CN114275799B - Flexible self-supporting graphene/manganese hexacyanoferrate composite material and preparation method and application thereof - Google Patents
Flexible self-supporting graphene/manganese hexacyanoferrate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flexible self-supporting graphene/manganese hexacyanoferrate composite material and a preparation method and application thereof. According to the preparation method, graphene oxide hydrogel is used as a matrix, manganese hexacyanoferrate is loaded in the graphene oxide hydrogel by a wet chemical method, and then the graphene/manganese hexacyanoferrate composite material is obtained through chemical reduction. The electronic conductivity of the whole composite electrode can be obviously enhanced after the graphene oxide framework is reduced. Meanwhile, the porous framework of the graphene oxide gel is loaded with the manganese hexacyanoferrate active substance, so that a sufficient transmission channel can be provided for the ion transportation in the electrode, and the diffusion of electrolyte ions is facilitated. The preparation method provided by the invention has the advantages of simple and convenient process, low cost and easy operation.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a flexible self-supporting graphene/manganese hexacyanoferrate composite material and a preparation method and application thereof.
Background
The manganese hexacyanoferrate has a structure similar to that of prussian blue, and the specific micropore and mesoporous structure of the manganese hexacyanoferrate is beneficial to charge transfer in a pore structure; meanwhile, the manganese hexacyanoferrate also has the advantages of no toxicity, low cost, environmental friendliness, good stability and the like. Therefore, the manganese ferricyanide has potential application prospects in the fields of sodium ion batteries/capacitors, super capacitors, zinc ion batteries and the like. At present, manganese hexacyanoferrate electrode materials mainly comprise powder, conductive additives, binders and other components are generally required to be introduced in the preparation process of electrodes, the components are fully stirred to form slurry, the slurry is coated on a current collector, and then the slurry is dried to obtain an electrode plate.
However, compared with self-supporting electrode materials, the electrode materials coated by adding the binder and the conductive additive have poor mechanical properties and are easy to fall off, the electrode preparation process is complex, and the time cost is high. Meanwhile, the self-supporting electrode material prepared based on the graphene film is difficult to avoid the problem of agglomeration among graphene sheet layers, so that the effective utilization rate of the electrode material is reduced. The invention with the publication number of CN113054175A discloses a flexible zinc ion battery anode material MnO2A preparation method of/C film for solving the problem of MnO prepared by the prior art2Short length of electrode material, no flexibility and no application in flexible zinc ion battery. The method uses ultra-long MnO2Nano wire as active material, adding conductive carbon material, ultrasonic dispersing and suction filtering to obtain self-supporting MnO with flexible characteristic2the/C film can be directly used as the anode material of the flexible zinc ion battery to be applied to the flexible zinc ion battery. Wherein, the ultra-long MnO2The nanowires are intertwined with each other to form a self-supporting film, so that the conductive carbon material is uniformly dispersed in MnO without adding an additional binder2The network of (2) gives the film excellent conductivity, and the content of the film is 10% -60%. Disclosed in this prior art is MnO2The preparation method of the electrode material with the self-supporting nanowire is complex, and the temperature is high during preparation.
The invention application with the publication number of CN110237868A discloses a supported ultrasmall Prussian blue analogue and a preparation method and application thereof. The preparation method comprises the following steps: 1) mixing a trivalent metal compound, a divalent metal compound, a first solvent, a ligand and graphene, reacting, and washing to obtain a graphene-loaded ultrasmall Prussian blue analogue; 2) and dispersing the turbid solution of the graphene supported ultra-small Prussian blue analogue in a first solvent, adding a reducing agent and an alkaline solution, and mixing and reacting to obtain the graphene supported ultra-small Prussian blue analogue after graphene reduction. The method can realize the synthesis of the graphene-loaded ultra-small Prussian blue analogue and the synthesis of the ultra-small Prussian blue analogue. The supported ultra-small Prussian blue analogue prepared by the method is a composite structure of the Prussian blue analogue and graphene, and can improve the conductivity of the catalyst. In the prior art, graphene and Prussian blue are mechanically mixed, the prepared electrode material does not have the characteristic of flexible self-support, and a conductive additive and a binder are required to be added in the assembly process of the electrode material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a flexible self-supporting graphene/manganese hexacyanoferrate composite material and a preparation method and application thereof.
