CN107240508A - A kind of preparation method of graphene/ferrite nano combination electrode material - Google Patents
A kind of preparation method of graphene/ferrite nano combination electrode material Download PDFInfo
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- CN107240508A CN107240508A CN201710194620.7A CN201710194620A CN107240508A CN 107240508 A CN107240508 A CN 107240508A CN 201710194620 A CN201710194620 A CN 201710194620A CN 107240508 A CN107240508 A CN 107240508A
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- 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
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Abstract
The present invention relates to a kind of preparation method of graphene/ferrite nano combination electrode material, including：(1) nano composite material presoma is prepared using hydro-thermal method；Presoma is dried, black powder is obtained, calcined, then ground obtain uniform graphene/ferrite nano composite；(2) activated carbon, CNT, carbon black, graphene/ferrite nano composite, polytetrafluoroethylene (PTFE) are scattered in ethanol or deionized water, heating stirring obtains the slurry of semi-solid state, using the multiple roll-in of twin rollers, produced.The electrode material that the present invention is prepared has larger ratio surface, good mechanical performance, chemical property and stable circulation performance, excellent adsorption desorption performance；Can serialization prepare broad-area electrode film, applied to technical fields such as capacitive deionization, ultracapacitors, technical support is provided for industrialized production.
Description
Technical field
The invention belongs to graphene composite material field, more particularly to a kind of graphene/ferrite nano combination electrode material
The preparation method of material.
Background technology
With the economic fast development of modernization, the continuous improvement of the living standard of scientific and technological level and the people, climate change,
Environmental pollution, distribution of water resources, and the whole world constantly rise to the demand of fresh water, and it is seriously short that many countries face freshwater resources
Scarce crisis.Freshwater resources crisis turns into countries in the world urgent problem to be solved, in face of severe situation, desalinization and water process
Technology receives the concern of more and more people, and it is that solution freshwater resources are short to seek the seawater desalination treatment technology with green high-efficient
Lack the important channel of problem.At present, widely used desalination technology includes：Counter-infiltration, electroosmose process and thermal evaporation etc..
But these technologies have certain limitation, generally existing high energy consumption, cost height and secondary pollution problems.In face of freshwater resources
Demand, the emerging technology such as method such as membrane distillation, electrodialysis, capacitive deionization continues to develop, and have developed with low cost, high
Efficiency and environment-friendly novel green desalting technology.Wherein capacitive deionization technology is a kind of energy conservation type technology, can be again
Raw excellent performance, and in the absence of secondary pollution problem, as the focus studied at present.
At present, it is capacitive deionization to prepare and be theoretically the electrode material of definite value with renewable ability and specific capacitance
(CDI) most important thing in technology.In desalting process, electrode material must have the ratio surface of superelevation and good electrical conductivity,
Usually porous conductive material, can provide more rooms, higher capacitance is provided in adsorption process and it is good from
Sub- transmission rate, improves the specific capacitance of electrode.In general, porous carbon materials can meet the above-mentioned condition of CDI electrodes, be one
Plant preferable CDI electrode materials.CDI electrodes are made, we can not only use carbon particle, but need what is be made up of these particles
Film.The carbon electrode material of research report mainly includes at present:Activated carbon, carbon aerogels, mesoporous carbon, CNT and graphene.
General CDI membrane electrodes preparation prepares similar to energy storage device electrode：Carbon material is thoroughly mixed with polymeric binder, roll-in, is done
It is dry, or be coated directly on current collector.Wherein, graphene be one kind by carbon atom with sp2The hexagonal honeycomb type of hybridized orbit composition
The two-dimension nano materials of plane, with good electric conductivity and than surface, become electrode material the most suitable.It is same with this
When, the special hollow structure of CNT, big specific surface area, low resistivity and high stability are widely used in it
Ultracapacitor, and achieve good desalting effect.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation of graphene/ferrite nano combination electrode material
Method, the electrode material that this method is prepared has larger ratio surface, good mechanical performance, chemical property and circulation
Stability, excellent adsorption desorption performance；Can serialization prepare broad-area electrode film, applied to capacitive deionization, super electricity
The technical fields such as container, technical support is provided for industrialized production.
