CN107633954A - A kind of graphene/MXene combination electrode materials and its application - Google Patents
A kind of graphene/MXene combination electrode materials and its application Download PDFInfo
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Abstract
The present invention relates to a kind of graphene/MXene combination electrode materials and its application, is made up of two kinds of materials of graphene and MXene；Its preparation method includes with MXene material suspensions uniformly mixing graphene oxide suspension, adds after hydrazine hydrate is reduced and is freeze-dried, obtains the graphene/MXene combination electrode materials, and the mass ratio of the graphene oxide and MXene materials is 1：（0.05~0.5）.The present invention can regard graphene and MXene compound tenses, irregular MXene granular materials as inserting agent and dispersant, enter graphene film interlayer, overcome the reuniting effect between graphene sheet layer, increase its available specific surface area.In addition, hydrophily and electric conductivity that MXene materials are excellent, meeting further improves the chemical property and capacitive deionization performance of composite.
Description
Technical field
The invention belongs to the preparation field of capacitive deionization combination electrode, more particularly to a kind of capacitive deionization graphite
The preparation method of alkene/MXene composites.
Background technology
With the fast development of human society, freshwater resources crisis turns into countries in the world urgent problem to be solved, water resource
Shortage has become the principal element for restricting multinational development.Capacitive deionization technology is a kind of energy-efficient, green takes off
Salt method, by applying electrostatic field, ion is forced to adsorb its electric double layer caused by electrode surface to both sides electrode transfer,
So as to reach the purpose of desalination.The key of capacitive deionization technology is the preparation of high performance electrode material, it is desirable to is had higher
Specific surface area, rational pore-size distribution and good electric conductivity and hydrophily.
Graphene has the theoretical specific surface area of superelevation and good electric conductivity, is a kind of preferably capacitive deionization electrode
Material.But due to graphene inevitable reuniting effect between layer by layer, actually available specific surface area is had a strong impact on, has been constrained
Its application as electrode material.
The content of the invention
In view of the above-mentioned problems, the present invention first using with excellent hydrophilic and electric conductivity in one MXene materials as
Inserting agent and dispersant are combined with redox graphene, prepare novel graphite alkenyl combination electrode material, it is therefore intended that
A kind of electrochemical performance, the preferable capacitive deionization electrode material of desalting performance are provided.
On the one hand, the invention provides a kind of graphene/MXene combination electrode materials, by two kinds of materials of graphene and MXene
Material composition, its preparation method include with MXene material suspensions uniformly mixing graphene oxide suspension, add hydrazine hydrate and enter
It is freeze-dried after row reduction, obtains the graphene/MXene combination electrode materials, the graphene oxide and MXene materials
Mass ratio is 1：(0.05~0.5).
MXene materials have the characteristics that good hydrophily and electric conductivity, larger specific capacitance, electrochemical performance.
The present invention can regard graphene and MXene compound tenses, irregular MXene granular materials as inserting agent and dispersant, enter
Graphene film interlayer, overcome the reuniting effect between graphene sheet layer, increase its available specific surface area.In addition, MXene materials are excellent
Different hydrophily and electric conductivity, it can further improve the chemical property and capacitive deionization performance of composite.
It is preferred that the MXene materials are Ti3C2Tx(TxFor functional groups such as-OH ,-F), Ti2CTx(TxFor officials such as-OH ,-F
Can group), Cr2CTx(TxAt least one of for functional groups such as-OH ,-F).
It is preferred that the volume ratio of the hydrazine hydrate and graphene oxide is (1~5)：200.
It is preferred that the freeze-drying is first precooling 6~12 hours at -50~-80 DEG C, it is cold at 0~20 DEG C
It is lyophilized dry 8~24 hours.
It is preferred that prepare graphene oxide suspension using modified Hummers methods.
It is preferred that MAX phase ceramics powders are added in high concentration HF solution, reaction is performed etching at a certain temperature,
Then using being then sonicated after ethanol, the abundant eccentric cleaning of deionized water, the MXene material suspensions are obtained.
