CN108538618B - Porous ZnO-C composite material and preparation method and application thereof - Google Patents
Porous ZnO-C composite material and preparation method and application thereof Download PDFInfo
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- CN108538618B CN108538618B CN201810495908.2A CN201810495908A CN108538618B CN 108538618 B CN108538618 B CN 108538618B CN 201810495908 A CN201810495908 A CN 201810495908A CN 108538618 B CN108538618 B CN 108538618B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a porous ZnO-C supercapacitor composite electrode material. The specific surface area of the porous ZnO-C prepared by the preparation method is 450-500 m2/g, the maximum specific capacitance can reach 550F g-1 when the current density is 5A g-1, 92-97% of the initial specific capacitance can be kept after 3000 times of cyclic charge and discharge under the heavy current density, the porous ZnO-C can show excellent electrochemical performance and good cyclic stability, and is suitable for being used as an electrode material of a super capacitor and the like.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to a porous ZnO-C composite material and a preparation method and application thereof.
background
supercapacitors have received attention from researchers throughout the world because they can store high energy and deliver high power in a short period of time. Carbon materials, transition metal oxides and conductive polymers have been heretofore electrode materials of conventional supercapacitors, but their applications have been limited due to the development of high performance of the supercapacitors. Therefore, it is important to develop a new electrode material having a high-performance supercapacitor.
research make internal disorder or usurp shows that ZnO can be used as the electrode material of super capacitor because of its high capacitance, low cost, environmental protection and stable electrochemical performance. However, as the charge storage capacity of ZnO is not stable enough, and the working voltage window is narrow, further application of ZnO materials in the field of supercapacitors is limited, in order to solve this problem, scientists have tried to introduce carbon materials, such as graphene, graphene oxide, carbon nanotubes, graphitic carbon nanofibers, carbon arrays, and the like, into ZnO electrode materials. The introduction of the carbon material increases the electric double layer capacitance value and the window voltage range of the composite material, however, the method has the defect that the bonding capability between ZnO and the carbon material is too poor, so that the electrode material is easy to damage in the charging and discharging processes, and therefore, the cycle stability of the supercapacitor is also poor. Therefore, it is urgent to design and synthesize a ZnO composite carbon material electrode having good cycle stability and higher energy density.
disclosure of Invention
the invention mainly aims to provide a porous ZnO-C composite material which is obtained by performing high-temperature anaerobic calcination on a vanillin-zinc complex MOF material, has high specific surface area of the obtained porous ZnO-C and good bonding performance between ZnO and C, can show higher energy density and good circulation stability when used as a supercapacitor electrode material, and is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
a porous ZnO-C composite material is prepared by carrying out high-temperature oxygen-free calcination on a vanillin-zinc complex MOF material; the specific surface area is 450 to 500m 2/g.
in the above scheme, the chemical formula of the vanillin-zinc complex is Zn (C8H7O3)2(H2O)2, the molecular formula is C16H18O8Zn, and the structure is characterized in that each central metal ion Zn2+ coordinates with 4 oxygen atoms of phenolic hydroxyl oxygen and methoxy oxygen in 2 vanillin groups and 2 oxygen atoms in 2 water molecules to form a molecular complex, and the coordination number is 6.
In the scheme, the preparation method of the vanillin-zinc complex comprises the following steps:
1) Dissolving zinc salt and organic alkali in an organic solvent, and uniformly mixing to obtain a solution I;
2) Dissolving vanillin in an organic solvent, and uniformly mixing to obtain a solution II;
3) Uniformly mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under stirring to obtain a reaction solution, carrying out solvothermal reaction on the reaction solution, and then cooling, washing and drying to obtain the vanillin-zinc complex MOF material.
The preparation method of the porous ZnO-C composite material comprises the following steps:
1) Dissolving zinc salt and organic alkali in an organic solvent, and uniformly mixing to obtain a solution I;
2) Dissolving vanillin in an organic solvent, and uniformly mixing to obtain a solution II;
3) uniformly mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under stirring to obtain a reaction solution, carrying out a solvothermal reaction on the reaction solution, and then cooling, washing and drying to obtain a vanillin-zinc complex MOF material;
4) And (3) carrying out anaerobic calcination on the vanillin-zinc complex MOF material to obtain the porous ZnO-C composite material.
In the scheme, the zinc salt can be selected from zinc chloride, zinc nitrate and the like.
In the scheme, the organic solvent can be absolute ethyl alcohol, methanol or isopropanol and the like.
In the above scheme, the organic base is a secondary amine or a primary amine.
in the scheme, the secondary amine can be dimethylamine, diethylamine or dipropylamine, etc.; the tertiary amine can be selected from trimethylamine, triethylamine or tripropylamine;
preferably, the secondary amine is diethylamine; the tertiary amine is triethylamine.
