CN111863461B - Self-assembled zinc oxide/graphene composite electrode membrane material and preparation method and application thereof - Google Patents
Self-assembled zinc oxide/graphene composite electrode membrane material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of electrode materials, and discloses a self-assembled zinc oxide/graphene composite electrode membrane material and a preparation method and application thereof. The preparation method comprises the steps of firstly preparing graphene oxide and metal oxide zinc oxide nanosheet components, preparing a graphene/zinc oxide composite electrode membrane material by a suction filtration self-assembly process, and improving the conductivity of the composite material by adopting a thermal reduction method. The prepared graphene/zinc oxide composite electrode material not only has the flexibility of graphene, but also has the pseudo-capacitance characteristic of metal oxide, and the composite material shows excellent electrochemical performance and cycle stability.
Description
Technical Field
The invention belongs to the field of electrode materials, and particularly relates to a self-assembled zinc oxide/graphene composite electrode membrane material and a preparation method and application thereof.
Background
Graphene, as a two-dimensional lamellar structure, has ultrahigh conductivity, specific surface area and chemical stability, and is commonly used as an electrode material of an electric double layer supercapacitor. Since the carbon ring of the graphene sheet layer is easy to generate a conjugation effect, the sheet layer is easy to agglomerate and stack, which is not beneficial to the penetration and diffusion of ions. Therefore, the actual specific capacitance value of graphene as an electrode material is lower than the theoretical value. In order to further improve the specific capacitance of the graphene-based capacitor, the composite electrode material can be constructed by compounding the transition metal and the conductive polymer and utilizing the synergistic effect of the transition metal and the conductive polymer. However, most of the current reports are graphene composite powder materials, the powder electrode materials need to be added with a binder such as polytetrafluoroethylene emulsion and a conductive agent such as carbon black and acetylene black when the electrode is assembled, and the additives obviously reduce the utilization rate of the composite material and improve the resistance of the electrode in electrolyte. In addition, the graphene composite membrane material mostly adopts a solution deposition method or an in-situ synthesis method, so that the graphene membrane structure is virtually destroyed, and the content of the added transition metal oxide and the added conductive polymer is not controllable. Therefore, designing a graphene-based composite film not only ensures excellent performance of the electrode material, but also improves dispersibility and controllability of the composite electrode material, which is still a challenge.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a self-assembled zinc oxide/graphene composite electrode membrane material.
The invention also aims to provide the self-assembled zinc oxide/graphene composite electrode membrane material prepared by the method.
The invention further aims to provide application of the self-assembled zinc oxide/graphene composite electrode film material in a super capacitor.
The purpose of the invention is realized by the following scheme:
a preparation method of a self-assembled zinc oxide/graphene composite electrode membrane material mainly comprises the following steps:
(1) dispersing graphene oxide powder in water to form uniformly dispersed graphene oxide dispersion liquid;
(2) adding sodium hydroxide and ethylenediamine into a zinc acetate aqueous solution, and heating and refluxing to react to generate a zinc oxide nano sheet;
(3) dispersing the zinc oxide nano-sheets prepared in the step (2) in water to form uniformly dispersed zinc oxide nano-sheet dispersion liquid;
(4) mixing the zinc oxide nano-sheet dispersion liquid obtained in the step (3) with the graphene oxide dispersion liquid obtained in the step (1), then performing ultrasonic dispersion, and performing suction filtration to obtain a uniform flexible membrane material;
(5) and (4) calcining the flexible membrane material obtained in the step (4) at high temperature to obtain the self-assembled zinc oxide/graphene composite electrode membrane material.
The mass concentration of the graphene oxide in the graphene oxide dispersion liquid in the step (1) is 1-5 mg/mL, and preferably 2 mg/mL;
the mass fraction of zinc acetate in the zinc acetate aqueous solution in the step (2) is 1-2%;
the molar ratio of the sodium hydroxide to the ethylenediamine in the step (2) is 1: 0.8-1.3; the ratio of the total molar weight of the sodium hydroxide and the ethylenediamine to the molar weight of the zinc acetate in the step (2) is 3-8: 1;
the heating reflux reaction in the step (2) is reflux reaction at 100 ℃ for 12-24 hours;
the method also comprises a purification step after the reaction in the step (2) is finished, and comprises the following specific steps: washing the obtained reaction liquid with water and ethanol respectively, and then carrying out vacuum filtration to obtain white zinc oxide nanosheet crystals.