It is preferred that the MAX phase ceramics powder is Ti3AlC2、Ti2AlC、Cr2At least one of AlC.
It is preferred that the concentration of the HF solution is 40%~49%, the certain temperature is 35~85 DEG C.
On the other hand, present invention also offers a kind of capacitive deionization use based on graphene/MXene combination electrode materials
Graphene/MXene combination electrodes.By graphene/MXene combination electrode material ball milling powderings, with a small amount of bonding agent, conductive charcoal
It is black to be well mixed according to certain ratio, add appropriate solvent, form the uniform colloid with certain viscosity, and by the glue
Body roll-in obtains capacitive deionization combination electrode on collector.
It is preferred that the binding agent be polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl alcohol, one kind in polypropylene or
It is several.
It is preferred that the mass ratio of the graphene/MXene combination electrode materials, binding agent and conductive black is (8~9):
(1~0.5):(1~0.5).
It is preferred that the collector is at least one of graphite cake, copper coin, nickel screen, titanium net.
Graphene/MXene combination electrodes prepared by the present invention have that good hydrophily, electric conductivity, specific surface area are big,
Ion spreads in electrode surface and transports fast, can improve the performance of electrode adsorption ion, suitable for capacitive deionization and super
Capacitor area.The present invention prepares graphene/MXene combination electrode materials and including graphene/MXene combination electrode material
Capacitive deionization is simple and easy with the method for graphene/MXene combination electrodes, is easy to large-scale industrialization promotion application.
Brief description of the drawings
Fig. 1 is graphene (rGO), the Ti of the preparation of embodiment 2 prepared by embodiment 13C2TxMaterial and embodiment 3,5,7 are made
Standby different Ti3C2TxGraphene/Ti of incorporation3C2TxThe XRD spectrum of combination electrode material；
Fig. 2 a are the SEM figures of graphene prepared by embodiment 1；
Fig. 2 b are Ti prepared by embodiment 23C2TxThe SEM shape appearance figures of material
Fig. 2 c are graphene and Ti prepared by embodiment 3,5,73C2TxThe internal structure schematic diagram of composite sample
Fig. 3 a are graphene/Ti prepared by embodiment 33C2TxCyclic voltammetric of -20% combination electrode under different scanning rates is bent
Line；
Fig. 3 b are graphene/Ti prepared by embodiment 33C2Tx- 20% combination electrode when sweep speed is 25mV/s, sweep by difference
Retouch the cyclic voltammetry curve of number；
Fig. 3 c are graphene/Ti prepared by embodiment 33C2TxThe constant current charge-discharge of the different cycle-indexes of -20% combination electrode
Collection of illustrative plates；
The different Ti that Fig. 4 a are graphene prepared by embodiment 1 and prepared by embodiment 3,5,73C2TxThe graphene of incorporation/
Ti3C2TxCyclic voltammetry curve of the combination electrode when sweep speed is 25mV/s；
The different Ti that Fig. 4 b are graphene prepared by embodiment 1 and prepared by embodiment 3,5,73C2TxThe graphene of incorporation/
Ti3C2TxThe constant current charge-discharge collection of illustrative plates of combination electrode；
The different Ti that Fig. 4 c are graphene prepared by embodiment 1 and prepared by embodiment 3,5,73C2TxThe graphene of incorporation/
Ti3C2TxThe electrochemical impedance collection of illustrative plates of combination electrode；
Fig. 5 a and Fig. 5 b are Ti prepared by Graphene electrodes, embodiment 2 prepared by embodiment 13C2TxIt is prepared by material and embodiment 3
Graphene/Ti3C2TxThe capacitive deionization performance test figure of -20% combination electrode；
Fig. 6 is capacitive deionization test device schematic diagram.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is by graphene oxide stable dispersions (e.g., graphene oxide suspension) and MXene stable dispersions
(e.g., MXene material suspensions) uniformly mixing after (such as first through magnetic agitation, after sonic oscillation), add hydrazine hydrate gone back
Original reaction, then freeze-drying obtain graphene/MXene combination electrode materials.Wherein, the graphene oxide and MXene of addition
The mass ratio of material is 1：(0.05~0.5).If the addition of MXene materials is less than the 5wt% of graphene oxide addition,
DeGrains of the MXene as graphene inserting agent, the specific surface area of composite are still smaller；If MXene materials add
Enter amount be more than graphene oxide addition 50wt% when, MXene materials are not easy to be uniformly dispersed with grapheme material, composite
Agglomerate is easily produced, its electric conductivity and specific surface area are affected.By graphene/MXene combination electrode material ball grinds
Shape, it is well mixed with a small amount of bonding agent, conductive black, adds appropriate solvent, forms the homogeneous paste thing with certain viscosity, profit
By pastel roll-in (~300um) in blocks and pressed on a current collector with small type calender, obtain capacitive deionization combination electrode.
