CN113979438A - Graphene titanium carbide composite porous gel film and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a graphene titanium carbide composite porous gel film and a preparation method and application thereof. The preparation method comprises the steps of preparing graphene oxide gel and Ti3C2Using graphene oxide gel and Ti as precursor3C2Mixing to form composite hydrogel, then realizing the preparation of the porous hydrogel composite film by utilizing the flocculation effect of sodium hydroxide, and obtaining graphene/Ti by adopting chemical reduction3C2And (3) compounding the gel film. graphene/Ti prepared by the method3C2The composite film has a porous structure of a graphene oxide gel skeleton, can increase ion diffusion channels and active sites in the electrode material, and improves the electrochemical performance of the electrode material.
Description
Technical Field
The invention relates to the technical field of graphene material preparation, in particular to a graphene titanium carbide composite porous gel film and a preparation method and application thereof.
Background
The graphene is a single-layer six-membered ring two-dimensional material formed by hybrid linking of carbon atoms SP2, has excellent mechanical properties, electrical properties and thermal properties, and is widely applied to the aspects of materials, energy storage and the like. Compared with other methods for obtaining graphene, the graphene film is prepared from graphene oxide generated by chemical stripping, can be assembled into a film by simple processes such as filtration, spraying, tape casting and the like, is low in cost and is suitable for large-scale production.
Like the graphene material, Ti3C2The material is also a two-dimensional layered structure, and has larger specific surface area and high conductivity (up to 10 ≈ 10)4S·cm-1) Excellent mechanical properties (Young's modulus ≈ 330 Gpa) and high specific capacitance (up to ≈ 1500F-cm)-3) Due to this series of excellent property combinations, Ti3C2The material is widely applied to the fields of various novel energy storage devices (lithium ion batteries, sodium ion batteries, zinc ion batteries and the like), environment-friendly materials, catalytic materials and the like.
However, layered Ti3C2The material is easy to stack in a layered material in the electrochemical reaction process, so that a large number of ion adsorption sites are lost, the ion diffusion resistance is increased, and the performance of a device is obviously reduced.
For example, the invention with publication number CN111816868A discloses a tin disulfide-coated two-dimensional layered titanium carbide electrode material, wherein titanium carbide with a layered structure is obtained by electrolytic oxidation of flaky titanium carbide, and electrolyte required by electrolysis is NH4Cl solution and tetramethyl ammonium hydroxide (TMA. OH) solution, the electrolyte contains a small amount of polar solvent N-N dimethyl amide, dimethyl sulfoxide and N-methyl pyrrolidone, and NH4 in the aqueous solution is generated in the reaction process+And OH produced at the cathode-The product obtained by the reaction and the anode product AlCl3Reaction to regenerate Cl-And polar solvents can promote Cl-The prepared two-dimensional layered titanium carbide is placed in a dimethyl tetrahydrofuran aqueous solution to be stirred overnight, and a tin disulfide containing trace dimethyl tetrahydrofuran coats the two-dimensional layerThe electrode material of titanium carbide is favorable to strengthening Li+The conductivity of the tin disulfide-coated two-dimensional layered titanium carbide electrode material can greatly improve the charge-discharge cycle efficiency and specific capacity of the tin disulfide-coated two-dimensional layered titanium carbide electrode material, and is beneficial to industrial production.
For another example, the invention with the publication number of CN111799097A discloses a method for preparing a flexible electrode material based on solid electrolyte graphene/MXene composite fiber and a weaveable supercapacitor, high-performance graphene oxide and MXene nanosheets are prepared by an improved Hummers method and an improved etching method, and a macroscopic graphene/MXene composite fiber electrode material is prepared by wet spinning and assembled into a supercapacitor by using the liquid crystal self-assembly behavior of the graphene oxide and the MXene nanosheets. The MXene nanosheets are inserted between the graphene sheet layers, so that not only can the stacking of the graphene sheet layers be effectively inhibited, but also the spacing between the graphite sheet layers can be increased to form a good alternate arrangement structure, the quick diffusion and transmission of electrolyte ions are facilitated, and the utilization rate of the electrolyte ions in the graphene/MXene composite fibers, the graphene and active point positions in the MXene material is improved; meanwhile, MXene has good conductivity, so that ions are easy to transfer quickly in the charging and discharging processes, the internal impedance is reduced, and the capacitance performance of the capacitor is greatly improved.