A preparation method of a flexible self-supporting graphene/manganese hexacyanoferrate composite material comprises the following steps:
(1) casting graphene oxide gel onto a substrate to form a gel film;
(2) dissolving manganese sulfate in an ethanol water solution to prepare a manganese sulfate solution;
(3) immersing the gel film in the step (1) and the matrix into the manganese sulfate solution prepared in the step (2);
(4) adding potassium ferricyanide into the solution obtained in the step (3) to react;
(5) and (5) taking out the gel film treated in the step (4) together with the substrate, reducing to obtain a graphene/manganese hexacyanoferrate film, and stripping the graphene/manganese hexacyanoferrate film from the substrate after cleaning to obtain the flexible self-supporting graphene/manganese hexacyanoferrate composite material.
Preferably, in the step (1), the concentration of the graphene oxide in the graphene oxide gel is 10-20 mg/ml.
Preferably, in the step (1), the thickness of the graphene oxide gel cast on the substrate is 2-4 mm.
Preferably, in the step (2), the concentration of manganese sulfate in the manganese sulfate solution is 2.96-9.47 mmol/L.
In the step (2), the ethanol is used for preventing the graphene oxide gel from being re-dispersed.
Preferably, in the step (4), the addition amount of the potassium ferricyanide is 0.63-2.01 g/L after the potassium ferricyanide is added.
Preferably, in the step (5), the reducing agent used for the reduction is at least one of hydroiodic acid, hydrazine hydrate, ascorbic acid, or sodium borohydride.
Preferably, in the step (5), the temperature is 80-180 ℃ during reduction, and the time is 30 min-3 h.
The invention also provides the flexible self-supporting graphene/manganese hexacyanoferrate composite material prepared by the preparation method.
The invention also provides application of the flexible self-supporting graphene/manganese hexacyanoferrate composite material in preparation of electrode materials.
According to the preparation method of the flexible self-supporting graphene/manganese hexacyanoferrate composite material, graphene oxide hydrogel is used as a matrix, manganese hexacyanoferrate is loaded in the graphene oxide gel by a wet chemical method, and the graphene/manganese hexacyanoferrate composite material is obtained through chemical reduction. The electronic conductivity of the whole composite electrode can be obviously enhanced after the graphene oxide framework is reduced. Meanwhile, the porous framework of the graphene oxide gel is loaded with the manganese hexacyanoferrate active substance, so that a sufficient transmission channel can be provided for the ion transportation in the electrode, and the diffusion of electrolyte ions is facilitated. The preparation method provided by the invention has the advantages of simple and convenient process, low cost and easy operation.
Drawings
Fig. 1 is a cross-sectional SEM image of the flexible self-supporting graphene/manganese ferricyanide composite of example 1.
Fig. 2 is a macroscopic photograph of the flexible self-supporting graphene/manganese hexacyanoferrate composite electrode material in example 1, where a is a graphene/manganese hexacyanoferrate composite film in a bent state, and B is a graphene/manganese hexacyanoferrate composite film in a natural state.
Fig. 3 is a surface topography of the flexible self-supporting graphene/manganese ferricyanide composite material of example 1.
Fig. 4 is a curve of specific capacity versus scan rate for the flexible self-supporting graphene/manganese ferricyanide composite of example 1.
Detailed Description
Example 1
Uniformly scraping and coating graphene oxide on a ceramic chip, soaking the ceramic chip in ferric cyanide hydrate solution, and then carrying out chemical reduction on the ceramic chip by using hydrazine hydrate. The specific experimental procedure is as follows:
0.045g manganese sulfate monohydrate is put into a beaker, and 60mL of a mixed solvent of ethanol and ionized water with the volume ratio of 1: 1 is added and stirred for 30 min.
The method comprises the steps of taking graphene oxide prepared by an improved Hummer's method as a raw material, diluting the graphene oxide to 20mg/ml by using deionized water to form graphene oxide gel, and casting a graphene oxide gel film with the thickness of 2mm and the size of 1cm multiplied by 2cm on a ceramic substrate by adopting a casting method. And placing the obtained graphene oxide gel film and the ceramic substrate in the fully stirred solution, and stirring for 30min at the stirring speed of 100 rpm. Then 0.066g of potassium ferricyanide was weighed and dissolved in 10mL of deionized water, and the potassium ferricyanide solution was added dropwise to the above solution using a dropper, and stirred well for 1 hour.