Illustrate to following exemplary the preparation method of capacitive deionization graphene/MXene combination electrode materials provided by the invention.
Graphene oxide suspension is prepared using modified Hummers methods.The example detailed as one, will be ground
Natural flake graphite is soaked in concentrated nitric acid and the concentrated sulfuric acid mixed solution (volume of concentrated nitric acid and the concentrated sulfuric acid at 70 DEG C~90 DEG C
Than that can be 1:0.5~1.) in 5~10h, be cooled to room temperature, filter, it is neutral, vacuum fully to be rinsed with deionized water to filtrate
Dry, the crystalline flake graphite pre-oxidized.Add a certain amount of concentrated sulfuric acid (body into the 1000ml beakers being placed in frozen water bath
Product can be 90~120ml), 2g pre-oxidation crystalline flake graphite, 1g sodium nitrate solids, stir 0.5~1h, after every 15 minutes add
A certain amount of potassium permanganate (the total addition of potassium permanganate can be 6~12g), reaction temperature are no more than 15 DEG C.Beaker is shifted
Into 35 DEG C of water-baths, continue stirring 2~4 hours.Then 100ml deionized waters are added, 95 DEG C is warming up to, adds 300ml
Deionized water is diluted.The hydrogen peroxide that 50ml concentration is 30% is added, continues to stir 30min, ultrasonic 2h.Centrifuge while hot, it is first
First centrifuged with 5% watery hydrochloric acid, then add deionized water and continue centrifugation to solution PH about 7, at the solution centrifuged ultrasound
Reason, you can obtain graphene oxide suspension.
The preparation of two dimensional crystal material MXene suspension (MXene material suspensions).Detailed process is：Will be ground
MAX phase ceramics powder is soaked in high concentration HF solution under certain temperature (temperature can be 35~85 DEG C), and (mass fraction can be
40%~49%) certain time in, afterwards with ethanol, the abundant eccentric cleaning of deionized water, after supersound process, solution it is as steady
Fixed MXene material suspensions.The MAX phase ceramics can be Ti3AlC2、Ti2AlC、Cr2One or more in AlC.Obtain
MXene materials can be Ti3C2Tx(TxFor functional groups such as-OH ,-F), Ti2CTx(TxFor functional groups such as-OH ,-F), Cr2CTx(Tx
For functional groups such as-OH ,-F) in one or more.
Graphene oxide suspension is uniformly mixed with MXene material suspensions through magnetic agitation, sonic oscillation, adds water
Close after hydrazine is reduced and be freeze-dried, obtain the graphene/MXene combination electrode materials.Wherein, graphene oxide with
The mass ratio of MXene materials can be 1:0.05-0.5.The volume ratio of hydrazine hydrate and graphene oxide is (2~10ml)：400ml.
The freeze-drying is first precooling 6~12 hours at -50~-80 DEG C, and it is small that 8~24 are freeze-dried at -50~-80 DEG C
When.