In the scheme, the molar ratio of the zinc salt to the organic base is 1 (1-3).
in the scheme, the molar ratio of the zinc salt to the vanillin in the reaction liquid is 1 (2-2.05).
In the scheme, the concentration of the zinc salt in the solution I is 0.05-0.10 mol/L; the concentration of vanillin in the solution II is 0.03-0.05 mol/L.
In the scheme, the solvothermal reaction temperature is 160-200 ℃, and the time is 6-24 h.
In the scheme, the solvothermal reaction adopts a high-pressure reaction kettle, and the filling degree of the high-pressure reaction kettle is 60-80%.
In the above scheme, the anaerobic calcination process comprises: firstly, heating from room temperature to 140 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-3h, then continuously heating to 800 ℃ at the speed of 1-3 ℃/min, preserving heat for 3-9h, and cooling to room temperature.
the porous ZnO-C composite material obtained by the scheme is used as a super capacitor electrode material, the highest discharge specific capacitance can reach 550g-1 (the discharge current is 5Ag-1), the capacity attenuation is small after 3000 charge-discharge cycles, and 92-97% of the initial specific capacity can be maintained; can show higher energy density and good cycle stability, and can effectively overcome the defects of the prior ZnO/C composite material.
the invention firstly proposes that a vanillin-zinc complex MOF material is used for preparing a porous ZnO-C composite material by anaerobic calcination; the metal organic framework is a three-dimensional reticular framework structure formed by a series of reactions of metal ions and organic ligands in a proper solvent, and has the advantages of large specific surface area, adjustable pore size, high porosity and the like; the porous ZnO-C is further calcined to prepare the porous ZnO-C as a precursor, so that the specific surface area of the obtained composite material and the bonding performance between ZnO and C can be effectively improved; the ZnO/C composite material is applied to the fields of super capacitor batteries and the like, can show high energy density and good circulation stability, and can effectively break through the application bottleneck of the existing ZnO/C composite material.
compared with the prior art, the invention has the beneficial effects that:
1) The invention firstly proposes that zinc salt and vanillin are used as main raw materials, a vanillin zinc complex MOF material is prepared by a solvothermal method, and then the material is calcined in an anaerobic environment to obtain a porous ZnO-C composite material, wherein the obtained porous ZnO-C composite material has a high specific surface area, a pore structure is uniformly distributed, and the bonding performance between ZnO and C is good;
2) The preparation process provided by the invention is simple, the raw materials are easy to obtain, the cost is low, and the efficiency is high;
3) The obtained porous ZnO-C composite material can be used as a super capacitor electrode material, and has the advantages of high energy density, good cycle stability and the like.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the ethanol used was absolute ethanol (AR).
Example 1
A preparation method of the porous ZnO-C composite material comprises the following steps:
1) Respectively weighing 0.1633g (1mmol) of ZnCl2, dissolving in 20ml of ethanol under stirring, adding 0.0731g (1mmol) of diethylamine (C4H11N), and stirring uniformly to obtain a solution I;
2) dissolving 0.304g (2mmol) of vanillin in 40ml of ethanol, and uniformly mixing to obtain a solution II;
3) mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under the stirring condition, uniformly stirring to obtain a reaction solution, then transferring the reaction solution into a 100mL high-pressure reaction kettle to react for 6 hours at 160 ℃, naturally cooling the reaction kettle to room temperature, centrifugally filtering the product, washing the product with ethanol for three times, and drying the product (drying the product at 80 ℃ for 12 hours) to obtain a vanillin-zinc complex material (MOF (C8H7O3)2(H2O)2 powder);
4) gradually heating the vanillin zinc complex MOF material from room temperature to 120 ℃ in a vacuum furnace at a heating rate of 10 ℃/min, keeping the temperature for 2h, then continuously heating to 600 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 9h, cooling the sample to room temperature, and thus obtaining the porous ZnO-C composite material.
the product obtained in the embodiment is analyzed by a BET test, and the specific surface area of the obtained powder product is 500m 2/g; when the material is used as an electrode material of a super capacitor, the specific capacitance is 550F g-1 when the current density is 5Ag-1, and after 3000 charge-discharge cycles, the specific capacitance is reduced by only 3% compared with the initial capacity.
