CN107633954B - graphene/MXene composite electrode material and application thereof - Google Patents
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Abstract
The invention relates to a graphene/MXene composite electrode material and application thereof, wherein the graphene/MXene composite electrode material consists of two materials, namely graphene and MXene; the preparation method comprises the steps of uniformly mixing a graphene oxide suspension and an MXene material suspension, adding hydrazine hydrate for reduction, and then freeze-drying to obtain the graphene/MXene composite electrode material, wherein the mass ratio of the graphene oxide to the MXene material is 1: (0.05-0.5). When the graphene and MXene are compounded, irregular MXene particle materials can be used as an intercalator and a dispersing agent and enter between graphene sheet layers, so that the agglomeration effect between the graphene sheet layers is overcome, and the usable specific surface area of the graphene is increased. In addition, MXene material has excellent hydrophilicity and conductivity, and can further improve the electrochemical performance and the capacitive deionization performance of the composite material.
Description
Technical Field
the invention belongs to the field of preparation of composite electrodes for capacitive deionization, and particularly relates to a preparation method of a graphene/MXene composite material for capacitive deionization.
background
With the rapid development of human society, the crisis of fresh water resources becomes an urgent problem to be solved in all countries in the world, and the shortage of water resources has become a main factor for restricting the development of multiple countries. The capacitive deionization technology is an efficient, energy-saving and environment-friendly desalting method, and the aim of desalting is fulfilled by applying an electrostatic field to force ions to migrate to electrodes on two sides and enabling the ions to be adsorbed by a double electric layer generated on the surfaces of the electrodes. The key of the capacitive deionization technology is the preparation of high-performance electrode materials, which are required to have higher specific surface area, reasonable pore size distribution and good conductivity and hydrophilicity.
The graphene has ultrahigh theoretical specific surface area and good conductivity, and is an ideal capacitive deionization electrode material. However, the inevitable agglomeration effect between graphene layers seriously affects the actual usable specific surface area, and restricts the application of the graphene layer as an electrode material.
Disclosure of Invention
In view of the above problems, the present invention combines MXene material having good hydrophilicity and conductivity as an intercalating agent and a dispersant with redox graphene for the first time to prepare a novel graphene-based composite electrode material, and aims to provide an electrode material for capacitive deionization having excellent electrochemical properties and desalination properties.
On one hand, the invention provides a graphene/MXene composite electrode material which is composed of graphene and MXene, wherein the preparation method comprises the steps of uniformly mixing a graphene oxide suspension and an MXene material suspension, adding hydrazine hydrate for reduction, and then carrying out freeze drying to obtain the graphene/MXene composite electrode material, wherein the mass ratio of the graphene oxide to the MXene material is 1: (0.05-0.5).
The MXene material has the characteristics of good hydrophilicity and conductivity, larger specific capacitance, excellent electrochemical performance and the like. When the graphene and MXene are compounded, irregular MXene particle materials can be used as an intercalator and a dispersing agent and enter between graphene sheet layers, so that the agglomeration effect between the graphene sheet layers is overcome, and the usable specific surface area of the graphene is increased. In addition, MXene material has excellent hydrophilicity and conductivity, and can further improve the electrochemical performance and the capacitive deionization performance of the composite material.
Preferably, the MXene material is Ti3C2Tx(TxIs a functional group such as-OH, -F), Ti2CTx(TxIs a functional group such as-OH, -F), Cr2CTx(TxIs a functional group such as-OH, -F, etc.).
Preferably, the volume ratio of the hydrazine hydrate to the graphene oxide is (1-5): 200.
Preferably, the freeze drying is pre-freezing for 6 to 12 hours at a temperature of between 50 ℃ below zero and 80 ℃ below zero, and then freeze drying for 8 to 24 hours at a temperature of between 0 and 20 ℃.
Preferably, the graphene oxide suspension is prepared by a modified Hummers method.
preferably, MAX phase ceramic powder is added into a high-concentration HF solution, etching reaction is carried out at a certain temperature, and then the MXene material suspension is obtained after full centrifugal cleaning by using ethanol and deionized water and ultrasonic treatment.
Preferably, the MAX phase ceramic powder is Ti3AlC2、Ti2AlC、Cr2At least one of AlC.
Preferably, the concentration of the HF solution is 40-49%, and the certain temperature is 35-85 ℃.