Present invention also offers a kind of capacitive deionization graphene/MXene combination electrodes.Specifically, by graphene/
MXene combination electrode material ball milling powderings, with a small amount of bonding agent (for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyethylene
Alcohol, polypropylene etc.), conductive black according to certain ratio (for example, 8:1:1) it is well mixed, adds appropriate solvent (for example, nothing
Water-ethanol, deionized water etc.), form the uniform colloid with certain viscosity.Again by the colloid roll-in to collector (example,
Graphite cake, copper coin, nickel screen and titanium net etc.) in flakes (thickness of electrode can be 150~300um)), obtain capacitive deionization with compound
Electrode.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
The preparation and capacitive deionization performance test of 1 pure Graphene electrodes of embodiment
Graphene oxide suspension is prepared using modified Hummers methods.By ground natural flake graphite at 70 DEG C -90 DEG C
Under, being soaked in concentrated nitric acid and concentrated sulfuric acid mixed solution, (volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1:1) 6h in, is cooled to room temperature,
Filtering, it is neutral, vacuum drying fully to be rinsed with deionized water to filtrate, the crystalline flake graphite pre-oxidized.To being placed on ice
Add the 100ml concentrated sulfuric acid, crystalline flake graphite, the 1g sodium nitrate solids of 2g pre-oxidation in 1000ml beakers in water-bath, stir 1h,
It is no more than 15 DEG C every the 15 minutes potassium permanganate for adding 6g, reaction temperature afterwards.Beaker is transferred in 35 DEG C of water-baths, continued
Stirring 4 hours.Then 100ml deionized waters are added, 95 DEG C is warming up to, adds 300ml deionized waters and be diluted.Add
50ml concentration is 30% hydrogen peroxide, continues to stir 30min, ultrasonic 2h.Centrifuge, centrifuged first with 5% watery hydrochloric acid, so while hot
Deionized water is added afterwards and continues centrifugation to solution PH about 7, the solution centrifuged is ultrasonically treated, you can obtain graphene oxide and hang
Supernatant liquid, according to volume ratio 100:1, hydrazine hydrate is added into the graphene oxide suspension of preparation, carries out reducing instead at 95 DEG C
2h is answered, by reaction product filtering cleaning to filtrate weakly acidic pH, obtains redox graphene solution；
The redox graphene solution of preparation is subjected to precooling processing 8h, rear utilization using freeze drying box at -80 DEG C
Freeze drying box is freeze-dried 24h at 5 DEG C.The graphene powder and 0.06g conductive blacks after 0.48g freeze-dryings are taken, is ground
Mill is sufficiently mixed it, after PTFE emulsion (mass fraction of PTFE emulsion be 60%) is slowly added dropwise, wherein PTFE quality is
0.06g, add a small amount of ethanol, stir into the pastel of certain viscosity, using small type calender by pastel roll-in in flakes (~
300um) and it is pressed on graphite cake, is dried in vacuo 8h, obtains pure Graphene electrodes (rGO).
Transposition schematic diagram is tested by Fig. 6 capacitive deionizations, takes the pure Graphene electrodes composition capacitive deionization test of two panels single
Member, it is about 200us.cm with initial conductivity-140ml NaCl solutions be desalting soln, target voltage be 1.6V condition
Lower progress capacitive deionization performance test.In NaCl solution electrical conductivity versus time curve (Fig. 5 a), pure Graphene electrodes
In the case of, the single loop desalination amount of pure Graphene electrodes is 2.78mg/g (see Fig. 5 b).