After stirring, taking out the graphene gel film and the ceramic sheet, placing the graphene gel film and the ceramic sheet in a container capable of being sealed, adding 1mL of hydrazine hydrate into the container, then sealing the container, and carrying out chemical reduction on the sample for 3 hours at the temperature of 80 ℃. And taking out the sample after the reduction is finished, cooling the sample in the air, soaking the sample in alcohol for 2 hours to wash out impurities on the surface, soaking the sample in deionized water for 2 hours again, and replacing the deionized water every 30min to wash out the alcohol on the surface.
The washed graphene/manganese ferricyanide film can be easily peeled from the ceramic substrate to obtain a self-supporting graphene/manganese ferricyanide film, the cross-sectional morphology of the self-supporting graphene/manganese ferricyanide film is shown in fig. 1, and as shown in the figure, the pore structure (porous structure) of the composite film can provide a channel for the diffusion of an electrolyte. As shown in fig. 2, which is a macroscopic photograph of the composite film in the bent and unbent states, the composite film still maintains good structural integrity in the bent state, and the composite film can be directly used as an electrode material without a binder and a conductive additive, indicating that the composite film has good self-supporting characteristics. Fig. 3 is a surface topography of the composite film, and table 1 is an energy spectrum analysis result of the composite film, which shows that the existence of iron and manganese elements in the composite film indirectly indicates that manganese ferricyanide is loaded in the graphene film.
TABLE 1 results of energy spectrum analysis
The film is cut into a square block of 1cm multiplied by 1cm, a two-electrode system is adopted, 1mol/L sodium sulfate and 0.5mol/L zinc sulfate are used as electrode liquid, a graphene/manganese ferricyanide composite material is used as an anode, a zinc sheet is used as a cathode to assemble a water system sodium ion battery, and the specific capacity of the water system sodium ion battery reaches 60mAh/g under the current density of 0.1A/g.
The supercapacitor is assembled by adopting a two-electrode stacking system and 6mol/L potassium hydroxide as electrolyte, and the experimental result is shown in figure 4 and is at 0.1mA/cm2The specific capacity of the obtained product reaches 107F/g under the current density of 2mA/cm2The specific capacity of the graphene film under the current density is still maintained to be 81F/g, and compared with the specific capacity of the pure graphene film under the same current density, the specific capacity of the pure graphene film is only 70F/g and 37F/g.
Example 2
Uniformly blade-coating graphene oxide on a ceramic chip, soaking the ceramic chip in a ferric cyanide manganese hydrate solution, and then chemically reducing the ceramic chip by using hydrazine hydrate. The specific experimental procedure is as follows:
0.045g manganese sulfate monohydrate is put into a beaker, and 60mL of a mixed solvent of ethanol and ionized water with the volume ratio of 1: 1 is added and stirred for 30 min.
The graphene oxide gel film with the thickness of 4mm and the size of 1cm multiplied by 2cm is cast on a ceramic substrate by a casting method by taking 20mg/ml graphene oxide gel as a raw material. And placing the obtained graphene oxide gel film and the ceramic substrate in the fully stirred solution, and stirring for 30min at the stirring speed of 100 rpm. Then 0.066g of potassium ferricyanide was weighed and dissolved in 10mL of deionized water, and the potassium ferricyanide solution was added dropwise to the above solution using a dropper, and stirred well for 1 hour.
After stirring, taking out the graphene gel film and the ceramic wafer, placing the graphene gel film and the ceramic wafer in a container capable of being sealed, adding 1mL of hydrazine hydrate into the container, then sealing the container, and carrying out chemical reduction on the sample for 3h at the temperature of 80 ℃. And taking out the sample after the reduction is finished, cooling the sample in the air, soaking the sample in alcohol for 2 hours to wash out impurities on the surface, soaking the sample in deionized water for 2 hours again, and replacing the deionized water every 30min to wash out the alcohol on the surface.