The mass concentration of the zinc oxide nanosheets in the zinc oxide nanosheet dispersion liquid in the step (3) is 0.1-5 mg/mL, preferably 0.1-1 mg/mL;
the dispersion in the step (1) and the dispersion in the step (3) are preferably subjected to ultrasonic dispersion at 40-100 kHz;
the usage amount of the zinc oxide nano-sheet dispersion liquid and the graphene oxide dispersion liquid in the step (4) meets the requirement that the mass ratio of the zinc oxide nano-sheets to the graphene oxide is 5-50: 100;
the ultrasonic dispersion in the step (4) is ultrasonic dispersion for 1-2 hours at 40-100 kHz;
the suction filtration in the step (4) is vacuum filtration by adopting a polytetrafluoroethylene microporous filter membrane, wherein the aperture of the polytetrafluoroethylene microporous filter membrane is 0.22 mu m;
the high-temperature calcination in the step (5) refers to high-temperature calcination in nitrogen or in an inert atmosphere; the high-temperature calcination refers to calcination at 600-800 ℃ for 2-8 h.
The self-assembled zinc oxide/graphene composite electrode membrane material prepared by the method.
The self-assembled zinc oxide/graphene composite electrode membrane material is applied to a super capacitor.
The mechanism of the invention is as follows:
the preparation method comprises the steps of firstly preparing graphene oxide and metal oxide zinc oxide nanosheet components, preparing a graphene oxide/zinc oxide composite electrode membrane material by a suction filtration self-assembly process, and improving the conductivity of the composite material by adopting a thermal reduction method. The prepared graphene/zinc oxide composite electrode membrane material can be directly used as a self-supporting electrode material. The graphene composite material has the flexibility of graphene, the pseudo-capacitance characteristic of metal oxide, and excellent electrochemical performance and cycle stability.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts mild conditions to prepare the zinc oxide nano-sheet and has excellent water dispersibility.
(2) According to the invention, zinc oxide nanosheets are used as pseudocapacitor components and graphene lamellar fillers, and a vacuum-assisted suction filtration self-assembly technology is adopted to obtain the flexible conductive film with controllable thickness and size.
(3) The invention has the advantages of wide raw material source, low price, simple preparation, high specific capacitance and high cycling stability.
Drawings
Fig. 1 is a schematic view of the appearance and transformation of a graphene oxide/zinc oxide and zinc oxide/graphene composite film according to the present invention.
Fig. 2 is an XPS chart of the graphene/zinc oxide composite film prepared in example 2.
Fig. 3 is an SEM image of the zinc oxide nanoplatelets prepared in example 5.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
0.5g of zinc acetate was weighed into 45.5mL of deionized water and stirred magnetically until completely dissolved. Then 5mL of 1M sodium hydroxide solution and 0.27mL of ethylenediamine were slowly added dropwise and the reaction was heated under reflux at 100 ℃ for 24 hours. Washing the obtained reaction solution with water and ethanol respectively, and then carrying out vacuum filtration to obtain the zinc oxide nano-sheet. Then, 200mg of graphene oxide and 10mg of zinc oxide nanosheets are weighed, ultrasonic dispersion is carried out for 2 hours at the ultrasonic power of 40kHz respectively at normal temperature, then mixing and ultrasonic treatment are carried out for 1 hour, uniform dispersion liquid is formed (the concentrations of the zinc oxide dispersion liquid and the graphene oxide dispersion liquid are 0.1mg/mL and 2mg/mL respectively), the dispersion liquid is placed into a Buchner funnel, a polytetrafluoroethylene microporous filter membrane (0.22 mu m) is adopted for carrying out reduced pressure suction filtration, a uniform composite membrane is obtained, the obtained composite membrane is placed into a tubular furnace (argon atmosphere), the temperature is set to 600 ℃, and the composite electrode membrane material of self-assembly zinc oxide/graphene is obtained after treatment for 8 hours.
The specific mass capacitance of the composite membrane reaches 150F/g under the current density of 0.2A/g, the composite membrane is cycled for 1000 times under the current density of 10A/g, and the capacitance retention rate is 98%.