Example 2
A preparation method of the porous ZnO-C composite material comprises the following steps:
1) Respectively weighing 0.1633g (1mmol) of ZnCl2, dissolving in 12ml of ethanol under stirring, adding 0.2014g (2mmol) of triethylamine (C6H15N), and stirring uniformly to obtain a solution I;
2) dissolving 0.312g (2.02mmol) of vanillin in 50ml of ethanol, and uniformly mixing to obtain a solution II;
3) mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under the stirring condition, uniformly stirring to obtain a reaction solution, then transferring the reaction solution into a 100mL high-pressure reaction kettle to react for 18H at 200 ℃, naturally cooling the reaction kettle to room temperature, centrifugally filtering the product, washing the product with ethanol for three times, and drying the product (drying the product at 80 ℃ for 12 hours) to obtain a vanillin-zinc complex material (MOF (C8H7O3)2(H2O)2 powder);
4) Gradually heating the vanillin zinc complex MOF material from room temperature to 100 ℃ in a vacuum furnace at a heating rate of 10 ℃/min, keeping the temperature for 3h, then continuously heating to 700 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 7h, cooling the sample to room temperature, and thus obtaining the porous ZnO-C composite material.
the product obtained in the embodiment is analyzed by a BET test, and the specific surface area of the obtained powder product is 450m 2/g; when the material is used as an electrode material of a super capacitor, the specific capacitance is 527F g-1 when the current density is 5Ag-1, and after 3000 charge-discharge cycles, the specific capacitance is reduced by only 5% compared with the initial capacity.
example 3
a preparation method of the porous ZnO-C composite material comprises the following steps:
1) Respectively weighing 163.3g (1mol) of ZnCl2, dissolving in 10L of ethanol under the condition of stirring, then adding 219.3g (3mol) of C4H11N, and stirring uniformly to obtain a solution I;
2)304.4g (2mol) of vanillin is dissolved in 60L of ethanol and is uniformly mixed to obtain a solution II;
3) Mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under stirring, uniformly stirring to obtain a reaction solution, then transferring the reaction solution into a 100L high-pressure reaction kettle to react for 24 hours at 180 ℃, naturally cooling the reaction kettle to room temperature, centrifugally filtering the product, washing the product with ethanol for three times, and drying the product (drying the product at 80 ℃ for 12 hours) to obtain a vanillin zinc complex MOF material (Zn (C8H7O3)2(H2O)2 powder);
4) Gradually heating the vanillin zinc complex MOF material from room temperature to 140 ℃ in a vacuum furnace at a heating rate of 10 ℃/min, keeping the temperature for 1h, then continuously heating to 800 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 3h, cooling the sample to room temperature, and thus obtaining the porous ZnO-C composite material.
The product obtained in the example is analyzed by a BET test, and the specific surface area of the obtained powder product is 471m 2/g; when the material is used as an electrode material of a super capacitor, the specific capacitance is 500F g-1 when the current density is 5Ag-1, and after 3000 charge-discharge cycles, the specific capacitance is reduced by only 4% compared with the initial capacity.
Example 4
A preparation method of the porous ZnO-C composite material comprises the following steps:
1) Respectively weighing 0.1633g (1mmol) of ZnCl2, dissolving in 20mL of ethanol under stirring, adding 0.2530g (2.5mmol) of C6H15N, and stirring uniformly to obtain a solution I;
2)0.319g (2.05mol) of vanillin is dissolved in 60mL of ethanol and is uniformly mixed to obtain a solution II;
3) Mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under the stirring condition, uniformly stirring to obtain a reaction solution, then transferring the reaction solution into a 100mL high-pressure reaction kettle to react for 20 hours at 170 ℃, naturally cooling the reaction kettle to room temperature, centrifugally filtering the product, washing the product with ethanol for three times, and drying the product (drying the product at 80 ℃ for 12 hours) to obtain a vanillin-zinc complex material (MOF (C8H7O3)2(H2O)2 powder);
4) The temperature of the vanillin zinc complex MOF material is gradually increased from room temperature to 130 ℃ in a vacuum furnace at the temperature increasing rate of 10 ℃/min, the temperature is kept for 2.5 hours, then the temperature is continuously increased to 750 ℃ at the temperature increasing rate of 2 ℃/min, the temperature is kept for 5 hours, and a sample is cooled to the room temperature, so that the porous ZnO-C composite material is obtained.
According to the BET test analysis of the product obtained in the embodiment, the specific surface area of the obtained powder product is 483m 2/g; when the material is used as an electrode material of a super capacitor, the specific capacitance is 540F g-1 when the current density is 5Ag-1, and after 3000 charge-discharge cycles, the specific capacitance is reduced by only 8% compared with the initial capacity.