The pure MXene Ti of embodiment 23C2TxElectrode prepares and capacitive deionization performance test
By 2gTi3AlC2Ceramic powder is added in 50ml 49%HF solution, reaction 18h is performed etching at 60 DEG C, then
Using being then sonicated after ethanol, the abundant eccentric cleaning of deionized water, Ti is obtained3C2TxMaterial suspension；
By the Ti of preparation3C2TxSuspension carries out precooling processing 8h using freeze drying box at -80 DEG C, is done afterwards using freezing
Dry case is freeze-dried 24h at 5 DEG C.Take the Ti after 0.64g freeze-dryings3C2TxPowder and 0.08g conductive blacks, grinding make it
Be sufficiently mixed, after PTFE emulsion (mass fraction of PTFE emulsion be 60%) is slowly added dropwise, wherein PTFE quality is 0.08g,
Add a small amount of ethanol, stir into the pastel of certain viscosity, using small type calender by pastel roll-in in flakes (~300um) simultaneously
It is pressed on graphite cake, is dried in vacuo 8h, obtains pure Ti3C2TxElectrode.
Transposition schematic diagram is tested by Fig. 6 capacitive deionizations, takes two panels Ti3C2TxElectrode forms capacitive deionization test cell,
It is about 200us.cm with initial conductivity-140ml NaCl solutions be desalting soln, target voltage be 1.6V under conditions of enter
Row capacitive deionization performance test.In Fig. 5 NaCl solution electrical conductivity versus time curves (see Fig. 5 a), combination electrode feelings
Under condition, the single loop desalination amount of electrode is 1.95mg/g (see Fig. 5 b).
3 graphenes of embodiment/MXene combination electrodes prepare and capacitive deionization performance test：
Ti prepared by the gained graphene oxide suspension of embodiment 1 and embodiment 23C2TxIn mass ratio 1:0.2, stirred through magnetic force
Mix, after ultrasonic vibration is well mixed, according to volume ratio 100:1, hydrazine hydrate is added into the composite suspension liquid of preparation, at 95 DEG C
Reduction reaction 2h is carried out, by reaction product filtering cleaning to filtrate weakly acidic pH, obtains graphene/MXene solution (rGO/
Ti3C2Tx- 20%)；
Preparation is contained into 20wt%Ti3C2TxGraphene/MXene composite solutions precooling is carried out at -80 DEG C with freeze drying box
Freeze processing 8h, be freeze-dried 24h at 5 DEG C using freeze drying box afterwards.Take the rGO/Ti after 0.56g freeze-dryings3C2Tx-
20% combination electrode material and 0.07g conductive blacks, grinding be sufficiently mixed it, after PTFE emulsion (PTFE emulsion is slowly added dropwise
Mass fraction for 60%), wherein PTFE quality is 0.07g, adds a small amount of ethanol, stirs into the pastel of certain viscosity,
Pastel roll-in (~300um) and is pressed on graphite cake in flakes using small type calender, is dried in vacuo 8h, obtain graphene/
MXene combination electrodes (rGO/Ti3C2Tx- 20%).
Transposition schematic diagram is tested by Fig. 6 capacitive deionizations, takes two panels combination electrode to form capacitive deionization test cell, is used
Initial conductivity is 200us.cm-140ml NaCl solutions be desalting soln, target voltage be 1.6V under conditions of carry out electricity
Hold deionization performance test.In Fig. 5 NaCl solution electrical conductivity versus time curves (see Fig. 5 a), in the case of combination electrode,
The single loop desalination amount of electrode is 4.56mg/g (see Fig. 5 b).
The Graphene electrodes of embodiment 4 prepare and electrochemical property test：
Graphene rGO electrode materials and 0.02g conductive blacks, grinding after the 0.16g freeze-dryings prepared in Example 1 make
It is sufficiently mixed, after PTFE emulsion (mass fraction of PTFE emulsion be 60%) is slowly added dropwise, wherein PTFE quality is
0.02g, add a small amount of ethanol, stir into the pastel of certain viscosity, using small type calender by pastel roll-in in flakes (~
300um) and it is pressed in porous nickel plate, is dried in vacuo 8h, obtains Graphene electrodes.Obtained electrode is being cut into 1cm*1cm just
Square to be used as working electrode, silver/silver chloride electrode is reference electrode, and platinum electrode is to electrode, using concentration as 1mol/L sodium chloride
Solution is test solution, and the electrifications such as cyclic voltammetry, constant current charge-discharge and electrochemical impedance are carried out using electrochemical workstation
Learn performance test.