On the other hand, the invention also provides a graphene/MXene composite electrode for capacitive deionization based on the graphene/MXene composite electrode material. The preparation method comprises the steps of grinding the graphene/MXene composite electrode material into powder, uniformly mixing the powder with a small amount of adhesive and conductive carbon black according to a certain proportion, adding a proper amount of solvent to form a uniform colloidal body with a certain viscosity, and rolling the colloidal body onto a current collector to obtain the composite electrode for capacitive deionization.
Preferably, the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol and polypropylene.
Preferably, the mass ratio of the graphene/MXene composite electrode material to the binder to the conductive carbon black is (8-9): 1-0.5.
Preferably, the current collector is at least one of a graphite plate, a copper plate, a nickel mesh and a titanium mesh.
The graphene/MXene composite electrode prepared by the method has good hydrophilicity, good conductivity and large specific surface area, ions can be rapidly diffused and transported on the surface of the electrode, the performance of the electrode for adsorbing the ions can be improved, and the graphene/MXene composite electrode is suitable for the fields of capacitive deionization and super capacitors. The method for preparing the graphene/MXene composite electrode material and the graphene/MXene composite electrode for capacitive deionization comprising the graphene/MXene composite electrode material is simple and easy to implement, and easy to popularize and apply in large-scale industrialization.
Drawings
FIG. 1 shows graphene (rGO) prepared in example 1 and Ti prepared in example 23C2TxMaterials and different Ti's prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxAn XRD spectrum of the composite electrode material;
Fig. 2a is an SEM image of graphene prepared in example 1;
FIG. 2b shows Ti prepared in example 23C2TxSEM topography of materials
FIG. 2c shows the graphene and Ti prepared in examples 3, 5 and 73C2TxSchematic diagram of internal structure of composite sample
FIG. 3a is graphene/Ti prepared in example 33C2TxCyclic voltammograms at different scan rates for 20% of the composite electrode;
FIG. 3b is the graphene/Ti prepared in example 33C2TxCyclic voltammograms of 20% composite electrode at a scan rate of 25mV/s for different scan times;
FIG. 3c is graphene/Ti prepared in example 33C2Tx-a constant current charge and discharge profile for different cycle times for 20% of the composite electrode;
FIG. 4a shows graphene prepared in example 1 and various Ti prepared in examples 3, 5 and 73C2Txdoped amount of graphene/Ti3C2TxCyclic voltammetry of the composite electrode at a scanning speed of 25 mV/s;
FIG. 4b shows the graphene prepared in example 1 and different Ti prepared in examples 3, 5 and 73C2Txdoped amount of graphene/Ti3C2TxConstant current charge and discharge spectra of the composite electrode;
FIG. 4c shows graphene prepared in example 1 and various Ti prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxAn electrochemical impedance profile of the composite electrode;
FIGS. 5a and 5b are the graphene electrode prepared in example 1, and the Ti electrode prepared in example 23C2TxMaterial and graphene/Ti prepared in example 33C2Tx-20% capacitive deionization performance test plot of composite electrode;
FIG. 6 is a schematic diagram of a capacitive deionization testing apparatus.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
according to the invention, after uniformly mixing a graphene oxide stable dispersion liquid (such as a graphene oxide suspension) and an MXene stable dispersion liquid (such as an MXene material suspension) (for example, firstly performing magnetic stirring and then ultrasonic oscillation), adding hydrazine hydrate for reduction reaction, and then performing freeze drying to obtain the graphene/MXene composite electrode material. Wherein the mass ratio of the added graphene oxide to the MXene material is 1: (0.05-0.5). If the addition amount of the MXene material is less than 5 wt% of that of the graphene oxide, the effect of the MXene as the graphene intercalator is not obvious, and the specific surface area of the composite material is still small; if the addition amount of the MXene material is more than 50 wt% of the addition amount of the graphene oxide, the MXene material and the graphene material are not easy to be uniformly dispersed, the composite material is easy to generate lumps, and the conductivity and the specific surface area of the composite material are affected. The graphene/MXene composite electrode material is ball-milled into powder, uniformly mixed with a small amount of adhesive and conductive carbon black, added with a proper amount of solvent to form uniform paste with certain viscosity, and the paste is rolled into sheets (300 mu m) by a small-sized roller press and pressed on a current collector to obtain the composite electrode for capacitive deionization. The following exemplarily illustrates a preparation method of the graphene/MXene composite electrode material for capacitive deionization provided by the present invention.
