:30).
4th step：1) the 25ml concentrated sulfuric acids, 5g potassium peroxydisulfates (K will be contained2S2O8) and 5g phosphorus pentoxides (P2O5) 100ml
Beaker is persistently stirred down and is heated to 80 DEG C；2) 80 DEG C of temperature, the beaker during 1) 5g graphite powders are slowly added under lasting stirring
In, after persistently stirring 4.5 hours, mixture is transferred in the beaker of 5L, the about deionized water of 1L is slowly added to, overnight；
3) will be dried at 60 DEG C after pretreated graphite filtration treatment；4) dried pretreating graphite powder is slowly added into and is contained
There is in the 1000ml beakers of the 230ml concentrated sulfuric acids (in ice-water bath), then again by 30g KMnO4It is slowly added into above-mentioned beaker,
Stir to KMnO4It is completely dissolved；5) after above-mentioned reaction system is reacted 2 hours at 35 DEG C, then 460ml deionized waters are slowly dripped
It is added in reaction system (holding temperature of reaction system is constant), after dripping, adds 1.4L deionized waters, continues at room temperature
Stirring 2 hours；6) under agitation toward the H of addition 25ml 30% in reaction system2O2Remove excessive KMnO4, at this moment mix
Closing liquid can become golden yellow；7) remove supernatant within static 12 hours, disposed the material of dissolving using 5% HCl solution, so
Graphene oxide is washed into neutrality with deionized water afterwards；8) it is oxidation that ultrasound 20min peels off graphite oxide under 800W power
Graphene suspension, the graphene oxide suspension centrifugation that then will be prepared removes unstripped graphite oxide；9) it is last
It is the inorganic ions in the bag filter removal graphene oxide suspension of 8000-14000 using molecular cut off, that is, obtains yellowish-brown
The homogeneous scattered mono-layer graphite oxide dilute suspension of color.
5th step：At room temperature, the graphene oxide suspension (solid content 0.5%) of 10.07mg is added to the 3rd step and obtains
NCF/MoS2(CNFs//MoS in suspension2It is 80 with GO mass ratioes:20), stirred and ultrasonically treated by lasting, until shape
Into uniform CNFs/MoS2, then be added to excessive VC-Na in above-mentioned suspension altogether by the common suspension of/GO, and 3min is straight for stirring
It is dissolved completely in common suspension to VC-Na.
6th step：1) by 10g NCF/MoS2/ GO- (VC-Na) suspension is poured into 20ml glass molds, then will be upper
State glass mold and be placed in 4-8h in hydrochloric acid atmosphere, in the presence of hydrogen bond, NCF/MoS2/ GO- (VC-Na) suspension gradually changes
It is NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel；2) by NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel is in 60-
Placed at 95 DEG C and prepare NCF/MoS in 6-24 hours2/ RGO nano hybridized hydrogels；3) NCF/ is washed using a large amount of deionized waters
MoS2/ RGO nano hybridized hydrogels, until NCF/MoS2/ RGO nano hybridized hydrogels pH is in neutrality；4) utilization absolute ethyl alcohol will
NCF/MoS2/ RGO nano hybridized hydrogels are replaced into NCF/MoS2/ RGO nano hybridization alcogel；5) supercritical CO is finally utilized2
Dry technology is by NCF/MoS2It is NCF/MoS that/RGO nano hybridizations alcogel is dried2/ RGO nano hybridization aeroges.
NCF/MoS obtained in the present embodiment2/ RGO nano hybridization aeroge hybrid supercapacitor electrode materials 0.5mA/
cm2Quality is 626.86F/g than capacitance under constant current charge-discharge；It is forthright again：Increase current strength to 10mA/cm2, specific capacitance
Value retains 68% initial specific capacitance；Cyclical stability：5mA/cm25000 constant current cycle charge-discharge specific capacitance values of lower experience
Retain 98% initial specific capacitance.