Example 2:
0.3g of zinc acetate was weighed into 27.5mL of deionized water and stirred magnetically until completely dissolved. Then 3.4mL of 1M sodium hydroxide solution and 0.23mL of ethylenediamine were slowly added dropwise and the reaction was heated under reflux at 100 ℃ for 24 hours. Washing the obtained reaction solution with water and ethanol respectively, and then carrying out vacuum filtration to obtain the zinc oxide nano-sheet. Then, 200mg of graphene oxide and 20mg of zinc oxide nanoplatelets were weighed, ultrasonically dispersed at 40kHz at room temperature for 2 hours, respectively, and then mixed with ultrasound for 1 hour to form a uniform dispersion (the concentrations of the zinc oxide dispersion and the graphene oxide dispersion are 0.2mg/mL and 2mg/mL, respectively). The dispersion was placed in a buchner funnel and filtered under reduced pressure using a polytetrafluoroethylene microporous membrane (0.22 μm) to obtain a homogeneous composite membrane. And (3) placing the obtained composite membrane in a tubular furnace (in an argon atmosphere), setting the temperature to be 650 ℃, and treating for 5 hours to obtain the self-assembled zinc oxide/graphene composite electrode membrane material. The XPS pattern of the resulting composite film is shown in fig. 2, and it can be seen from fig. 2 that the composite material contains zinc oxide.
The specific mass capacitance of the composite membrane reaches 220F/g under the current density of 0.2A/g by using a three-electrode test (the composite membrane is a working electrode, a platinum sheet is a counter electrode, and a calomel electrode is a reference electrode), and the capacitance retention rate is 97 percent after the composite membrane is cycled for 1000 times under the current density of 10A/g.
Example 3:
0.8g of zinc acetate was weighed into 79.2mL of deionized water and stirred magnetically until completely dissolved. Then, 10.4mL of 1M sodium hydroxide solution and 0.77mL of ethylenediamine were slowly added dropwise, and the reaction was heated under reflux at 100 ℃ for 24 hours. Washing the obtained reaction liquid with water and ethanol respectively, and then carrying out vacuum filtration to obtain the zinc oxide nanosheet. Then, 200mg of graphene oxide and 26mg of zinc oxide nanoplatelets were weighed, ultrasonically dispersed at an ultrasonic power of 40kHz for 2 hours at normal temperature, respectively, and then mixed and ultrasonically treated for 1 hour to form a uniform dispersion liquid (the concentrations of the zinc oxide dispersion liquid and the graphene oxide dispersion liquid are 0.26mg/mL and 2mg/mL, respectively). The dispersion was placed in a buchner funnel and filtered under reduced pressure using a polytetrafluoroethylene microporous membrane (0.22 μm) to obtain a homogeneous composite membrane. And (3) placing the obtained composite membrane in a tubular furnace (in an inert atmosphere of argon), setting the temperature at 750 ℃, and treating for 4 hours to obtain the self-assembled zinc oxide/graphene composite electrode membrane material.
The specific mass capacitance of the composite membrane reaches 280F/g under the current density of 0.2A/g, and the capacitance retention rate is 98 percent after the composite membrane is cycled for 1000 times under the current density of 10A/g by using a three-electrode test (the composite membrane is a working electrode, a platinum sheet is a counter electrode, and a calomel electrode is a reference electrode).
Example 4:
1g of zinc acetate was weighed, added to 90mL of deionized water, and magnetically stirred until completely dissolved. Then, 11.4mL of 1M sodium hydroxide solution and 7.6mL of ethylenediamine were slowly added dropwise, and the reaction was heated under reflux at 100 ℃ for 24 hours. Washing the obtained reaction solution with water and ethanol respectively, and then carrying out vacuum filtration to obtain the zinc oxide nano-sheet. Then, 200mg of graphene oxide and 54mg of zinc oxide nanoplatelets were weighed, ultrasonically dispersed at 40kHz at room temperature for 2 hours, respectively, and then mixed with ultrasound for 1 hour to form a uniform dispersion (the concentrations of the zinc oxide dispersion and the graphene oxide dispersion are 0.54mg/mL and 2mg/mL, respectively). The dispersion was placed in a buchner funnel and filtered under reduced pressure using a polytetrafluoroethylene microporous membrane (0.22 μm) to obtain a homogeneous composite membrane. And (3) placing the obtained composite membrane in a tubular furnace (in an inert atmosphere of argon gas), setting the temperature at 800 ℃, and treating for 3 hours to obtain the self-assembled zinc oxide/graphene composite electrode membrane material.
The specific mass capacitance of the composite membrane reaches 350F/g under the current density of 0.2A/g, and the capacitance retention rate is 95 percent after the composite membrane is cycled for 1000 times under the current density of 10A/g by using a three-electrode test (the composite membrane is a working electrode, a platinum sheet is a counter electrode, and a calomel electrode is a reference electrode).