A kind of preparation method of graphene/ferrite nano combination electrode material of the present invention, including：
(1) molysite and other metal salts are dissolved in deionized water, stir to being uniformly dissolved, obtain mixing salt solution；So
Mixing salt solution is mixed with graphene afterwards, stirring obtains dispersion liquid A；Wherein, the mol ratio of molysite and other metal salts is 1.5
~2.5:1, the mass ratio of graphene and other metal salts is 1.5~2.5:1；
(2) by polyvinyl alcohol and oxalic acid in mass ratio 1:5~10 are dissolved in deionized water, and heating stirring uniformly obtains poly- second
The mixed solution of enol and oxalic acid；Mixed solution is added in above-mentioned dispersion liquid A, stirring, ultrasound obtain dispersion liquid B；
(3) dispersion liquid B is transferred in reactor and carries out hydro-thermal reaction, product is by centrifuging, drying, under protective atmosphere
Calcining, grinding, obtain graphene/ferrite nano composite；
(4) by activated carbon, CNT, carbon black and graphene/ferrite nano composite in mass ratio 1~8:0.5
~1.5:0.5~1.5:0.5~1.5 is scattered in deionized water or ethanol solution, and ultrasonic disperse obtains carbon material dispersion liquid；
Then polytetrafluoroethylene (PTFE) concentrate is scattered in ethanol solution, stirring obtains polytetrafluoroethyldispersion dispersion, adds to carbon materials
Expect in dispersion liquid, sonicated, heating stirring obtains semi solid slurry；Finally semi solid slurry is rolled on roll squeezer,
Produce graphene/ferrite nano combination electrode material.
Other metal salts in the step (1) are the one or more in zinc salt, manganese salt, cobalt salt；Molysite and other gold
The anion for belonging to salt is nitrate ion, sulfate ion or chlorion.
The molecular weight of polyvinyl alcohol in the step (2) is 700~1500.
The mol ratio of oxalic acid and other metal salts in the step (2) is 2.5~3.5:1.
Ultrasonic specific process parameter in the step (2) is：100~400w of power of ultrasonic dispersing machine, when ultrasonic
Between be 0.3~12h.
Stir speed (S.S.) in the step (1) and (2) is 2500~3500r/min, and mixing time is 20~40min.
Hydrothermal temperature in the step (3) is 120~200 DEG C, and the reaction time is 6~24h.
Centrifugal speed in the step (3) is 6000~10000r/min, and centrifugation time is 10~30min；Dry temperature
Spend for 60~100 DEG C, drying time is 6~12h；Calcining heat is 400~500 DEG C, and programming rate is 1~2 DEG C/min, calcining
Time is 1~4h.
The concentration of polytetrafluoroethylene (PTFE) concentrate in the step (4) is 98wt%；Poly- four in polytetrafluoroethyldispersion dispersion
PVF is 0.1~6wt%；Polytetrafluoroethyldispersion dispersion content in carbon material dispersion liquid is 5~20wt%；Activated carbon is with gathering
The mass ratio of tetrafluoroethene is 1~8:0.5~1.5.
Ultrasonic disperse and ultrasonically treated specific process parameter in the step (4) are：The power of ultrasonic dispersing machine is
100~400w；Ultrasonic time is 0.3~12h；Heating stirring specific process parameter is：Heating-up temperature is 30~70 DEG C, stirring speed
Rate is 2500~3500r/min, and mixing time is 0.5~6h.
Roll squeezer roller distance in the step (4) is 50~1000 μm, and rotating speed is 5~90r/min.
Iron-based composite oxides adsorbent has that advantages of good adsorption effect, preparation manipulation are simple, cost is low, material source is wide, simultaneously
And the advantages of will not produce secondary pollution after use, the present invention is by introducing answering for iron-based oxide/graphene into carbon material
Product is closed, laminated film is prepared, the advantage of each component is played, to improve the performance of electrode material and the desalting effect of CDI technologies.