However, the products prepared in the above prior art still have a layered structure, and the related problems still remain. The two-dimensional Mxene structure in the invention application with publication number CN111816868A and the invention application with publication number CN111799097A is mainly based on planar sheets, and during the process of assembling macroscopic films or fibers, the high specific surface area of Mxene causes the sheets to be stacked layer by layer, thereby reducing the effective active sites of the actual composite films or fibers.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a graphene titanium carbide composite porous gel film and a preparation method and application thereof. The preparation method comprises the steps of preparing graphene oxide gel and Ti3C2Using graphene oxide gel and Ti as precursor3C2Mixing to form composite hydrogel, and then using hydrogen and oxygenThe preparation of the porous hydrogel composite film is realized by the flocculation of sodium hydroxide, and graphene/Ti is obtained by chemical reduction3C2And (3) compounding the gel film. graphene/Ti prepared by the method3C2The composite film has a porous structure of a graphene oxide gel skeleton, can increase ion diffusion channels and active sites in the electrode material, and improves the electrochemical performance of the electrode material.
A preparation method of a graphene titanium carbide composite porous gel film comprises the following steps:
(1) mixing graphene oxide with Ti3C2Dispersing in water and mixing uniformly to form graphene oxide/Ti3C2The dispersion liquid is mixed with the aqueous dispersion liquid,
wherein, the graphene oxide and Ti3C2The mass ratio of (A) to (B) is 2-4: 1;
(2) oxidizing the graphene oxide/Ti in the step (1)3C2Casting the mixed dispersion liquid on a substrate to generate graphene oxide/Ti3C2Compounding a film;
(3) oxidizing the graphene oxide/Ti in the step (2)3C2Immersing the composite film into a sodium hydroxide gel pool to generate graphene oxide/Ti3C2Compounding a porous hydrogel film;
(4) oxidizing the graphene oxide/Ti in the step (3)3C2Reducing the composite porous hydrogel film to generate graphene/Ti3C2Compounding a porous hydrogel film;
(5) mixing the graphene/Ti obtained in the step (4)3C2Drying the composite porous hydrogel film to obtain the graphene titanium carbide composite porous gel film (namely graphene/Ti)3C2Composite porous gel film).
Preferably, in step (1), graphene oxide/Ti3C2The concentration of the graphene oxide in the mixed dispersion liquid is 13.3-16 mg/ml, and the concentration of Ti is3C2The concentration of (b) is 3.3-6.7 mg/ml. More preferably, in step (1), graphene oxide and Ti are first mixed3C2Respectively dispersing in water to form graphene oxide dispersion liquid and Ti3C2Dispersing the graphene oxide into a dispersion liquid, and mixing, wherein the mass concentration of the graphene oxide dispersion liquid is 20mg/ml, and the Ti content is3C2The mass concentration of the dispersion liquid is 10-20 mg/ml.
Preferably, in the step (2), the graphene oxide/Ti formed by casting onto the substrate3C2The thickness of the composite film was 0.3 mm.
Preferably, in the step (3), the concentration of sodium hydroxide in the sodium hydroxide gel pool is 5-10 wt%.
Preferably, in step (3), graphene oxide/Ti3C2The time for immersing the composite film into the sodium hydroxide gel pool is 10 min.
Preferably, in the step (4), the reduction is carried out by a hydrothermal reduction method or by adding a reducing agent. More preferably, in the step (4), the reducing agent is hydroiodic acid solution or hydrazine hydrate.
The invention also provides the graphene titanium carbide composite porous gel film prepared by the preparation method.
The invention also provides application of the graphene titanium carbide composite porous gel film in preparing an electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides graphene/Ti3C2Preparation method of composite porous gel film by using graphene oxide and Ti3C2Interfacial synergy between nanosheets, Ti-O-C covalent bonds and stacked Ti3C2graphene/Ti produced by slip-casting of nanosheets3C2The composite porous gel film has better toughness. Mixing Ti3C2The graphene is introduced into the graphene to prepare the porous gel film, so that the ion transmission rate among sheets is increased, the available active ion adsorption sites on the surface of the material are increased, the specific surface area of the material is greatly increased, and Ti is added3C2The resistivity of the nano-sheets in the direction vertical to the interlayer is obviously reduced, so that the Ti content is greatly improved3C2The electrochemical energy storage performance of the material as an electrode.