The washed graphene/manganese hexacyanoferrate film can be easily peeled off from a ceramic substrate, and cut into a square block of 1cm multiplied by 1cm, a two-electrode system is adopted, 1mol/L sodium sulfate and 0.5mol/L zinc sulfate are used as electrode liquid, a graphene/manganese hexacyanoferrate composite material is used as an anode, a zinc sheet is used as a cathode, and an aqueous sodium ion battery is assembled at 0.1mA/cm2The specific capacity of the current density of the battery reaches 54 mAh/g.
Example 3
The electrode of the experiment is that graphene is evenly coated on a ceramic chip in a scraping way, and then the ceramic chip is soaked in a ferric cyanide solution, and then hydrazine hydrate is used for carrying out chemical reduction on the ceramic chip. The specific experimental procedure is as follows:
0.03g of manganese sulfate monohydrate is put into a beaker, and 60mL of a mixed solvent of ethanol and ionized water with the volume ratio of 1: 1 is added and stirred for 30 min.
The graphene oxide gel film with the thickness of 3mm and the size of 1cm multiplied by 2cm is cast on a ceramic substrate by a casting method by taking 20mg/ml graphene oxide gel as a raw material. And placing the obtained graphene oxide gel film and the ceramic substrate in the fully stirred solution, and stirring for 30min at the stirring speed of 100 rpm. Then 0.044g of potassium ferricyanide was weighed and dissolved in 10mL of deionized water, and the potassium ferricyanide solution was added dropwise to the above solution using a dropper, and stirred well for 1 hour.
After stirring, taking out the graphene gel film and the ceramic wafer, placing the graphene gel film and the ceramic wafer in a container capable of being sealed, adding 1mL of hydrazine hydrate into the container, then sealing the container, and carrying out chemical reduction on the sample for 3h at the temperature of 80 ℃. And taking out the sample after the reduction is finished, after the sample is cooled, soaking the sample in alcohol for 2 hours to wash off impurities on the surface, soaking the sample again for 2 hours by using deionized water, and replacing the deionized water every 30min to wash off the alcohol on the surface.
The washed graphene/manganese hexacyanoferrate film can be easily peeled off from a ceramic substrate, and is cut into a square block of 1cm multiplied by 1cm, a symmetrical two-electrode system is adopted, 6mol/L potassium hydroxide is taken as electrolyte, and the super capacitor is assembled, wherein the concentration of the electrolyte is 0.1mA/cm2The specific capacity of the obtained product reaches 105F/g under the current density.
Example 4
Uniformly blade-coating graphene oxide on a ceramic chip, soaking the ceramic chip in a ferric cyanide manganese hydrate solution, and then chemically reducing the ceramic chip by using hydrazine hydrate. The specific experimental procedure is as follows:
0.06g of manganese sulfate monohydrate is put into a beaker, and 60mL of a mixed solvent of ethanol and ionized water with the volume ratio of 1: 1 is added and stirred for 30 min.
The graphene oxide gel film with the thickness of 3mm and the size of 1cm multiplied by 2cm is cast on a ceramic substrate by a casting method by taking 20mg/ml graphene oxide gel as a raw material. And placing the obtained graphene oxide gel film and the ceramic substrate in the fully stirred solution, and stirring for 30min at the stirring speed of 100 rpm. Then 0.088g of potassium ferricyanide was weighed and dissolved in 10mL of deionized water, and the potassium ferricyanide solution was added dropwise to the above solution using a dropper, and stirred well for 1 h.
After stirring, taking out the graphene gel film and the ceramic sheet, placing the graphene gel film and the ceramic sheet in a container capable of being sealed, adding 1mL of hydrazine hydrate into the container, then sealing the container, and carrying out chemical reduction on the sample for 3 hours at the temperature of 80 ℃. And taking out the sample after the reduction is finished, after the sample is cooled, soaking the sample in alcohol for 2 hours to wash off impurities on the surface, soaking the sample again for 2 hours by using deionized water, and replacing the deionized water every 30min to wash off the alcohol on the surface.