Embodiment 3
The first step：1) TEMPO of 0.05g is weighed, the NaBr of 0.5g is added sequentially in the deionized water of 400mL, 10 DEG C
Under, it is sufficiently stirred for said mixture using magnetic stirring apparatus；2) after TEMPO, NaBr are completely dissolved, added in reaction system
10g never dried wood pulp cellulose；3) it is stirred vigorously after wood pulp cellulose is uniformly dispersed, then to adding 70g in system
NaClO, the pH of reaction system is controlled 10 or so by the NaOH solution that 0.5mol/L is constantly added dropwise, until PH is protected substantially
When holding constant, reaction terminates；4) it is washed with deionized 3-5 times and obtains oxycellulose, then will be aoxidized using deionized water
Cellulose is configured to the slurry of 2mg/ml, and in ice-water bath, it is fiber that ultrasound 20min peels off oxycellulose under 300W power
Plain nanofiber, the cellulose nano-fibrous suspension that then will be prepared is under 10000r, and centrifugation 20min removals are unstripped
Oxycellulose, take supernatant liquor, that is, obtain NCF suspension.
Second step：1.2g Na2MoO4﹒ 2H2O is dissolved in 70ml deionized waters；2) in above-mentioned solution again plus the Guangs of 3g L- half
Propylhomoserin, is moved in polytetrafluoroethylene (PTFE) water heating kettle after being sufficiently stirred for, and 200 DEG C of hydro-thermal reaction 24h, last precipitation is washed through washing, alcohol
After be dried to obtain MoS2Powder.
3rd step：Take step 2) prepare nano flower-like MoS2Powder 42.85mg ultrasonic disperses are in step 1) prepare 50g
(NCF and MoS in NCF (solids content 0.2%) suspension2Mass ratio is 70:30).
4th step：1) the 25ml concentrated sulfuric acids, 5g potassium peroxydisulfates (K will be contained2S2O8) and 5g phosphorus pentoxides (P2O5) 100ml
Beaker is persistently stirred down and is heated to 80 DEG C；2) 80 DEG C of temperature, the beaker during 1) 5g graphite powders are slowly added under lasting stirring
In, after persistently stirring 4.5 hours, mixture is transferred in the beaker of 5L, the about deionized water of 1L is slowly added to, overnight；
3) will be dried at 60 DEG C after pretreated graphite filtration treatment；4) dried pretreating graphite powder is slowly added into and is contained
There is in the 1000ml beakers of the 230ml concentrated sulfuric acids (in ice-water bath), then again by 30g KMnO4It is slowly added into above-mentioned beaker,
Stir to KMnO4It is completely dissolved；5) after above-mentioned reaction system is reacted 2 hours at 35 DEG C, then 460ml deionized waters are slowly dripped
It is added in reaction system (holding temperature of reaction system is constant), after dripping, adds 1.4L deionized waters, continues at room temperature
Stirring 2 hours；6) under agitation toward the H of addition 25ml 30% in reaction system2O2Remove excessive KMnO4, at this moment mix
Closing liquid can become golden yellow；7) remove supernatant within static 12 hours, disposed the material of dissolving using 5% HCl solution, so
Graphene oxide is washed into neutrality with deionized water afterwards；8) it is oxidation that ultrasound 20min peels off graphite oxide under 800W power
Graphene suspension, the graphene oxide suspension centrifugation that then will be prepared removes unstripped graphite oxide；9) it is last
It is the inorganic ions in the bag filter removal graphene oxide suspension of 8000-14000 using molecular cut off, that is, obtains yellowish-brown
The homogeneous scattered mono-layer graphite oxide dilute suspension of color.
5th step：At room temperature, the graphene oxide suspension (solid content 0.5%) of 4.48mg is added to what the 3rd step was obtained
NCF/MoS2(CNFs//MoS in suspension2It is 90 with GO mass ratioes:10), stirred and ultrasonically treated by lasting, until being formed
Uniform CNFs/MoS2, then be added to excessive VC-Na in above-mentioned suspension altogether by/GO suspension altogether, stirring 3min until
VC-Na is dissolved completely in common suspension.