And preparing the graphene oxide suspension by using a modified Hummers method. As a detailed example, the ground natural crystalline flake graphite is soaked in a mixed solution of concentrated nitric acid and concentrated sulfuric acid (the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid can be 1: 0.5-1.) at 70-90 ℃ for 5-10 h, cooled to room temperature, filtered, fully washed with deionized water until the filtrate is neutral, and dried in vacuum to obtain pre-oxidized crystalline flake graphite. Adding a certain amount of concentrated sulfuric acid (the volume can be 90-120 ml), 2g of pre-oxidized crystalline flake graphite and 1g of sodium nitrate solid into a 1000ml beaker placed in an ice water bath kettle, stirring for 0.5-1 h, and then adding a certain amount of potassium permanganate (the total addition amount of potassium permanganate can be 6-12 g) every 15 minutes, wherein the reaction temperature is not more than 15 ℃. And transferring the beaker to a 35 ℃ water bath kettle, and continuously stirring for 2-4 hours. Then 100ml deionized water was added, the temperature was raised to 95 ℃ and 300ml deionized water was added for dilution. Adding 50ml of 30% hydrogen peroxide, stirring for 30min, and performing ultrasonic treatment for 2 h. And (3) centrifuging while hot, firstly centrifuging by using 5% dilute hydrochloric acid, then adding deionized water, continuing to centrifuge until the pH value of the solution is about 7, and carrying out ultrasonic treatment on the centrifuged solution to obtain the graphene oxide suspension.
Preparation of a two-dimensional crystalline material MXene suspension (MXene material suspension). The specific process is as follows: the grinded MAX phase ceramic powder is soaked in a high-concentration HF solution (the mass fraction can be 40% -49%) for a certain time at a certain temperature (the temperature can be 35-85 ℃), then the solution is fully centrifugally cleaned by ethanol and deionized water, and the solution is a stable MXene material suspension after ultrasonic treatment. The MAX phase ceramic may be Ti3AlC2、Ti2AlC、Cr2One or more of AlC. The MXene material can be Ti3C2Tx(TxIs a functional group such as-OH, -F), Ti2CTx(TxIs a functional group such as-OH, -F), Cr2CTx(TxIs one or more of-OH, F and other functional groups).
And (3) uniformly mixing the graphene oxide suspension and the MXene material suspension through magnetic stirring and ultrasonic oscillation, adding hydrazine hydrate, reducing, and freeze-drying to obtain the graphene/MXene composite electrode material. Wherein the mass ratio of the graphene oxide to the MXene material can be 1: 0.05-0.5. The volume ratio of hydrazine hydrate to graphene oxide is (2-10 ml): 400 ml. The freeze drying is pre-freezing for 6-12 hours at the temperature of-50 to-80 ℃, and then freeze drying for 8-24 hours at the temperature of-50 to-80 ℃.
The invention also provides a graphene/MXene composite electrode for capacitive deionization. Specifically, the graphene/MXene composite electrode material is ground into powder, uniformly mixed with a small amount of adhesive (such as polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, polypropylene and the like) and conductive carbon black according to a certain proportion (such as 8:1:1), and added with a proper amount of solvent (such as absolute ethyl alcohol, deionized water and the like) to form a uniform colloidal body with a certain viscosity. And rolling the colloidal body onto a current collector (such as a graphite plate, a copper plate, a nickel net and a titanium net) to form a sheet (the thickness of the electrode can be 150-300 um)), so as to obtain the composite electrode for capacitive deionization.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1 preparation of pure graphene electrode and capacitive deionization Performance test