Comparative example
A ZnO-C composite material is prepared by carrying out hydrothermal reaction on glucose at 180 ℃ for 10h to obtain carbon spheres, and compounding the obtained carbon spheres with ZnO to obtain a ZnO/carbon sphere nano composite material with a molar ratio of 1:1 (the specific preparation process is shown in 'synthesis of ZnO hollow spheres and ZnO/carbon sphere nano composite material and gas sensitivity and electrochemical performance research' of 2016 Korean beautiful Master thesis of Yunnan university).
the specific surface area of the obtained ZnO/carbon sphere nano composite material is 115.699m 2/g; when the material is used as an electrode material of a super capacitor, the specific capacitance is 459F g-1 when the current density is 5Ag-1, and after 1000 charge-discharge cycles, the specific capacitance is reduced by 18.6 percent compared with the initial capacity.
the result shows that the porous ZnO-C obtained by the invention has high specific surface area and good bonding performance between ZnO and C, and the porous ZnO-C can show higher energy density and good cycle stability when used as a super capacitor electrode material, and can effectively widen the application field of ZnO-C composite materials.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (9)
1. A porous ZnO-C composite material is characterized in that the porous ZnO-C composite material is prepared by carrying out anoxybiotic calcination on a vanillin-zinc complex MOF material; the specific surface area is 450-500 m 2/g;
The chemical formula of the vanillin zinc complex MOF material is Zn (C8H7O3)2(H2O)2, the molecular formula is C16H18O8Zn, and the structure is characterized in that each central metal ion Zn2+ is coordinated with 4 oxygen atoms of phenolic hydroxyl oxygen and methoxy oxygen in 2 vanillin groups and 2 oxygen atoms in 2 water molecules to form a molecular complex, and the coordination number is 6.
2. the porous ZnO-C composite material according to claim 1, wherein the preparation method of the vanillin-zinc complex comprises the following steps:
1) dissolving zinc salt and organic alkali in an organic solvent, and uniformly mixing to obtain a solution I;
2) Dissolving vanillin in an organic solvent, and uniformly mixing to obtain a solution II;
3) uniformly mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under stirring to obtain a reaction solution, carrying out solvothermal reaction on the reaction solution, and then cooling, washing and drying to obtain the vanillin-zinc complex MOF material.
3. a method for preparing a porous ZnO-C composite according to claim 1 or 2, characterized in that it comprises the following steps:
1) dissolving zinc salt and organic alkali in an organic solvent, and uniformly mixing to obtain a solution I;
2) Dissolving vanillin in an organic solvent, and uniformly mixing to obtain a solution II;
3) Uniformly mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) under stirring to obtain a reaction solution, carrying out a solvothermal reaction on the reaction solution, and then cooling, washing and drying to obtain a vanillin-zinc complex MOF material;
4) and (3) carrying out anaerobic calcination on the vanillin-zinc complex MOF material to obtain the porous ZnO-C composite material.
4. the method of claim 3, wherein the organic base is a secondary or primary amine.
5. the preparation method according to claim 3, wherein the molar ratio of the zinc salt to the organic base is 1 (1-3).
6. The preparation method according to claim 3, wherein the molar ratio of the zinc salt to vanillin in the reaction solution is 1 (2-2.05).
7. The method as claimed in claim 3, wherein the solvothermal reaction is carried out at a temperature of 160 ℃ to 200 ℃ for 6 to 24 hours.
8. the preparation method according to claim 3, wherein the anaerobic calcination process is: firstly, heating from room temperature to 140 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-3h, then continuously heating to 800 ℃ at the speed of 1-3 ℃/min, preserving heat for 3-9h, and cooling to room temperature.
9. The use of the porous ZnO-C composite of claim 1 in supercapacitor electrode materials.
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| CN109110745A (en) * | 2018-09-27 | 2019-01-01 | 北京长城华冠汽车科技股份有限公司 | A kind of preparation method of the hollow Nano carbon balls composite material of N doping multi-pore channel |
| CN112794359B (en) * | 2020-12-31 | 2022-10-11 | 浙江工业大学 | ZnO @ C composite material and preparation method and application thereof |
| CN113707467A (en) * | 2021-09-10 | 2021-11-26 | 安徽工业大学 | MOF-derived ZnO @ C cubic electrode material, and preparation method and application thereof |
| CN113871211B (en) * | 2021-09-15 | 2023-10-03 | 深圳市宏卓远电子科技有限公司 | Super capacitor with high energy density |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784658A (en) * | 2016-12-01 | 2017-05-31 | 中南大学 | A kind of Morphological control method of lithium ion battery metal oxide/carbon negative pole material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (4)
| Title |
|---|
| Lun Pan等.MOF-derived C-doped ZnO prepared via a two-step calcination for efficient photocatalysis.《Applied Catalysis B: Environmental》.2016,第189卷 * |
| Seung Jae Yang等.MOF-derived ZnO and ZnO@C composites with high photocatalytic activity and adsorption capacity.《Journal of Hazardous Materials》.2010,第186卷 * |
| Yonghai Song等.Hollow metal organic frameworks-derived porous ZnO/C nanocages as anode materials for lithium-ion batteries.《Journal of Alloys and Compounds》.2016,第694卷 * |
| 张慧等.基于金属 - 有机骨架前驱体的先进功能材料.《化学进展》.2015,第27卷 * |
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