CN113990674A - Preparation method and application of composite material with sandwich structure - Google Patents
Preparation method and application of composite material with sandwich structure Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a composite material with a sandwich structure, which are carried out according to the following steps: (1) adopting citrate as precursor to make high-temp. carbonization treatment, pickling with dilute hydrochloric acid, filtering, washing with water and drying treatment to obtain the invented productPreparing carbon nano sheets; (2) dispersing the prepared carbon nano sheet into an aqueous solution, stirring, and ultrasonically preparing carbon nano sheet aqueous dispersion with different concentrations; (3) adding a certain amount of potassium permanganate into the carbon nanosheet dispersion liquid, and preparing MnO with a sandwich structure through high-temperature hydrothermal reaction2Carbon nano sheet/MnO2A composite material. MnO of the sandwich structure2Carbon nano sheet/MnO2The composite material electrode has high specific capacity and good electrochemical performance in the super capacitor.
Description
Technical Field
The invention belongs to carbon/MnO2The technical field of composite material preparation, in particular to preparation of MnO with a sandwich structure by using citrate derived carbon sheets2Carbon nano sheet/MnO2Method for preparing composite material, and MnO with sandwich structure prepared by the preparation method2Carbon nano sheet/MnO2Use of a composite material in a supercapacitor.
Background
With the large consumption of non-renewable fossil energy and the aggravation of environmental pollution, the development of new energy materials and energy storage devices is imminent. Among various chemical energy storage devices, the super capacitor has the advantages of rapid charge and discharge, long cycle life, high power density and the like. The development of electrode materials is the key to high performance supercapacitors. In the existing electrode materials, a carbon/metal oxide composite material prepared by compounding a carbon-based material with a double electric layer characteristic and a pseudocapacitance material such as a metal oxide is a research hotspot in the field of electrode materials of supercapacitors. In many carbon material families, carbon nanosheets, carbon nanotubes, carbon fibers and the like can be prepared by high-temperature carbonization of a carbon-containing precursor. Compared with graphene, the carbon materials prepared by the carbonization method have the advantages of low cost, simple preparation and the like. The citrate comprises potassium citrate, sodium citrate, zinc citrate, ferric citrate, calcium citrate and the like, and can be used for preparing the carbon nano-sheet with the mesoporous structure through high-temperature carbonization. However, when the carbon nano-sheets are used as electrode materials, the specific capacitance is only 100-200F/g. Mixing the carbon nano-sheet with MnO2Carbon nano sheet/MnO prepared by compounding2The composite material can obviously improve the specific capacity of the electrode material. Thus, how to controllably adjust the carbon nanosheet/MnO2The improvement of the electrochemical properties of composite materials by their microscopic morphology is currently a critical need in this fieldKey scientific problems to be solved.
At present, with respect to carbon/MnO2In the related reports of the composite material, chinese patent with patent application number CN201710375031.9, entitled preparation method of manganese dioxide/carbon composite electrode material, coats and solidifies sugar on the surface of carbon material to obtain carbon material with hydroxyl on the surface, and reacts the carbon material with permanganate and/or manganate to finally prepare manganese dioxide/carbon composite electrode material. The patent application number is CN201910544472.6, and is named as a flower-shaped manganese dioxide/carbon composite material, a preparation method thereof and Chinese patents applying the same, wherein a carbon material and an acid solution are mixed to obtain a dispersion liquid, and the carbon material is one or more of acetylene black ACEF, conductive carbon black Super P, Ketjen black EC-300J or cabot carbon black. Adding a potassium permanganate solution into the dispersion liquid, and reacting at 60-95 ℃ to prepare the flower-shaped manganese dioxide/carbon composite material. In addition, chinese patent with patent application No. CN201710375031.9, entitled a method for preparing manganese dioxide/carbon composite electrode material, coats and solidifies sugar on the surface of carbon material to obtain carbon material with hydroxyl on the surface, and reacts the carbon material with permanganate and/or manganate to finally prepare manganese dioxide/carbon composite electrode material.