The washed graphene/manganese hexacyanoferrate film can be easily peeled off from a ceramic substrate, and is cut into a square block of 1cm multiplied by 1cm, a symmetrical two-electrode system is adopted, 6mol/L potassium hydroxide is taken as electrolyte, and the super capacitor is assembled, wherein the concentration of the electrolyte is 0.1mA/cm2Current ofThe specific capacity under the density reaches 109F/g and is 5mA/cm2The specific capacity still keeps 54F/g.
Example 5
Uniformly blade-coating graphene oxide on a ceramic chip, soaking the ceramic chip in a ferric cyanide manganese hydrate solution, and then chemically reducing the ceramic chip by using hydrazine hydrate. The specific experimental procedures were as follows:
0.096g of manganese sulfate monohydrate was put into a beaker, and 60mL of a mixed solvent of ethanol and ionized water in a volume ratio of 1: 1 was added thereto, followed by stirring for 30 min.
The graphene oxide gel film with the thickness of 3mm and the size of 1cm multiplied by 2cm is cast on a ceramic substrate by using a casting method and taking 10mg/ml graphene oxide gel as a raw material. And placing the obtained graphene oxide gel film and the ceramic substrate in the fully stirred solution, and stirring for 30min at the stirring speed of 100 rpm. 0.1408g of potassium ferricyanide was then weighed and dissolved in 10mL of deionized water, and the potassium ferricyanide solution was added dropwise to the above solution using a dropper, and stirred well for 1 h.
After stirring, taking out the graphene gel film and the ceramic sheet, placing the graphene gel film and the ceramic sheet in a container capable of being sealed, adding 1mL of hydrazine hydrate into the container, then sealing the container, and carrying out chemical reduction on the sample for 0.5h at 180 ℃. And taking out the sample after the reduction is finished, cooling the sample in the air, soaking the sample in alcohol for 2 hours to wash out impurities on the surface, soaking the sample in deionized water for 2 hours again, and replacing the deionized water every 30min to wash out the alcohol on the surface.
The washed graphene/manganese hexacyanoferrate film can be easily peeled off from a ceramic substrate, and cut into a square block of 1cm multiplied by 1cm, a graphene/manganese hexacyanoferrate composite material is used as an anode, a graphene/manganese hexacyanoferrate composite material is used as an electrode solution, a zinc sheet is used as a cathode to assemble a water system sodium ion battery, and the specific capacity of the water system sodium ion battery reaches 39mAh/g under the current density of 0.1A/g.
Claims (9)
1. A preparation method of a flexible self-supporting graphene/manganese hexacyanoferrate composite material is characterized by comprising the following steps:
(1) casting graphene oxide gel onto a substrate to form a gel film;
(2) dissolving manganese sulfate in an ethanol water solution to prepare a manganese sulfate solution;
(3) immersing the gel film in the step (1) and the matrix into the manganese sulfate solution prepared in the step (2);
(4) adding potassium ferricyanide into the solution obtained in the step (3) to react;
(5) and (4) taking out the gel film treated in the step (4) together with the substrate, reducing to obtain a graphene/manganese hexacyanoferrate film, and stripping the graphene/manganese hexacyanoferrate film from the substrate after cleaning to obtain the flexible self-supporting graphene/manganese hexacyanoferrate composite material.
2. The preparation method according to claim 1, wherein in the step (1), the concentration of graphene oxide in the graphene oxide gel is 10-20 mg/ml.
3. The method according to claim 1, wherein in the step (1), the graphene oxide gel is cast onto the substrate to a thickness of 2 to 4 mm.
4. The method according to claim 1, wherein in the step (2), the concentration of manganese sulfate in the manganese sulfate solution is 2.96-9.47 mmol/L.
5. The method according to claim 1, wherein in the step (4), the potassium ferricyanide is added in an amount of 0.63 to 2.01g/L in concentration after addition.
6. The method according to claim 1, wherein in the step (5), the reducing agent used for the reduction is at least one of hydroiodic acid, hydrazine hydrate, ascorbic acid, or sodium borohydride.
7. The method of claim 1, wherein in step (5), the temperature is 80 ℃ to 180 ℃ and the time is 30min to 3 h.
8. The flexible self-supporting graphene/manganese hexacyanoferrate composite material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the flexible self-supporting graphene/manganese ferricyanide composite material of claim 8 in the preparation of an electrode material.
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