And preparing the graphene oxide suspension by using a modified Hummers method. The method comprises the steps of soaking ground natural crystalline flake graphite in a mixed solution of concentrated nitric acid and concentrated sulfuric acid (the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1:1) at 70-90 ℃ for 6h, cooling to room temperature, filtering, fully washing with deionized water until the filtrate is neutral, and drying in vacuum to obtain pre-oxidized crystalline flake graphite. 100ml of concentrated sulfuric acid, 2g of pre-oxidized crystalline flake graphite and 1g of sodium nitrate solid are added into a 1000ml beaker placed in an ice water bath kettle, the mixture is stirred for 1 hour, 6g of potassium permanganate are added every 15 minutes, and the reaction temperature is not more than 15 ℃. The beaker was transferred to a 35 ℃ water bath and stirring was continued for 4 hours. Then 100ml deionized water was added, the temperature was raised to 95 ℃ and 300ml deionized water was added for dilution. Adding 50ml of 30% hydrogen peroxide, stirring for 30min, and performing ultrasonic treatment for 2 h. Centrifuging while hot, firstly centrifuging with 5% dilute hydrochloric acid, then adding deionized water and continuing to centrifuge until the pH of the solution is about 7, carrying out ultrasonic treatment on the centrifuged solution to obtain a graphene oxide suspension, adding hydrazine hydrate into the prepared graphene oxide suspension according to the volume ratio of 100:1, carrying out reduction reaction for 2 hours at 95 ℃, filtering and cleaning a reaction product until the filtrate is nearly neutral, and obtaining a redox graphene solution;
Pre-freezing the prepared redox graphene solution at-80 ℃ for 8h by using a freeze drying oven, and then freeze-drying the solution for 24h at 5 ℃ by using the freeze drying oven. Taking 0.48g of freeze-dried graphene powder and 0.06g of conductive carbon black, grinding to fully mix the graphene powder and the conductive carbon black, slowly dropwise adding PTFE emulsion (the mass fraction of the PTFE emulsion is 60%), wherein the mass of the PTFE is 0.06g, adding a small amount of ethanol, stirring to form paste with certain viscosity, rolling the paste into sheets (300 um) by using a small roller press, pressing the sheets on a graphite plate, and performing vacuum drying for 8 hours to obtain a pure graphene electrode (rGO).
According to the schematic diagram of the capacitive deionization test device in FIG. 6, two pure graphene electrodes are taken to form a capacitive deionization test unit, and the initial conductivity is about 200us-1the 40ml NaCl solution was desalted and the capacitive deionization performance test was conducted under a target voltage of 1.6V. In the NaCl solution conductivity curve with time (fig. 5a), the single-cycle desalting amount of the pure graphene electrode was 2.78mg/g in the case of the pure graphene electrode (see fig. 5 b).
Example 2 pure MXene Ti3C2TxElectrode preparation and capacitive deionization performance test
2g of Ti3AlC2Adding the ceramic powder into 50ml of 49% HF solution, carrying out etching reaction for 18h at 60 ℃, then fully centrifugally cleaning by using ethanol and deionized water, then carrying out ultrasonic treatment,To obtain Ti3C2Txa material suspension;
Ti to be prepared3C2TxThe suspension is pre-frozen at-80 deg.C for 8 hr in a freeze drying oven, and then freeze-dried at 5 deg.C for 24 hr in a freeze drying oven. 0.64g of freeze-dried Ti was taken3C2TxGrinding the powder and 0.08g of conductive carbon black to fully mix the powder and the conductive carbon black, slowly dripping PTFE emulsion (the mass fraction of the PTFE emulsion is 60 percent) into the mixture, adding a small amount of ethanol into the mixture, stirring the mixture into paste with certain viscosity, rolling the paste into sheets (about 300 mu m) by using a small-sized roller press, pressing the sheets on a graphite plate, and drying the sheets in vacuum for 8 hours to obtain pure Ti3C2TxAnd an electrode.
According to the schematic diagram of FIG. 6, two sheets of Ti are taken3C2TxThe electrodes constitute a capacitive deionization test cell with an initial conductivity of about 200us-1The 40ml NaCl solution was desalted and the capacitive deionization performance test was conducted under a target voltage of 1.6V. FIG. 5 shows the conductivity of the NaCl solution as a function of time (see FIG. 5a), in the case of the composite electrode, the desalination rate per cycle of the electrode is 1.95mg/g (see FIG. 5 b).