In summary, the existing carbon/MnO2The carbon source selected in the preparation process of the composite material is generally porous carbon or hydroxyl modified carbon, and the carbon nanosheet with the two-dimensional structure is rarely involved. In addition, the reaction of carbon with potassium permanganate generally adopts a common chemical method, and MnO is generated in situ based on the oxidation-reduction reaction of potassium permanganate and carbon2Attached to the surface of the carbon material. Therefore, MnO having a sandwich structure is difficult to be prepared by using the existing carbon material and the common chemical method2Carbon nano sheet/MnO2Composite materials, in turn leading to existing carbon/MnO2The composite material electrode has low specific capacity and poor electrochemical performance when being used for a super capacitor.
Disclosure of Invention
In order to solve the existing carbon/MnO2The invention discloses a method for preparing a composite material with a sandwich structure, and provides a method for preparing a composite material electrode with a sandwich structure, namely a method for preparing a composite material electrode with a sandwich structureThe method comprises the steps of preparing carbon nano-sheets by high-temperature carbonization by using citrate as a precursor, and performing oxidation-reduction reaction on the carbon nano-sheets serving as two-dimensional sacrificial templates and potassium permanganate under a high-temperature hydrothermal condition to realize MnO2Coating the nanosheet array on the upper surface and the lower surface of the residual carbon nanosheet to finally prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material. In the hydrothermal reaction process, the mass ratio of the carbon nanosheets to the potassium permanganate can be regulated and controlled to further optimize the sandwich structure and improve the specific capacitance and the electrochemical performance of the composite material.
In order to further achieve the purpose, the invention adopts the following technical scheme: a preparation method of a composite material with a sandwich structure comprises the following steps:
(1) performing high-temperature carbonization treatment by using citrate as a precursor, and performing dilute hydrochloric acid pickling, filtering, washing and drying treatment to prepare carbon nano sheets;
(2) dispersing the prepared carbon nano sheet into an aqueous solution, stirring, and ultrasonically preparing carbon nano sheet aqueous dispersion with different concentrations;
(3) adding a certain amount of potassium permanganate into the carbon nanosheet dispersion liquid, performing high-temperature hydrothermal reaction, filtering, washing and drying to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
In the method, the citrate in the step (1) is one or a mixture of several of commercial potassium citrate, sodium citrate, ferric citrate, zinc citrate and calcium citrate in any proportion; the high-temperature carbonization temperature is 700-1000 ℃, the heat preservation time is 1-5 h, and the temperature rise rate is 3-5 ℃/min.
In the method, the concentration of the dispersion liquid of the carbon nano sheet in the step (2) is 0.2-10.0 mg mL-1。
In the method, the mass ratio of the potassium permanganate to the carbon nanosheets in the step (3) is 10/1-20/1; the hydrothermal reaction temperature is 170-190 ℃, and the reaction time is 8-12 h. The reference electrode used in the electrochemical test is a calomel electrode, and the counter electrode is a platinum sheet or a platinum wire mesh.
Accordingly, the invention is also claimedMnO with sandwich structure prepared by preparation method2Carbon nano sheet/MnO2Application of composite material in super capacitor and MnO with sandwich structure2Carbon nano sheet/MnO2The composite material electrode has high specific capacity and good electrochemical performance in a super capacitor.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) the carbon nano-sheets with uniform thickness can be prepared after the carbonization of the citrate precursor, and the carbon nano-sheets are used as a two-dimensional sacrificial template to perform oxidation-reduction reaction with potassium permanganate under the hydrothermal condition, so that MnO with a sandwich structure is finally prepared2Carbon nano sheet/MnO2A composite material.
(2) The residual carbon nano-sheets after the hydrothermal reaction are clamped between two layers of MnO2MnO with sandwich structure formed in the middle2Carbon nano sheet/MnO2The special micro-morphology of the composite material is beneficial to the exertion of the electrochemical performance of the composite material, and the composite material electrode shows high specific capacitance and electrochemical performance in a three-electrode super capacitor.
Drawings
FIG. 1 is a carbon nanosheet prepared by charring sodium citrate in example 1 of the present invention;
FIG. 2 shows preparation of MnO in example 1 of the present invention2Carbon nano sheet/MnO2Scanning electron micrographs of the composite;
FIG. 3 shows preparation of MnO in example 1 of the present invention2Carbon nano sheet/MnO2A charge-discharge curve and a specific capacity graph of the composite material;
FIG. 4 shows preparation of MnO in example 2 of the present invention2Carbon nano sheet/MnO2Scanning electron micrographs of the composite;
FIG. 5 shows preparation of MnO in example 2 of the present invention2Carbon nano sheet/MnO2The charge-discharge curve and specific capacity graph of the composite material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, the scanning electron microscope is JSM7500F, Japan Electron Co.