6th step：1) by 10g NCF/MoS2/ GO- (VC-Na) suspension is poured into 20ml glass molds, then will be upper
State glass mold and be placed in 4h in hydrochloric acid atmosphere, in the presence of hydrogen bond, NCF/MoS2/ GO- (VC-Na) suspension is gradually converted into
NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel；2) by NCF/MoS2/ GO- (VC-Na) nano hybridized hydrogel is in 60-95
Placed at DEG C and prepare NCF/MoS in 6-24 hours2/ RGO nano hybridized hydrogels；3) NCF/ is washed using a large amount of deionized waters
MoS2/ RGO nano hybridized hydrogels, until NCF/MoS2/ RGO nano hybridized hydrogels pH is in neutrality；4) utilization absolute ethyl alcohol will
NCF/MoS2/ RGO nano hybridized hydrogels are replaced into NCF/MoS2/ RGO nano hybridization alcogel；5) supercritical CO is finally utilized2
Dry technology is by NCF/MoS2It is NCF/MoS that/RGO nano hybridizations alcogel is dried2/ RGO nano hybridization aeroges.
NCF/MoS obtained in the present embodiment2/ RGO nano hybridization aeroge hybrid supercapacitor electrode materials 0.5mA/
cm2Quality is 575.28F/g than capacitance under constant current charge-discharge；It is forthright again：Increase current strength to 10mA/cm2, specific capacitance
Value retains 69% initial specific capacitance；Cyclical stability：5mA/cm25000 constant current cycle charge-discharge specific capacitance values of lower experience
Retain 98% initial specific capacitance.
Claims (10)
1. a kind of nano hybridization aeroge electrode material for super capacitor, it is characterised in that：Including following component：Cellulose nanometer
Fiber, molybdenum bisuphide, redox graphene.
2. nano hybridization aeroge electrode material for super capacitor according to claim 1, it is characterised in that：The fiber
Plain nanofiber, the solid masses ratio of molybdenum bisuphide are 7：3, described cellulose nano-fibrous and molybdenum bisuphide total amount and graphite
The solid masses ratio of alkene is (7-27)：3.
3. nano hybridization aeroge electrode material for super capacitor according to claim 2, it is characterised in that：Electrochemistry is surveyed
Take temperature in levying, specific capacitance value：0.5mA/cm2Quality is (575.28-657.7) F/g than capacitance under constant current charge-discharge；Multiplying power
Property：Increase current strength to 10mA/cm2, quality than capacitance retain be not less than 68% initial mass specific capacitance；Stable circulation
Property：5mA/cm2Lower 5000 constant current cycle charge-discharge specific capacitance values of experience retain the initial specific capacitance for being not less than 98%.
4. the preparation side of the nano hybridization aeroge electrode material for super capacitor as described in any one in claims 1 to 3
Method, it is characterised in that：Including step：
S1. NCF/MoS is prepared2Suspension：By nano flower-like molybdenum bisuphide powder ultrasonic disperse in cellulose nano-fibrous suspension
In obtain NCF/MoS2Suspension；
S2. GO soliquids are prepared：Graphene oxide colloidal dispersions are obtained into GO soliquids in water；
S3. NCF/MoS is prepared2/ GO- (VC-Na) suspension：By the GO soliquids and the NCF/MoS2Suspension is mixed
Stirring is closed, it is then ultrasonically treated to forming uniform NCF/MoS2/ GO altogether suspension, be subsequently adding VC-Na stir to completely it is molten
Solution forms NCF/MoS in common suspension2/ GO- (VC-Na) suspension；
S4. NCF/MoS is prepared2/ RGO nano hybridization aeroges：By the NCF/MoS2/ GO- (VC-Na) suspension is placed in hydrochloric acid
NCF/MoS is formed in atmosphere2/ GO- (VC-Na) nano hybridized hydrogel, places to NCF/MoS2/ RGO nano hybridized hydrogel shapes
Into neutrality being then washed with water to, with absolute ethyl alcohol by the NCF/MoS2/ RGO nano hybridized hydrogels are replaced into NCF/
MoS2/ RGO nano hybridization alcogel, using supercritical CO2Dry technology is by the NCF/MoS2/ RGO nano hybridizations alcogel is done
Dry is NCF/MoS2/ RGO nano hybridization aeroges.