5 graphenes of embodiment/MXene combination electrodes prepare and electrochemical property test：
Ti prepared by the gained graphene oxide suspension of embodiment 1 and embodiment 23C2TxIn mass ratio 1:0.05, stirred through magnetic force
Mix, after ultrasonic vibration is well mixed, according to volume ratio 100:1, hydrazine hydrate is added into the composite suspension liquid of preparation, at 95 DEG C
Reduction reaction 2h is carried out, by reaction product filtering cleaning to filtrate weakly acidic pH, obtains graphene/MXene solution (rGO/
Ti3C2Tx- 5%)；
Preparation is contained into 5wt%Ti3C2TxGraphene/MXene composite solutions precooling is carried out at -80 DEG C with freeze drying box
Freeze processing 8h, be freeze-dried 24h at 5 DEG C using freeze drying box afterwards, obtain rGO/Ti3C2Tx- 5% combination electrode material.Take
RGO/Ti after 0.16g freeze-dryings3C2Tx- 5% combination electrode material and 0.02g conductive blacks, grinding are sufficiently mixed it,
PTFE emulsion (mass fraction of PTFE emulsion is 60%) is slowly added dropwise afterwards, wherein PTFE quality is 0.02g, adds a small amount of second
Alcohol, the pastel of certain viscosity is stirred into, by pastel roll-in (~300um) in blocks and porous nickel is pressed in using small type calender
On plate, 8h is dried in vacuo, obtains graphene/MXene combination electrodes (rGO/Ti3C2Tx- 5%).Obtained electrode is cut into
1cm*1cm squares be used as working electrode, and silver/silver chloride electrode is reference electrode, platinum electrode for electrode, using concentration as
1mol/L sodium chloride solutions are test solution, and cyclic voltammetry, constant current charge-discharge and electrification are carried out using electrochemical workstation
Learn the electrochemical property tests such as impedance.
6 graphenes of embodiment/MXene combination electrodes prepare and electrochemical property test：
RGO/Ti after the 0.16g freeze-dryings prepared in Example 33C2Tx- 20% combination electrode material and 0.02g are conductive
Carbon black, grinding are sufficiently mixed it, after PTFE emulsion (mass fraction of PTFE emulsion be 60%) is slowly added dropwise, wherein PTFE's
Quality is 0.02g, adds a small amount of ethanol, stirs into the pastel of certain viscosity, is rolled into pastel using small type calender
Piece (~300um) is simultaneously pressed in porous nickel plate, is dried in vacuo 8h, is obtained graphene/MXene combination electrodes (rGO/Ti3C2Tx-
20%).Obtained electrode is cut into 1cm*1cm squares as working electrode, silver/silver chloride electrode is reference electrode, platinum
Electrode is to electrode, take 1mol/L sodium chloride solutions as test solution of concentration, and cyclic voltammetric is carried out using electrochemical workstation
The electrochemical property tests such as method, constant current charge-discharge and electrochemical impedance.
7 graphenes of embodiment/MXene combination electrodes prepare and electrochemical property test：
Ti prepared by the gained graphene oxide suspension of embodiment 1 and embodiment 23C2TxIn mass ratio 1:0.35, stirred through magnetic force
Mix, after ultrasonic vibration is well mixed, according to volume ratio 100:1, hydrazine hydrate is added into the composite suspension liquid of preparation, at 95 DEG C
Reduction reaction 2h is carried out, by reaction product filtering cleaning to filtrate weakly acidic pH, obtains graphene/MXene solution (rGO/
Ti3C2Tx- 35%)；
Preparation is contained into 35wt%Ti3C2TxGraphene/MXene composite solutions precooling is carried out at -80 DEG C with freeze drying box
Freeze processing 8h, be freeze-dried 24h at 5 DEG C using freeze drying box afterwards, obtain rGO/Ti3C2Tx- 35% combination electrode material.