The electrochemical performance in the embodiment of the present invention employs an electrochemical workstation (660E) which is shanghai chen hua limited.
Example 1:
weighing 10g of potassium citrate powder for high-temperature carbonization, wherein the specific conditions are as follows: the carbonization temperature is 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. The obtained black powder was washed with 5% diluted hydrochloric acid, filtered, washed with water, and dried at 60 ℃ for 12 hours to obtain 0.89g of carbon nanosheets (fig. 1). And weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and ultrasonically dispersing to obtain the carbon nano-sheet dispersion liquid. And adding 1.5g of weighed potassium permanganate into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and keeping the temperature at 180 ℃ for 12 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2The composite material, microstructure is shown in figure 2.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. And (3) uniformly smearing the slurry on a foam nickel electrode plate, and testing the electrochemical properties of the electrode material in a 5M KOH electrolyte by taking a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, wherein the specific properties are shown in a figure 3 and a table 1.
Example 2:
weighing 4g of potassium citrate and 6g of sodium citrate powder for high-temperature carbonization, wherein the specific conditions are as follows: the carbonization temperature is 700 ℃, the heat preservation time is 3h, and the heating rate is 3 ℃/min. The obtained black powder was washed with 5% diluted hydrochloric acid, filtered, washed with water, and dried at 60 ℃ for 12 hours to obtain 0.81g of carbon nanosheet. Weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and super-treatingAnd performing acoustic dispersion to obtain the carbon nanosheet dispersion liquid. And adding 2.0g of potassium permanganate weighed into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and preserving heat at 190 ℃ for 10 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2The composite material, microstructure is shown in figure 4.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. And (3) uniformly smearing the slurry on a foam nickel electrode plate, and testing the electrochemical properties of the electrode material in a 5M KOH electrolyte by taking a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, wherein the specific properties are shown in a figure 5 and a table 1.
Example 3:
weighing 2g of ferric citrate, 2g of sodium citrate and 6g of zinc citrate powder, and carrying out high-temperature carbonization on the weighed materials under the specific conditions: the carbonization temperature is 900 ℃, the heat preservation time is 1h, and the heating rate is 4 ℃/min. And washing the obtained black powder with 5% diluted hydrochloric acid, filtering, washing with water, and drying at 60 ℃ for 12 hours to obtain 0.92g of carbon nanosheets. And weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and ultrasonically dispersing to obtain the carbon nano-sheet dispersion liquid. And adding 1.0g of weighed potassium permanganate into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and keeping the temperature at 175 ℃ for 8 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. And (3) uniformly smearing the slurry on a foam nickel electrode plate, and testing the electrochemical properties of the electrode material in a 5M KOH electrolyte by taking a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, wherein the specific properties are shown in Table 1.
Example 4:
weighing 4g of calcium citrate, 4g of sodium citrate and 2g of potassium citrate powder, carrying out high-temperature carbonization,the specific conditions are as follows: the carbonization temperature is 1000 ℃, the heat preservation time is 1h, and the heating rate is 3 ℃/min. The obtained black powder was washed with 5% diluted hydrochloric acid, filtered, washed with water, and dried at 60 ℃ for 12 hours to obtain 0.86g of carbon nanosheets. And weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and ultrasonically dispersing to obtain the carbon nano-sheet dispersion liquid. And adding 1.2g of weighed potassium permanganate into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and preserving heat at 190 ℃ for 10 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. And (3) uniformly smearing the slurry on a foam nickel electrode plate, and testing the electrochemical properties of the electrode material in a 5M KOH electrolyte by taking a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, wherein the specific properties are shown in Table 1.
Example 5:
weighing 5g of sodium citrate and 5g of calcium citrate powder for high-temperature carbonization, wherein the specific conditions are as follows: the carbonization temperature is 800 ℃, the heat preservation time is 3h, and the heating rate is 5 ℃/min. The obtained black powder was washed with 5% diluted hydrochloric acid, filtered, washed with water, and dried at 60 ℃ for 12 hours to obtain 0.93g of carbon nanosheets. And weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and ultrasonically dispersing to obtain the carbon nano-sheet dispersion liquid. And adding 1.8g of weighed potassium permanganate into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and keeping the temperature at 185 ℃ for 9 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. Smearing the slurry on a nickel foam electrode plate uniformly, in 5M KOH electrolyte, using a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, and testing the electrode materialThe electrochemical properties, specific properties, are shown in Table 1.