2. Book (I)The invention relates to graphene oxide dispersion liquid and Ti3C2The dispersion being a precursor, Ti3C2Good dispersibility in water, graphene oxide dispersion and Ti3C2Mixed dispersion Ti3C2The graphene/Ti is uniformly dispersed in the graphene oxide, so that the graphene/Ti prepared by the method3C2The graphene oxide in the composite porous gel film is uniformly wrapped in continuous Ti3C2In a network.
3. The invention uses sodium hydroxide solution as a gel pool, Ti3C2The nano-sheet can be rapidly flocculated in NaOH, Na+Intercalation between layers results in a larger interlayer spacing and terminal groups substituted with more chemically reactive hydroxyl groups. The effect of restacking can be effectively inhibited by alkalization and sodium ion intercalation, and sodium ions and Ti3C2Form an open three-dimensional porous structure. The relatively high specific surface area can increase the interface contact area between the electrode and the solution, which is beneficial to ion adsorption.
4. The invention adopts the wet spinning principle to form the film, and can control the graphene/Ti by controlling the size and the thickness of the matrix3C2The length, width and thickness of the composite porous gel film, so that the graphene/Ti prepared by the method3C2The composite porous gel film realizes controllable size.
Drawings
FIG. 1 shows graphene/Ti in example 2 of the present invention3C2Scanning electron microscope image of the cross section of the composite porous gel film.
Fig. 2 is a scanning electron microscope image of a cross section of a pure graphene thin film prepared by the experimental method in embodiment 2 of the present invention.
FIG. 3 shows graphene/Ti in example 2 of the present invention3C2And (3) cyclic voltammetry curves of the composite porous gel film at 2 mV/s.
FIG. 4 shows graphene/Ti in example 2 of the present invention3C2The composite porous gel film is at 0.5mA/cm2Constant current charge and discharge curve under current density.
FIG. 5 is an embodiment of the present inventiongraphene/Ti in example 23C2Nyquist plot for composite porous gel films.
Detailed Description
Example 1
The graphene/Ti provided in this example3C2The preparation method of the composite porous gel film comprises the following steps:
s1: 4ml of graphene oxide with the concentration of 20mg/ml and 2ml of Ti with the concentration of 20mg/ml3C2Stirring the dispersion liquid for 2 hours under the ultrasonic frequency of 40kHz and 200rpm to uniformly mix the dispersion liquid to form the graphene oxide/Ti3C2Mixing the dispersion, graphene oxide and Ti3C2The mass ratio is 2: 1.
S2: subjecting the graphene oxide/Ti3C2Casting the mixed dispersion liquid onto a substrate of 1 multiplied by 2.5cm with the thickness of 0.3mm to generate the graphene oxide/Ti3C2And (3) compounding the film.
S3: subjecting the graphene oxide/Ti3C2And soaking the composite film in a gel pool for 10min, wherein the volume of the solution in the gel pool is 200ml, and the content of sodium hydroxide is 5 wt%. The graphene oxide/Ti3C2The composite film contacts with a gel pool solution to generate graphene oxide/Ti3C2And (3) compounding the porous hydrogel film.
S4: preparing the graphene oxide/Ti prepared in the step S33C2Placing the composite porous hydrogel film in a reaction kettle, adding 10ml of water, and carrying out hydrothermal reduction for 12 hours at 180 ℃ to generate graphene/Ti3C2And (3) compounding the porous hydrogel film.
S5: preparing the graphene/Ti prepared in the step S43C2Drying the composite porous hydrogel film in the air at normal temperature for 48 hours to obtain graphene/Ti3C2And (3) compounding the porous gel film.
The graphene/Ti prepared in the example3C2And (5) carrying out performance test on the composite porous gel film. And (3) assembling the zinc ion battery by taking the porous film with the thickness of 1cm multiplied by 1cm as a working electrode, a metal zinc sheet as a counter electrode and zinc sulfate solution as electrolyte. Under the condition of charging and discharging 0.2mA, the composite film is thinThe specific discharge capacity of the film capacitor is 27mAh g-l。
Example 2
The graphene/Ti provided in this example3C2The preparation method of the composite porous gel film comprises the following steps:
s1: 8ml of graphene oxide with the concentration of 20mg/ml and 2ml of Ti with the concentration of 20mg/ml3C2Stirring the dispersion liquid for 2 hours under the ultrasonic frequency of 40kHz and 200rpm to uniformly mix the dispersion liquid to form the graphene oxide/Ti3C2Mixing the dispersion, graphene oxide and Ti3C2The mass ratio is 4: 1.