Take the rGO/Ti after 0.16g freeze-dryings3C2Tx- 35% combination electrode material and 0.02g conductive blacks, grinding make it fully mixed
Close, after PTFE emulsion (mass fraction of PTFE emulsion be 60%) is slowly added dropwise, wherein PTFE quality be 0.02g, adds and lacks
Ethanol is measured, stirs into the pastel of certain viscosity, by pastel roll-in (~300um) in blocks and is pressed in more using small type calender
In the nickel plate of hole, 8h is dried in vacuo, obtains graphene/MXene combination electrodes (rGO/Ti3C2Tx- 35%).Obtained electrode is cut out
Be cut into 1cm*1cm squares and be used as working electrode, silver/silver chloride electrode is reference electrode, platinum electrode for electrode, using concentration as
1mol/L sodium chloride solutions are test solution, and cyclic voltammetry, constant current charge-discharge and electrification are carried out using electrochemical workstation
Learn the electrochemical property tests such as impedance.
Fig. 1 is graphene (rGO), the Ti of the preparation of embodiment 2 prepared by embodiment 13C2TxMaterial and embodiment 3,5,7 are made
Standby different Ti3C2TxGraphene/Ti of incorporation3C2TxThe XRD spectrum of combination electrode material.It is it can be seen that various
Graphene/Ti3C2TxGraphene and Ti are shown in the XRD spectrum of combination electrode material simultaneously3C2TxCharacteristic peak, and with
Ti3C2TxContent increases, and the intensity increase of its characteristic peak, shows that combination electrode material is successfully prepared.
Fig. 2 a-2c are respectively graphene, the Ti of the preparation of embodiment 2 prepared by embodiment 13C2TxThe SEM shape appearance figures of material and
Graphene and Ti prepared by embodiment 3,5,73C2TxThe internal structure schematic diagram of composite.It can be seen that graphene
With MXene compound tenses, irregular MXene little particles serve dispersant effect, inserted in graphene layer, to a certain extent
Overcome the reuniting effect of graphene.
Fig. 3 a are graphene/Ti prepared by embodiment 33C2TxCirculation volt of -20% combination electrode under different scanning rates
Pacify curve, be can be seen that from Fig. 3 a under arbitrary scan speed, occur without obvious redox peaks, show that combination electrode has
Good electric double layer capacitance performance.In addition, cyclic voltammetry curve has obvious symmetry, it is excellent to show that combination electrode has
Ionic adsorption/De contamination invertibity.rGO/Ti3C2Tx- 20% electrode, can be with from Fig. 3 b, 3c after 100 charge and discharge cycles
Find out that its cyclic voltammetry collection of illustrative plates and the change of constant current charge-discharge collection of illustrative plates are smaller, it was demonstrated that rGO/Ti3C2TxThe circulation of -20% electrode
Stability is preferable.
The different Ti that Fig. 4 a are graphene prepared by embodiment 1 and prepared by embodiment 3,5,73C2TxThe graphene of incorporation/
Ti3C2TxCyclic voltammetry curve of the combination electrode when sweep speed is 25mV/s, from the cyclic voltammetry figure of Fig. 4 a different materials
RGO/Ti is can be seen that in spectrum3C2Tx- 20% combination electrode material has a more excellent electrochemical properties, its specific capacitance more preferably, electrode
Excellent in stability.The different Ti that Fig. 4 b are graphene prepared by embodiment 1 and prepared by embodiment 3,5,73C2TxThe graphite of incorporation
Alkene/Ti3C2TxThe constant current charge-discharge collection of illustrative plates of combination electrode, it can be seen that rGO/ from Fig. 4 b constant current charge-discharge collection of illustrative plates
Ti3C2Tx- 20% voltage drop iR is smaller, shows that its internal equivalent resistance is smaller.Fig. 4 c be embodiment 1 prepare graphene and
Different Ti prepared by embodiment 3,5,73C2TxGraphene/Ti of incorporation3C2TxThe electrochemical impedance collection of illustrative plates of combination electrode, from figure
In 4c, it has also been discovered that rGO/Ti3C2TxThe contact resistance and series equivalent resistance of -20% electrode are smaller.