Example 3 graphene/MXene composite electrode preparation and capacitive deionization performance testing:
The graphene oxide suspension obtained in example 1 and the Ti prepared in example 2 were mixed3C2TxUniformly mixing the raw materials in a mass ratio of 1:0.2 through magnetic stirring and ultrasonic oscillation, adding hydrazine hydrate into the prepared composite suspension in a volume ratio of 100:1, carrying out reduction reaction for 2 hours at 95 ℃, filtering and cleaning reaction products until the filtrate is nearly neutral to obtain a graphene/MXene solution (rGO/Ti)3C2Tx-20％)；
The prepared alloy contains 20 wt% of Ti3C2TxThe graphene/MXene composite solution is pre-frozen for 8 hours at-80 ℃ by using a freeze drying box, and then is freeze-dried for 24 hours at 5 ℃ by using the freeze drying box. Taking 0.56g of freeze-dried rGO/Ti3C2Tx-20% composite electrode materialAnd 0.07g of conductive carbon black, grinding to fully mix the conductive carbon black, slowly dropwise adding PTFE emulsion (the mass fraction of the PTFE emulsion is 60 percent), wherein the mass of the PTFE is 0.07g, adding a small amount of ethanol, stirring to form paste with certain viscosity, rolling the paste into sheets (about 300um) by using a small roller press and pressing the sheets on a graphite plate, and performing vacuum drying for 8 hours to obtain the graphene/MXene composite electrode (rGO/Ti)3C2Tx-20％)。
According to the schematic diagram of the capacitive deionization test device in FIG. 6, two composite electrodes are used to form a capacitive deionization test unit with initial conductivity of 200us-1The 40ml NaCl solution was desalted and the capacitive deionization performance test was conducted under a target voltage of 1.6V. FIG. 5 shows the conductivity of the NaCl solution as a function of time (see FIG. 5a), with a combined electrode, the desalination rate per cycle of the electrode is 4.56mg/g (see FIG. 5 b).
Example 4 graphene electrode preparation and electrochemical performance testing:
0.16g of the freeze-dried graphene rGO electrode material prepared in the example 1 and 0.02g of conductive carbon black are taken, ground and fully mixed, then PTFE emulsion (the mass fraction of the PTFE emulsion is 60%) is slowly added dropwise, wherein the mass of the PTFE is 0.02g, a small amount of ethanol is added, the mixture is stirred into paste with certain viscosity, the paste is rolled into sheets (300 um) by a small-sized roller press and pressed on a porous nickel plate, and the graphene electrode is obtained after vacuum drying for 8 hours. Cutting the obtained electrode into a square with the thickness of 1cm by 1cm to be used as a working electrode, taking a silver/silver chloride electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a sodium chloride solution with the concentration of 1mol/L as a test solution, and carrying out electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrochemical impedance and the like by utilizing an electrochemical workstation.
Example 5 graphene/MXene composite electrode preparation and electrochemical performance testing:
The graphene oxide suspension obtained in example 1 and the Ti prepared in example 2 were mixed3C2TxAccording to the mass ratio of 1:0.05, after being uniformly mixed by magnetic stirring and ultrasonic oscillation, hydrazine hydrate is added into the prepared composite suspension according to the volume ratio of 100:1, reduction reaction is carried out for 2h at the temperature of 95 ℃, and the obtained product is obtainedFiltering and cleaning reaction products until the filtrate is nearly neutral to obtain a graphene/MXene solution (rGO/Ti)3C2Tx-5％)；
The prepared Ti content of 5 wt% is3C2TxThe graphene/MXene composite solution is pre-frozen for 8 hours at-80 ℃ by using a freeze drying box, and then is freeze-dried for 24 hours at 5 ℃ by using the freeze drying box to obtain rGO/Ti3C2Tx-5% composite electrode material. Taking 0.16g of freeze-dried rGO/Ti3C2TxGrinding 5% of composite electrode material and 0.02g of conductive carbon black to fully mix the materials, then slowly adding PTFE emulsion (the mass fraction of the PTFE emulsion is 60%) dropwise, wherein the mass of the PTFE is 0.02g, adding a small amount of ethanol, stirring to form paste with certain viscosity, rolling the paste into sheets (300 um) by using a small roller press and pressing the sheets on a porous nickel plate, and drying in vacuum for 8 hours to obtain the graphene/MXene composite electrode (rGO/Ti)3C2Tx-5%). Cutting the obtained electrode into a square with the thickness of 1cm by 1cm to be used as a working electrode, taking a silver/silver chloride electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a sodium chloride solution with the concentration of 1mol/L as a test solution, and carrying out electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrochemical impedance and the like by utilizing an electrochemical workstation.