S2: subjecting the graphene oxide/Ti3C2Casting the mixed dispersion liquid onto a substrate of 1 multiplied by 2.5cm with the thickness of 0.3mm to generate the graphene oxide/Ti3C2And (3) compounding the film.
S3: subjecting the graphene oxide/Ti3C2And soaking the composite film in a gel pool for 10min, wherein the volume of the solution in the gel pool is 50ml, and the content of sodium hydroxide is 10 wt%. The graphene oxide/Ti3C2The composite film contacts with a gel pool solution to generate graphene oxide/Ti3C2A porous hydrogel film.
S4: preparing the graphene oxide/Ti prepared in the step S33C2Reducing the composite porous hydrogel film in 48% hydriodic acid at 80 ℃ for 8 hours to generate graphene/Ti3C2And (3) compounding the porous hydrogel film.
S5: preparing the graphene/Ti prepared in the step S43C2Vacuum drying the composite porous hydrogel film at 70 ℃ for 12 hours to obtain graphene/Ti3C2And (3) compounding the porous gel film.
Referring to fig. 1 and 2, fig. 1 shows the graphene/Ti prepared in this embodiment3C2Scanning electron microscope image of the cross section of the composite porous gel film. Using the experimental procedure of example 2, no Ti was added during the preparation3C2Preparing a pure graphene film, and fig. 2 is a scanning electron microscope image of a cross section of the graphene film. As can be seen from FIG. 2, the cross section of the graphene film exhibits a regularly arranged layered structureSuch a dense structure results in a limited specific surface area of the film. graphene/Ti 3C compared to graphene thin films2The composite porous gel film has a spongy porous appearance, and graphene/Ti can be seen3C2The composite porous gel film presents an irregular porous structure. These open three-dimensional porous structures render graphene/Ti3C2The composite porous gel film has relatively high specific surface area, so that the interface contact area between an electrode and a solution can be increased, ion adsorption is facilitated, and the stacking of sheets can be effectively prevented.
See tables 1 and 2, where tables 1 and 2 are the graphene film cross-section and graphene/Ti, respectively3C2Scanning electron microscope energy spectrum test of the cross section of the composite porous gel film, wherein graphene/Ti3C2The titanium element content of the composite porous gel film is obviously higher than that of the graphene film, which shows that Ti3C2Is uniformly dispersed in the film, and the mass percentage of the film is about 20 percent. And graphene thin film and graphene/Ti3C2The composite porous gel films all contain a certain amount of sodium element, which indicates that sodium ions can successfully enter interlamination Ti3C2The sheets flocculate, creating a porous structure.
Table 1 scanning electron microscopy spectroscopy of graphene film cross-section
TABLE 2 graphene/Ti3C2Scanning electron microscope energy spectrum test for composite porous gel film section
The graphene/Ti prepared in the example3C2And (5) carrying out performance test on the composite porous gel film.
Referring to fig. 3, fig. 3 is graphene/Ti3C2Cyclic voltammetry curve of composite porous gel film at 2 mV/s for the 1cm2Porous filmAnd as a working electrode, the metal zinc sheet is a counter electrode, and the zinc sulfate solution is electrolyte, so that the zinc ion battery is assembled. Under the scanning rate of 2 mV/s, a cyclic voltammogram can see a remarkable redox peak at 1.2-1.6V.
Referring to fig. 4, fig. 4 is graphene/Ti3C2The composite porous gel film is at 0.5mA/cm2The specific discharge capacity of the constant-current charge-discharge curve under current reaches 25 mAh.g-1。
Referring to fig. 5, fig. 5 is graphene/Ti3C2The composite porous gel film Nyquist curve has small inherent impedance and charge transfer impedance, and improves the performance and the service life of the battery.
Example 3
The graphene/Ti provided in this example3C2The preparation method of the composite porous gel film comprises the following steps:
s1: 4ml of graphene oxide with the concentration of 20mg/ml and 2ml of Ti with the concentration of 10mg/ml are mixed3C2Stirring the dispersion liquid for 1h at the ultrasonic frequency of 40kHz and 200rpm to uniformly mix the dispersion liquid to form the graphene oxide/Ti3C2Mixing the dispersion, graphene oxide and Ti3C2The mass ratio is 4: 1.