5. the preparation method of nano hybridization aeroge electrode material for super capacitor according to claim 4, its feature exists
In：Cellulose nano-fibrous suspension is prepared as follows in the step S1：
It is raw material to use wet wood pulp, and oxycellulose is prepared using TEMPO methods, will be obtained using Ultrasonic cell smash
Oxycellulose ultrasound, will gained mixture be centrifuged after take supernatant liquor, that is, obtain NCF suspension.
6. the preparation method of nano hybridization aeroge electrode material for super capacitor according to claim 4, its feature exists
In：Nano flower-like molybdenum bisuphide powder is prepared as follows in the step S1：
It is raw material to use sodium molybdate and Cys, and hydro-thermal method prepares dispersed nano flower-like MoS2Powder.
7. the preparation method of nano hybridization aeroge electrode material for super capacitor according to claim 4, its feature exists
In：GO soliquids are prepared as follows in the step S2：
With graphite powder as raw material, graphene oxide colloid is prepared using improved Hummers methods, after then being diluted with deionized water
Homogeneous scattered GO soliquids are obtained after ultrasonically treated, dispersion dialysis is carried out to it.
8. the preparation method of nano hybridization aeroge electrode material for super capacitor according to claim 4, its feature exists
In：NCF/MoS obtained by being prepared in the step S42/ GO- (VC-Na) nano hybridized hydrogel is placed at a temperature of 60-95 DEG C
6-24h obtains NCF/MoS2/ RGO nano hybridized hydrogels.
9. the preparation method of nano hybridization aeroge electrode material for super capacitor according to claim 4, its feature exists
In：The addition of the VC-Na in the step S3 is excessive.
10. a kind of nano hybridization aeroge electrode material for super capacitor as described in any one in claims 1 to 3 should
With or nano hybridization aeroge super capacitor electrode that in claim 4 to 9 prepared by preparation method as described in any one
The application of pole material, it is characterised in that：For preparing all-solid-state flexible ultracapacitor.
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| CN108172420A (en) * | 2017-12-18 | 2018-06-15 | 北京理工大学 | Nano carbon balls fiber hybrid aerogel electrode material for super capacitor and its preparation method and application |
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| CN108172420A (en) * | 2017-12-18 | 2018-06-15 | 北京理工大学 | Nano carbon balls fiber hybrid aerogel electrode material for super capacitor and its preparation method and application |
| CN109036874A (en) * | 2018-06-12 | 2018-12-18 | 中国林业科学研究院林业新技术研究所 | A kind of composite electrochemical energy storage Carbon Materials and its preparation method and application |
| CN109610024A (en) * | 2018-11-20 | 2019-04-12 | 华南理工大学 | A kind of cellulose-molybdenum disulfide aeroge composite fibre and its preparation method and application |
| CN112852145A (en) * | 2021-01-08 | 2021-05-28 | 天津科技大学 | Novel nanocellulose-based pressure sensing material and preparation method thereof |
| CN114324517A (en) * | 2021-12-08 | 2022-04-12 | 常州大学 | Electrode for detecting hydrogen peroxide, electrochemical sensor and detection method thereof |
| CN114195122A (en) * | 2021-12-22 | 2022-03-18 | 北京理工大学 | Composite porous carbon aerogel material and preparation method and application thereof |
| CN114195122B (en) * | 2021-12-22 | 2023-08-08 | 北京理工大学 | Composite porous carbon aerogel material and preparation method and application thereof |
| CN115083789A (en) * | 2022-06-23 | 2022-09-20 | 横店集团东磁股份有限公司 | CNF/zinc-cobalt-nickel oxide/graphene aerogel electrode and preparation method and application thereof |
| CN115083789B (en) * | 2022-06-23 | 2023-12-19 | 横店集团东磁股份有限公司 | CNF/zinc cobalt nickel oxide/graphene aerogel electrode and preparation method and application thereof |
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