Example 6 graphene/MXene composite electrode preparation and electrochemical performance testing:
0.16g of freeze-dried rGO/Ti prepared in example 3 was taken3C2Tx-20% of composite electrode material and 0.02g of conductive carbon black, grinding to fully mix the materials, then slowly dripping PTFE emulsion (the mass fraction of the PTFE emulsion is 60%), wherein the mass of the PTFE is 0.02g, adding a small amount of ethanol, stirring to form paste with certain viscosity, rolling the paste into sheets (300 um) by a small roller press and pressing the sheets on a porous nickel plate, and drying in vacuum for 8 hours to obtain the graphene/MXene composite electrode (rGO/Ti)3C2Tx-20%). Cutting the obtained electrode into 1 cm-1 cm squares as a working electrode, taking a silver/silver chloride electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a sodium chloride solution with the concentration of 1mol/L as a test solution, and utilizing an electrochemical workstationAnd performing electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrochemical impedance and the like.
Example 7 graphene/MXene composite electrode preparation and electrochemical performance testing:
The graphene oxide suspension obtained in example 1 and the Ti prepared in example 2 were mixed3C2TxUniformly mixing the raw materials in a mass ratio of 1:0.35 through magnetic stirring and ultrasonic oscillation, adding hydrazine hydrate into the prepared composite suspension in a volume ratio of 100:1, carrying out reduction reaction for 2 hours at 95 ℃, filtering and cleaning reaction products until the filtrate is nearly neutral to obtain a graphene/MXene solution (rGO/Ti)3C2Tx-35％)；
The prepared alloy contains 35 wt% of Ti3C2TxThe graphene/MXene composite solution is pre-frozen for 8 hours at-80 ℃ by using a freeze drying box, and then is freeze-dried for 24 hours at 5 ℃ by using the freeze drying box to obtain rGO/Ti3C2Tx-35% composite electrode material. Taking 0.16g of freeze-dried rGO/Ti3C2TxGrinding 35% of composite electrode material and 0.02g of conductive carbon black to fully mix the materials, then slowly adding PTFE emulsion (the mass fraction of the PTFE emulsion is 60%) dropwise, wherein the mass of the PTFE is 0.02g, adding a small amount of ethanol, stirring to form paste with certain viscosity, rolling the paste into sheets (300 um) by using a small roller press and pressing the sheets on a porous nickel plate, and drying in vacuum for 8 hours to obtain the graphene/MXene composite electrode (rGO/Ti)3C2Tx-35%). Cutting the obtained electrode into a square with the thickness of 1cm by 1cm to be used as a working electrode, taking a silver/silver chloride electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a sodium chloride solution with the concentration of 1mol/L as a test solution, and carrying out electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrochemical impedance and the like by utilizing an electrochemical workstation.
FIG. 1 shows graphene (rGO) prepared in example 1 and Ti prepared in example 23C2TxMaterials and different Ti's prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxXRD pattern of the composite electrode material. From the figure canit is seen that various graphene/Ti3C2TxGraphene and Ti are simultaneously displayed in XRD (X-ray diffraction) pattern of composite electrode material3C2TxWith Ti3C2Txthe content is increased, and the intensity of the characteristic peak is increased, which indicates that the composite electrode material is successfully prepared.
FIGS. 2a-2c show the graphene prepared in example 1 and the Ti prepared in example 2, respectively3C2TxSEM topography of the Material and graphene and Ti prepared in examples 3, 5 and 73C2TxSchematic diagram of the internal structure of the composite material. As can be seen from the figure, when the graphene is compounded with the MXene, irregular MXene small particles play a role of a dispersing agent and are inserted into the graphene layer, so that the agglomeration effect of the graphene is overcome to a certain extent.
FIG. 3a is graphene/Ti prepared in example 33C2TxAnd (3) cyclic voltammetry curves of 20% of the composite electrode at different scanning rates, and as can be seen from fig. 3a, no obvious redox peak appears at any scanning rate, which indicates that the composite electrode has good double-layer capacitance performance. In addition, the cyclic voltammetry curve has obvious symmetry, which indicates that the composite electrode has excellent ion adsorption/desorption reversibility. rGO/Ti3C2TxAfter 100 charge-discharge cycles of the-20% electrode, the changes of the cyclic voltammetry spectrum and the constant current charge-discharge spectrum are small as can be seen from figures 3b and 3c, and the result proves that the rGO/Ti3C2TxThe cycling stability of the-20% electrode is better.