Therefore, the capacity of the ultracapacitor based on the dilute electrode of graphite can reach more than 600F/g, graphene/ferrite of the invention
(XFe2O4) nanometer combined electrode material has huge applications potentiality in CDI technologies, be current CDI investigations of materials focus it
One.
Beneficial effect
(1) preparation method of the present invention is simple, and cost of manufacture is cheap, it is easy to operate, and is that one kind easily prepares electrode material
Technique；Can serialization prepare broad-area electrode film, be work applied to technical fields such as capacitive deionization, ultracapacitors
The production of industry metaplasia provides technical support；
(2) present invention is compound by graphene and ferrite hydro-thermal, and ferrite is equably grown on graphenic surface, prepares
Obtain graphene/ferrite composite material with purer crystalline phase.
(3) present invention is compound by graphene and ferritic hydro-thermal so that the advantage of both graphene and ferrite is filled
That divides is combined together, and effectively suppresses graphene and ferritic from reuniting, so that compound for the high-performance for preparing multilevel hierarchy
Material is laid a good foundation.
(4) the capacitive deionization electrode material prepared by the present invention has good mechanical performance, chemical property and inhales de-
Attached performance.These good physical and chemical properties ensure that electrode material under extra applied voltage, is filled by water process
Put and show good adsorption desorption ability, have a good application prospect.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares graphene/ferrite nano composite；
Fig. 2 is the cyclical stability curve map that embodiment 1 prepares graphene/ferrite nano combination electrode material；
Fig. 3 is the CV curve maps that Examples 1 and 2 prepare graphene/ferrite nano combination electrode material；
Fig. 4 is the adsorption desorption that embodiment 1 prepares the graphene/salt of ferrite nano combination electrode material under certain condition
Curve map；
Fig. 5 is the scanning electron microscope (SEM) photograph that embodiment 2 prepares graphene/ferrite nano combination electrode material；
Fig. 6 is the adsorption desorption curve map for the nitrogen that embodiment 2 prepares graphene/ferrite nano combination electrode material；
Fig. 7 is the XRD that embodiment 3 prepares graphene/ferrite composite material；
Fig. 8 is the infrared curve map that embodiment 3 prepares graphene/ferrite composite material.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) 2.78g ferrous sulfate heptahydrates are weighed, 1.435g white vitriols, mixing is dissolved in 50ml deionized waters, is stirred
To being uniformly dissolved, Fe is configured to:Zn molar concentration ratios are 2:1 mixing salt solution；
(2) weigh 0.5g molecular weight be 1300 polyvinyl alcohol and be dissolved in 30ml deionized waters, heating stirring to mix
Uniformly；
(3) 1.89g oxalic acid (H is weighed2C2O4·2H2O) and be added to step (2) preparation solution in, mix to equal
It is even；(4) weigh 2.87g graphene and be added in the mixed solution of step (1) preparation, then high-speed stirred, stir speed (S.S.)
For 3500r/min, mixing time is 40min, is finally dispersed in graphene uniform in mixed solution；
(5) mixed liquor for preparing step (3) is added slowly to step (4) preparation under conditions of high-speed stirred
In dispersion liquid, after stirring 60min, dispersion liquid is carried out in cell disruptor ultrasonically treated, ultrasonic time is 60min, is obtained
Dispersion liquid B；
(6) dispersion liquid B is transferred in reactor, 12h, natural cooling is reacted at 120 DEG C；
(7) obtained black suspension is centrifuged or suction filtration, centrifugal speed is 8000r/min, and centrifugation time is
30min, repeatedly washing, is dried in vacuo in vacuum drying chamber；
(8) by obtained powder argon gas protection under calcined, set initial temperature be 20 DEG C, programming rate for 2 DEG C/
Min, calcining heat is 450 DEG C, and calcination time is natural cooling after 2h, high temperature cabonization, obtains graphene/ferrite nano and is combined
Material；
(9) obtained graphene/ferrite nano composite is ground, particle size is made and is less than or equal to 500
Purpose composite.
(10) it is 5 in mass ratio:1:1.5:1.5:1 weigh respectively activated carbon 4.0g, CNT 0.8g, carbon black 1.2g,
Graphene/ferrite nano composite 1.2g, polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) 0.8g.