Example 6:
weighing 1g of sodium citrate, 5g of zinc citrate and 4g of calcium citrate powder, and carrying out high-temperature carbonization on the sodium citrate, wherein the specific conditions are as follows: the carbonization temperature is 700 ℃, the heat preservation time is 3h, and the heating rate is 3 ℃/min. The obtained black powder was washed with 5% diluted hydrochloric acid, filtered, washed with water, and dried at 60 ℃ for 12 hours to obtain 0.96g of carbon nanosheets. And weighing 100mg of carbon nano-sheets, putting the carbon nano-sheets into 60mL of deionized water, stirring and ultrasonically dispersing to obtain the carbon nano-sheet dispersion liquid. And adding 1.6g of weighed potassium permanganate into the carbon nanosheet dispersion liquid, dissolving and uniformly dispersing the potassium permanganate, then placing the mixture into a 100mL reaction kettle, and keeping the temperature at 190 ℃ for 11 hours. Filtering and washing the hydrothermal product, and drying at 60 ℃ for 12h to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
MnO to be prepared2Carbon nano sheet/MnO2The composite material, a conductive agent and a binder are mixed according to the mass ratio of 85/10/5, and N-methyl pyrrolidone is used as a solvent to prepare slurry. And (3) uniformly smearing the slurry on a foam nickel electrode plate, and testing the electrochemical properties of the electrode material in a 5M KOH electrolyte by taking a calomel electrode as a reference electrode and a platinum plate electrode as a counter electrode, wherein the specific properties are shown in Table 1.
TABLE 1 different MnO2Carbon nano sheet/MnO2Chemical properties of composite electrode
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. The preparation method of the composite material with the sandwich structure is characterized by comprising the following steps of:
(1) performing high-temperature carbonization treatment by using citrate as a precursor, and performing dilute hydrochloric acid pickling, filtering, washing and drying treatment to prepare carbon nano sheets;
(2) dispersing the prepared carbon nano sheet into an aqueous solution, stirring, and ultrasonically preparing carbon nano sheet aqueous dispersion with different concentrations;
(3) adding a certain amount of potassium permanganate into the carbon nanosheet dispersion liquid, performing high-temperature hydrothermal reaction, filtering, washing and drying to prepare MnO with a sandwich structure2Carbon nano sheet/MnO2A composite material.
2. The method for preparing a composite material with a sandwich structure according to claim 1, wherein the citrate in the step (1) is one or a mixture of several of potassium citrate, sodium citrate, ferric citrate, zinc citrate and calcium citrate in any proportion.
3. The preparation method of the composite material with the sandwich structure according to claim 1, wherein the high-temperature carbonization temperature in the step (1) is 700-1100 ℃, the heat preservation time is 1-5 h, and the temperature rise rate is 3-5 ℃/min.
4. The preparation method of the composite material with the sandwich structure according to claim 1, wherein the concentration of the aqueous dispersion of the carbon nanosheets of the step (2) is 0.2-10.0 mg mL-1。
5. The preparation method of the composite material with the sandwich structure according to claim 1, wherein the mass ratio of the potassium permanganate to the carbon nanosheets in the step (3) is 10/1-20/1.
6. The preparation method of the composite material with the sandwich structure according to claim 1, wherein the hydrothermal reaction temperature in the step (3) is 170-190 ℃ and the reaction time is 8-12 h.
7. The method for preparing a composite material with a sandwich structure according to claim 1, wherein the reference electrode in the electrochemical test in the step (3) is a calomel electrode, and the counter electrode is a platinum sheet or a platinum wire mesh.
8. A sandwich structured composite material prepared according to the method for preparing a composite material having a sandwich structure of any one of claims 1 to 7.
9. Use of a composite material according to claim 8 having a sandwich structure in a supercapacitor.
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2021
- 2021-11-11 CN CN202111334935.XA patent/CN113990674A/en active Pending
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| CN101923960A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN103545122A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method for manganese dioxide/carbon composite materials used for super capacitor |
| CN106683890A (en) * | 2016-11-01 | 2017-05-17 | 浙江农林大学 | Carbon/manganese oxide composite material, preparation method thereof and application thereof |
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