S2: subjecting the graphene oxide/Ti3C2Casting the mixed dispersion liquid onto a substrate of 1 multiplied by 2cm with the thickness of 0.3mm to generate the graphene oxide/Ti3C2And (3) compounding the film.
S3: subjecting the graphene oxide/Ti3C2And soaking the composite film in a gel pool for 10min, wherein the volume of the solution in the gel pool is 50ml, and the content of sodium hydroxide is 5 wt%. The graphene oxide/Ti3C2The composite film contacts with a gel pool solution to generate graphene oxide/Ti3C2And (3) compounding the porous hydrogel film.
S4: mixing the graphene oxide/Ti in the step S33C2Adding 80% hydrazine hydrate solution into the composite porous hydrogel film, and reducing for 12 hours at 90 ℃ to generate graphene/Ti3C2And (3) compounding the porous hydrogel film.
S5: will step withgraphene/Ti prepared in step S43C2Freeze drying the composite porous hydrogel film for 12 hours to obtain graphene/Ti3C2And (3) compounding the porous gel film.
graphene/Ti prepared in this example3C2The thickness of the composite porous gel film is 0.3mm, and Ti3C2The film is uniformly distributed and forms a porous appearance. The graphene/Ti prepared in the example3C2The composite porous zinc ion battery material is assembled by using zinc sulfate solution with the concentration of 1mol/L as electrolyte, and the specific discharge capacity of the zinc ion battery material reaches 28 mAh.g-l。
Claims (10)
1. The preparation method of the graphene titanium carbide composite porous gel film is characterized by comprising the following steps:
(1) mixing graphene oxide with Ti3C2Dispersing in water and mixing uniformly to form graphene oxide/Ti3C2The dispersion liquid is mixed with the aqueous dispersion liquid,
wherein, the graphene oxide and Ti3C2The mass ratio of (A) to (B) is 2-4: 1;
(2) oxidizing the graphene oxide/Ti in the step (1)3C2Casting the mixed dispersion liquid on a substrate to generate graphene oxide/Ti3C2Compounding a film;
(3) oxidizing the graphene oxide/Ti in the step (2)3C2Immersing the composite film into a sodium hydroxide gel pool to generate graphene oxide/Ti3C2Compounding a porous hydrogel film;
(4) oxidizing the graphene oxide/Ti in the step (3)3C2Reducing the composite porous hydrogel film to generate graphene/Ti3C2Compounding a porous hydrogel film;
(5) mixing the graphene/Ti obtained in the step (4)3C2And drying the composite porous hydrogel film to obtain the graphene titanium carbide composite porous gel film.
2. Preparation according to claim 1The method is characterized in that in the step (1), graphene oxide/Ti is used3C2The concentration of the graphene oxide in the mixed dispersion liquid is 13.3-16 mg/ml, and the concentration of Ti is3C2The concentration of (b) is 3.3-6.7 mg/ml.
3. The method according to claim 2, wherein in the step (1), graphene oxide and Ti are first prepared3C2Respectively dispersing in water to form graphene oxide dispersion liquid and Ti3C2Dispersing the graphene oxide into a dispersion liquid, and mixing, wherein the mass concentration of the graphene oxide dispersion liquid is 20mg/ml, and the Ti content is3C2The mass concentration of the dispersion liquid is 10-20 mg/ml.
4. The method according to claim 1, wherein in the step (2), the graphene oxide/Ti formed on the substrate is cast3C2The thickness of the composite film was 0.3 mm.
5. The preparation method according to claim 1, wherein in the step (3), the mass percentage concentration of the sodium hydroxide in the sodium hydroxide gel pool is 5-10 wt%.
6. The method according to claim 1, wherein in the step (3), graphene oxide/Ti is used3C2The time for immersing the composite film into the sodium hydroxide gel pool is 10 min.
7. The method according to claim 1, wherein in the step (4), the reduction is carried out by a hydrothermal reduction method or by adding a reducing agent.
8. The method according to claim 7, wherein in the step (4), the reducing agent is a hydroiodic acid solution or hydrazine hydrate.
9. The graphene titanium carbide composite porous gel film prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the graphene titanium carbide composite porous gel film according to claim 9 in the preparation of electrode materials.
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