(11) activated carbon, CNT, carbon black and the graphene weighed step (10)/ferrite nano composite point
Dissipate in 100ml ethanol solutions, ultrasonic disperse, ultrasonic power is 100w, ultrasonic time is 40min, obtains 72mg/ml carbon materials
Expect dispersion liquid；
(12) polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) that step (10) is weighed is scattered in 50ml ethanol, stirred
Mix the polytetrafluoroethyldispersion dispersion for obtaining 16mg/ml；
(13) polytetrafluoroethyldispersion dispersion of configuration in step (11) is slowly added into the step (10) under stirring
Ultrasonically treated in the carbon material dispersion liquid of middle configuration, ultrasonic power is 100w, and ultrasonic time is 60min, finally to being completely dispersed
Uniformly, heating stirring is carried out immediately, and heating-up temperature is 65 DEG C, and stir speed (S.S.) is 3000r/min, and the time is 60min, and ethanol is gradually
Volatilization, finally obtains the slurry of semisolid；
(14) slurry for obtaining step (12) is rolled on roll squeezer, and the humidity of slurry is adjusted with alcohol spraying, right
The roller speed of roller machine is 30r/min, and 700 μm of roller spacing is 5 times to roller number of times, obtains complete film；
(15) roller spacing is gradually reduced, 600 μm are contracted to, 500 μm, 400 μm, 300 μm, with bar same in step (13)
Part roll-in, the humidity of film is adjusted with alcohol spraying, can obtain 300 μm of electrode material.
(16) roller spacing is gradually reduced in 300 μm of the electrode material that step (14) is obtained, is contracted to 250 μm, 200 μm,
150 μm, 100 μm, 50 μm, the humidity of film is adjusted with alcohol spraying, you can obtain 50 μm of electrode material.
Embodiment 2
(1) 2.78g ferrous sulfate heptahydrates are weighed, 0.845g manganese sulfate monohydrates, mixing is dissolved in 50ml deionized waters, is stirred
To being uniformly dissolved, Fe is configured to:Mn molar concentration ratios are 2:1 mixing salt solution；
(2) weigh 0.5g molecular weight be 1300 polyvinyl alcohol and be dissolved in 30ml deionized waters, heating stirring to mix
Uniformly；
(3) 1.89g oxalic acid (H is weighed2C2O4·2H2O) and be added to step (2) preparation solution in, mix to equal
It is even；(4) weigh 1.69g graphene and be added in the mixed solution of step (1) preparation, then high-speed stirred, stir speed (S.S.)
For 3500r/min, mixing time is 40min, is finally dispersed in graphene uniform in mixed solution；
(5) mixed liquor for preparing step (3) is added slowly to step (4) preparation under conditions of high-speed stirred
In dispersion liquid, after stirring 60min, dispersion liquid is carried out in cell disruptor ultrasonically treated, ultrasonic time is 60min, is obtained
Dispersion liquid B；
(6) dispersion liquid B is transferred in reactor, 12h, natural cooling is reacted at a temperature of 120 DEG C；
(7) obtained black suspension is centrifuged or suction filtration, centrifugal speed is 8000r/min, and centrifugation time is
30min, repeatedly washing, is dried in vacuo in vacuum drying chamber；
(8) by obtained powder argon gas protection under calcined, set initial temperature be 20 DEG C, programming rate for 2 DEG C/
Min, calcining heat is 450 DEG C, and calcination time is natural cooling after 2h, high temperature cabonization, obtains graphene/ferrite nano and is combined
Material；
(9) obtained graphene/ferrite nano composite is ground, particle size is made and is less than or equal to 500
Purpose composite.
(10) it is 5 in mass ratio:1:1.5:1.5:1 weigh respectively activated carbon 4.0g, CNT 0.8g, carbon black 1.2g,
Graphene/ferrite nano composite 1.2g, polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) 0.8g.