Claims (9)
1. a kind of graphene/MXene combination electrode materials, it is characterised in that be made up of two kinds of materials of graphene and MXene；Its
Preparation method includes with MXene material suspensions uniformly mixing graphene oxide suspension, after addition hydrazine hydrate is reduced
Freeze-drying, obtains the graphene/MXene combination electrode materials, the mass ratio of the graphene oxide and MXene materials is
1：（0.05~0.5）.
2. graphene according to claim 1/MXene combination electrode materials, it is characterised in that the MXene materials are
Ti3C2Tx、Ti2CTx、 Cr2CTxAt least one of, wherein TxFor-OH functional groups or/and-F functional groups.
3. graphene according to claim 1 or 2/MXene combination electrode materials, it is characterised in that the hydrazine hydrate with
The volume ratio of graphene oxide is（1~5）：200.
4. graphene/MXene combination electrode materials according to any one of claim 1-3, it is characterised in that described cold
It is first precooling 6~12 hours at -50~-80 DEG C to freeze dry, is freeze-dried 8~24 hours at 0~20 DEG C.
5. graphene/MXene combination electrode materials according to any one of claim 1-4, it is characterised in that using changing
Property Hummers methods prepare graphene oxide suspension.
6. graphene/MXene combination electrode materials according to any one of in claim 1-5, it is characterised in that will
MAX phase ceramics powders are added in high concentration HF solution, perform etching reaction at a certain temperature, then using ethanol, go from
It is then sonicated after the sub- abundant eccentric cleaning of water, obtains the MXene material suspensions.
7. graphene according to claim 6/MXene combination electrode materials, it is characterised in that the MAX phase ceramics powder
Body is Ti3AlC2、Ti2AlC、Cr2At least one of AlC.
8. graphene/MXene combination electrode materials according to claim 6 or 7, it is characterised in that the HF solution
Concentration is 40%~49%, and the certain temperature is 35~85 DEG C.
9. one kind includes the capacitive deionization stone of graphene/MXene combination electrode materials any one of claim 1-8
Black alkene/MXene combination electrodes.
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| CN111999360B (en) * | 2020-09-01 | 2021-10-29 | 上海大学 | Graphene-based non-enzymatic glucose sensor and preparation method and application thereof |
| CN112038641A (en) * | 2020-09-09 | 2020-12-04 | 宁波富理电池材料科技有限公司 | MXene silicon-carbon composite material, preparation method thereof, negative electrode and lithium ion battery |
| CN112038641B (en) * | 2020-09-09 | 2022-10-28 | 宁波富理电池材料科技有限公司 | MXene silicon-carbon composite material, preparation method thereof, cathode and lithium ion battery |
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| CN113979430A (en) * | 2021-10-21 | 2022-01-28 | 中国科学院兰州化学物理研究所 | GO/MXene composite aerogel, preparation method thereof and multi-environment sensing application |
| CN113998693A (en) * | 2021-10-22 | 2022-02-01 | 北京石墨烯技术研究院有限公司 | Preparation method of graphene nano-roll |
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| CN114371200A (en) * | 2021-12-31 | 2022-04-19 | 上海工程技术大学 | MXene-ERHG electrochemical sensor with high pollution resistance and preparation method thereof |
| CN114371200B (en) * | 2021-12-31 | 2023-10-31 | 上海工程技术大学 | High-stain-resistance MXene-ERHG electrochemical sensor and preparation method thereof |
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