FIG. 4a shows graphene prepared in example 1 and various Ti prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxThe cyclic voltammetry curve of the composite electrode at a scanning speed of 25mV/s shows that rGO/Ti can be seen from the cyclic voltammetry maps of different materials in FIG. 4a3C2TxThe-20% composite electrode material has more excellent electrochemical characteristics, better specific capacitance and excellent electrode stability. FIG. 4b shows the graphene prepared in example 1 and different Ti prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxThe constant current charge-discharge atlas of the composite electrode, from FIG. 4b the rGO/Ti constant current charge-discharge atlas is seen3C2TxThe voltage drop iR of-20% is small, indicating that its internal equivalent resistance is small. FIG. 4c shows graphene prepared in example 1 and various Ti prepared in examples 3, 5 and 73C2TxDoped amount of graphene/Ti3C2TxElectrochemical impedance mapping of the composite electrode, from FIG. 4c, rGO/Ti can also be found3C2TxThe contact resistance and the series equivalent resistance of the-20% electrode are small.
Claims (8)
1. The graphene/MXene composite electrode material for capacitive deionization is characterized by consisting of a graphene sheet layer and an irregular MXene granular material entering the graphene sheet layer, wherein the MXene granular material is Ti3C2Tx、Ti2CTx、 Cr2CTxAt least one of (1), wherein TxIs an-OH function or/and a-F function; the preparation method comprises the steps of uniformly mixing a graphene oxide suspension and an MXene material suspension, adding hydrazine hydrate for reduction, and then freeze-drying to obtain the graphene/MXene composite electrode material, wherein the mass ratio of the graphene oxide to the MXene material is 1: (0.05-0.35).
2. The graphene/MXene composite electrode material according to claim 1, wherein the volume ratio of hydrazine hydrate to graphene oxide is (1-5): 200.
3. The graphene/MXene composite electrode material according to claim 1, wherein the freeze drying is pre-freezing at-50 to-80 ℃ for 6 to 12 hours, and then freeze drying at 0 to 20 ℃ for 8 to 24 hours.
4. the graphene/MXene composite electrode material according to claim 1, wherein the graphene oxide suspension is prepared by a modified Hummers method.
5. The graphene/MXene composite electrode material according to claim 1, wherein MAX phase ceramic powder is added into a high-concentration HF solution, an etching reaction is performed at a certain temperature, and then the MXene material suspension is obtained by fully centrifuging and cleaning with ethanol and deionized water and then performing ultrasonic treatment.
6. The graphene/MXene composite electrode material of claim 5, wherein the MAX phase ceramic powder is Ti3AlC2、Ti2AlC、Cr2At least one of AlC.
7. The graphene/MXene composite electrode material according to claim 5 or 6, wherein the concentration of the HF solution is 40% -49%, and the certain temperature is 35-85 ℃.
8. A graphene/MXene composite electrode for capacitive deionization comprising the graphene/MXene composite electrode material of any one of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529455A (en) * | 2014-12-23 | 2015-04-22 | 陕西科技大学 | Low-temperature preparation method of titanium dioxide/two-dimensional layered titanium carbide composite material |
| CN105098162A (en) * | 2015-09-14 | 2015-11-25 | 哈尔滨工业大学 | Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery |
| CN105129775A (en) * | 2015-07-15 | 2015-12-09 | 江南大学 | Three-dimensional porous graphene electrode and preparation method thereof |
| WO2016049109A2 (en) * | 2014-09-25 | 2016-03-31 | Drexel University | Physical forms of mxene materials exhibiting novel electrical and optical characteristics |
-
2016
- 2016-07-19 CN CN201610570545.5A patent/CN107633954B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016049109A2 (en) * | 2014-09-25 | 2016-03-31 | Drexel University | Physical forms of mxene materials exhibiting novel electrical and optical characteristics |
| CN104529455A (en) * | 2014-12-23 | 2015-04-22 | 陕西科技大学 | Low-temperature preparation method of titanium dioxide/two-dimensional layered titanium carbide composite material |
| CN105129775A (en) * | 2015-07-15 | 2015-12-09 | 江南大学 | Three-dimensional porous graphene electrode and preparation method thereof |
| CN105098162A (en) * | 2015-09-14 | 2015-11-25 | 哈尔滨工业大学 | Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| MXene材料与三维石墨烯复合及其超级电容器性能;汪浩，等;《装备制造技术》;20150531;第263-265页 * |
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