(11) activated carbon, CNT, carbon black and the graphene weighed step (10)/ferrite nano composite point
Dissipate in 100ml ethanol solutions, ultrasonic disperse, ultrasonic power is 100w, ultrasonic time is 40min, obtains 72mg/ml carbon materials
Expect dispersion liquid；
(12) polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) that step (10) is weighed is scattered in 50ml ethanol, stirred
Mix the polytetrafluoroethyldispersion dispersion for obtaining 16mg/ml；
(13) polytetrafluoroethyldispersion dispersion of configuration in step (11) is slowly added into the step (10) under stirring
Ultrasonically treated in the carbon material dispersion liquid of middle configuration, ultrasonic power is 100w, and ultrasonic time is 60min, finally to being completely dispersed
Uniformly, heating stirring is carried out immediately, and heating-up temperature is 65 DEG C, and stir speed (S.S.) is 3000r/min, and the time is 60min, and ethanol is gradually
Volatilization, finally obtains the slurry of semisolid；
(14) slurry for obtaining step (12) is rolled on roll squeezer, and the humidity of slurry is adjusted with alcohol spraying, right
The roller speed of roller machine is 30r/min, and 700 μm of roller spacing is 5 times to roller number of times, obtains complete film；
(15) roller spacing is gradually reduced, 600 μm are contracted to, 500 μm, 400 μm, 300 μm, with bar same in step (13)
Part roll-in, the humidity of film is adjusted with alcohol spraying, can obtain 300 μm of electrode material.
(16) roller spacing is gradually reduced in 300 μm of the electrode material that step (14) is obtained, is contracted to 250 μm, 200 μm,
150 μm, 100 μm, 50 μm, the humidity of film is adjusted with alcohol spraying, you can obtain 50 μm of electrode material.
Embodiment 3
(1) 2.78g ferrous sulfate heptahydrates are weighed, the water cobaltous sulfates of 1.135g six, mixing is dissolved in 50ml deionized waters, is stirred
To being uniformly dissolved, Fe is configured to:Co molar concentration ratios are 2:1 mixing salt solution；
(2) weigh 0.5g molecular weight be 1300 polyvinyl alcohol and be dissolved in 30ml deionized waters, heating stirring to mix
Uniformly；
(3) 1.89g oxalic acid (H is weighed2C2O4·2H2O) and be added to step (2) preparation solution in, mix to equal
It is even；(4) weigh 2.63g graphene and be added in the mixed solution of step (1) preparation, then high-speed stirred, stir speed (S.S.)
For 3500r/min, mixing time is 40min, is finally dispersed in graphene uniform in mixed solution；
(5) mixed liquor for preparing step (3) is added slowly to step (4) preparation under conditions of high-speed stirred
In dispersion liquid, after stirring 60min, dispersion liquid is carried out in cell disruptor ultrasonically treated, ultrasonic time is 60min, is obtained
Dispersion liquid B；
(6) dispersion liquid B is transferred in reactor, 12h, natural cooling is reacted at a temperature of 120 DEG C；
(7) obtained black suspension is centrifuged or suction filtration, centrifugal speed is 8000r/min, and centrifugation time is
30min, repeatedly washing, is dried in vacuo in vacuum drying chamber；
(8) by obtained powder argon gas protection under calcined, set initial temperature be 20 DEG C, programming rate for 2 DEG C/
Min, calcining heat is 450 DEG C, and calcination time is natural cooling after 2h, high temperature cabonization, obtains graphene/ferrite nano and is combined
Material；
(9) obtained graphene/ferrite nano composite is ground, particle size is made and is less than or equal to 500
Purpose composite.
(10) it is 5 in mass ratio:1:1.5:1.5:1 weigh respectively activated carbon 4.0g, CNT 0.8g, carbon black 1.2g,
Graphene/ferrite nano composite 1.2g, polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) 0.8g.
(11) activated carbon, CNT, carbon black and the graphene weighed step (10)/ferrite nano composite point
Dissipate in 100ml ethanol solutions, ultrasonic disperse, ultrasonic power is 100w, ultrasonic time is 40min, obtains 72mg/ml carbon materials
Expect dispersion liquid；
(12) polytetrafluoroethylene (PTFE) (PTFE) concentrate (98wt%) that step (10) is weighed is scattered in 50ml ethanol, stirred
Mix the polytetrafluoroethyldispersion dispersion for obtaining 16mg/ml；
(13) polytetrafluoroethyldispersion dispersion of configuration in step (11) is slowly added into the step (10) under stirring
Ultrasonically treated in the carbon material dispersion liquid of middle configuration, ultrasonic power is 100w, and ultrasonic time is 60min, finally to being completely dispersed
Uniformly, heating stirring is carried out immediately, and heating-up temperature is 65 DEG C, and stir speed (S.S.) is 3000r/min, and the time is 60min, and ethanol is gradually
Volatilization, finally obtains the slurry of semisolid；
(14) slurry for obtaining step (12) is rolled on roll squeezer, and the humidity of slurry is adjusted with alcohol spraying, right
The roller speed of roller machine is 30r/min, and 700 μm of roller spacing is 5 times to roller number of times, obtains complete film；
(15) roller spacing is gradually reduced, 600 μm are contracted to, 500 μm, 400 μm, 300 μm, with bar same in step (13)
Part roll-in, the humidity of film is adjusted with alcohol spraying, can obtain 300 μm of electrode material.
(16) roller spacing is gradually reduced in 300 μm of the electrode material that step (14) is obtained, is contracted to 250 μm, 200 μm,
150 μm, 100 μm, 50 μm, the humidity of film is adjusted with alcohol spraying, you can obtain 50 μm of electrode material.
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene/ferrite nano composite prepared by embodiment 1, it can be seen that：Iron oxygen
Body is uniformly grown on the surface of graphene, and graphene and ferrite are carried out into compound can prepare uniformly using hydro-thermal method
Nano composite material, be effectively prevented graphene and ferrite itself from agglomeration, the preparation to later stage electrode material
Lay a good foundation.
Fig. 2 is the sodium chloride for being 1mol/L in electrolyte of graphene/ferrite combination electrode material prepared by embodiment 1
Solution, electrode are 1*1cm2, effective area is 1*0.5cm2, under sweep speed is 10mV/s, has carried out 1000 CV circulation and surveyed
Examination, it can be seen that：Stabilization is reached at 50 times or so, with good cyclical stability, its stability reaches 97.9%.
Fig. 3 is that embodiment 1 has done electric capacity with three electrode modes using electrochemical workstation from embodiment 2 to different electrodes
The test of performance, this figure be electrode material be 1mol/L in electrolyte sodium chloride solution, electrode be 1*1cm2, effective area is
1*0.5cm2, sweep the CV curves that speed is 5mV/s, it can be seen that the capacitance of electrode material can reach more than 600F/g, contain
There is good chemical property.
Fig. 4 is that graphene/ferrite combination electrode material prepared by embodiment 1 utilizes CDI devices under the conditions of 2.0V, with
100mol/L sodium chloride solution carries out adsorption desorption test, and adsorption time is 0h~3h, and desorption time is 3h~3.7h, test knot
Fruit shows that, when CDI devices both sides add voltage, sodium ion and chlorion are adsorbed in electrode two ends respectively, form electric double layer, with
The increase rate of adsorption of time gradually lowers, and finally reaches stable state, and maximum desalination rate changes electrode two ends up to more than 50%
Positive negativity, the negative ions disengaging electrode material for being adsorbed in electrode both sides is returned in solution.
Fig. 5 is the scanning electron microscope (SEM) photograph of graphene/ferrite combination electrode material section prepared by embodiment 2, it can be seen that：
The nano composite material of ferrite and graphene and other carbon materials are dispersed in electrode material, and contain compared with concrete dynamic modulus, this
One is characterized as that the adsorption desorption of capacitive deionization technical field ion provides more rooms.
Fig. 6 is the adsorption desorption curve of graphene/ferrite combination electrode material nitrogen prepared by embodiment 2, it can be seen that：This
Electrode material has very big ratio surface, can reach 1176.9m2/ g, with good adsorption desorption energy-absorbing, can be used for electric capacity
The fields such as deionization.
Fig. 7 is the XRD analysis image of graphene/ferrite composite material prepared by embodiment 3, it can be seen that：This figure contains
There are the CoFe such as (220) (311), (400), (511), (440)2O4, also there is graphene in the characteristic diffraction peak of each crystal face
(001) characteristic diffraction peak, occurs without miscellaneous peak, obtains purer crystalline phase.Such composite is adapted to later stage electrode material
Prepare.
Fig. 8 is the infrared curve of graphene/ferrite composite material prepared by embodiment 3, and thus figure is it can be seen that difference
The appearance of functional group, it was demonstrated that have the appearance of graphene/ferrite composite material.
Claims (10)
1. a kind of preparation method of graphene/ferrite nano combination electrode material, including：
(1) molysite and other metal salts are dissolved in deionized water, stir to being uniformly dissolved, obtain mixing salt solution；Then will
Mixing salt solution is mixed with graphene, and stirring obtains dispersion liquid A；Wherein, the mol ratio of molysite and other metal salts for 1.5~
2.5:1, the mass ratio of graphene and other metal salts is 1.5~2.5:1；
(2) by polyvinyl alcohol and oxalic acid in mass ratio 1:5~10 are dissolved in deionized water, and heating stirring uniformly obtains polyvinyl alcohol
With the mixed solution of oxalic acid；Mixed solution is added in above-mentioned dispersion liquid A, stirring, ultrasound obtain dispersion liquid B；
(3) dispersion liquid B is transferred in reactor and carries out hydro-thermal reaction, product is by centrifuging, drying, forged under protective atmosphere
Burn, grind, obtain graphene/ferrite nano composite；
(4) by activated carbon, CNT, carbon black and graphene/ferrite nano composite in mass ratio 1~8:0.5~
1.5:0.5~1.5:0.5~1.5 is scattered in deionized water or ethanol solution, and ultrasonic disperse obtains carbon material dispersion liquid；So
Polytetrafluoroethylene (PTFE) concentrate is scattered in ethanol solution afterwards, stirring obtains polytetrafluoroethyldispersion dispersion, adds to carbon material
In dispersion liquid, sonicated, heating stirring obtains semi solid slurry；Finally semi solid slurry is rolled on roll squeezer, i.e.,
Obtain graphene/ferrite nano combination electrode material.
2. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：Other metal salts in the step (1) are the one or more in zinc salt, manganese salt, cobalt salt；Molysite and other metal salts
Anion is nitrate ion, sulfate ion or chlorion.
3. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：The molecular weight of polyvinyl alcohol in the step (2) is 700~1500.
4. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：The mol ratio of oxalic acid and other metal salts in the step (2) is 2.5~3.5:1.
5. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：Ultrasonic specific process parameter in the step (2) is：100~400w of power of ultrasonic dispersing machine, ultrasonic time is
0.3~12h.
6. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：Hydrothermal temperature in the step (3) is 120~200 DEG C, and the reaction time is 6~24h.
7. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：Centrifugal speed in the step (3) is 6000~10000r/min, and centrifugation time is 10~30min；Drying temperature is 60
~100 DEG C, drying time is 6~12h；Calcining heat is 400~500 DEG C, and programming rate is 1~2 DEG C/min, and calcination time is
1~4h.
8. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：The concentration of polytetrafluoroethylene (PTFE) concentrate in the step (4) is 98wt%；Polytetrafluoroethylene (PTFE) in polytetrafluoroethyldispersion dispersion
For 0.1~6wt%；Polytetrafluoroethyldispersion dispersion content in carbon material dispersion liquid is 5~20wt%；Activated carbon and polytetrafluoroethyl-ne
The mass ratio of alkene is 1~8:0.5~1.5.
9. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature exists
In：Ultrasonic disperse and ultrasonically treated specific process parameter in the step (4) are：The power of ultrasonic dispersing machine be 100~
400w；Ultrasonic time is 0.3~12h；Heating stirring specific process parameter is：Heating-up temperature is 30~70 DEG C, and stir speed (S.S.) is
2500~3500r/min, mixing time is 0.5~6h.
10. a kind of preparation method of graphene/ferrite nano combination electrode material according to claim 1, its feature
It is：Roll squeezer roller distance in the step (4) is 50~1000 μm, and rotating speed is 5~90r/min.
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