Example 5:
1g of zinc acetate was weighed, added to 90mL of deionized water, and magnetically stirred until completely dissolved. Then 8.3mL of 1M sodium hydroxide solution and 0.66mL of ethylenediamine were slowly added dropwise, and the reaction was carried out at 100 ℃ under reflux for 24 hours to obtain zinc oxide nanoplatelets (SEM image is shown in FIG. 3). Then, 200mg of graphene oxide and 70mg of zinc oxide nanoplatelets were weighed, ultrasonically dispersed at 40kHz at room temperature for 2 hours, respectively, and then mixed with ultrasound for 1 hour to form a uniform dispersion (the concentrations of the zinc oxide dispersion and the graphene oxide dispersion are 0.7mg/mL and 2mg/mL, respectively). The dispersion was placed in a buchner funnel and filtered under reduced pressure using a polytetrafluoroethylene microporous membrane (0.22 μm) to obtain a homogeneous composite membrane. And (3) placing the obtained composite membrane in a tubular furnace (in an inert atmosphere of argon gas), setting the temperature at 600 ℃, and treating for 8 hours to obtain the self-assembled zinc oxide/graphene composite electrode membrane material.
The specific mass capacitance of the composite membrane reaches 400F/g under the current density of 0.2A/g by using a three-electrode test (the composite membrane is a working electrode, a platinum sheet is a counter electrode, and a calomel electrode is a reference electrode), and the capacitance retention rate is 93 percent after the composite membrane is cycled for 1000 times under the current density of 10A/g.
Example 6:
1.5g of zinc acetate was weighed into 80.5mL of deionized water and stirred magnetically until completely dissolved. 13.7mL of 1M sodium hydroxide solution and 0.92mL of ethylenediamine were then slowly added dropwise and the reaction was heated at 100 ℃ under reflux for 24 hours. Then, 200mg of graphene oxide and 100mg of zinc oxide nanoplatelets are weighed, and are subjected to ultrasonic dispersion for 2 hours at the ultrasonic power of 40kHz respectively at normal temperature, and then are mixed and subjected to ultrasonic treatment for 1 hour to form uniform dispersion liquid (the concentrations of the zinc oxide dispersion liquid and the graphene oxide dispersion liquid are 1mg/mL and 2mg/mL respectively). The dispersion was placed in a buchner funnel and filtered under reduced pressure using a polytetrafluoroethylene microporous membrane (0.22 μm) to obtain a homogeneous composite membrane. And (3) placing the obtained composite membrane in a tubular furnace (in an inert atmosphere of argon gas), setting the temperature at 600 ℃, and treating for 8 hours to obtain the self-assembled zinc oxide/graphene composite electrode membrane material.
The specific mass capacitance of the composite membrane reaches 300F/g under the current density of 0.2A/g by using a three-electrode test (the composite membrane is a working electrode, a platinum sheet is a counter electrode, and a calomel electrode is a reference electrode), and the capacitance retention rate is 82 percent after the composite membrane is cycled for 1000 times under the current density of 10A/g.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a self-assembled zinc oxide/graphene composite electrode membrane material is characterized by comprising the following steps:
(1) dispersing graphene oxide powder in water to form uniformly dispersed graphene oxide dispersion liquid;
(2) adding sodium hydroxide and ethylenediamine into a zinc acetate aqueous solution, and heating and refluxing to react to generate a zinc oxide nano sheet;
(3) dispersing the zinc oxide nano-sheets prepared in the step (2) in water to form uniformly dispersed zinc oxide nano-sheet dispersion liquid;
(4) mixing the zinc oxide nano-sheet dispersion liquid obtained in the step (3) with the graphene oxide dispersion liquid obtained in the step (1), then performing ultrasonic dispersion, and performing suction filtration to obtain a uniform flexible membrane material;
(5) calcining the flexible membrane material obtained in the step (4) at high temperature to obtain a self-assembled zinc oxide/graphene composite electrode membrane material;
the amount of the aqueous solution of the zinc oxide nano-sheets and the aqueous solution of the graphene oxide in the step (4) is 5-35: 100.
2. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
the mass concentration of the graphene oxide in the graphene oxide aqueous solution in the step (1) is 1-5 mg/mL.
3. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
the mass fraction of zinc acetate in the zinc acetate aqueous solution in the step (2) is 1-2%;
the molar ratio of the sodium hydroxide to the ethylenediamine in the step (2) is 1: 0.8-1.3; the ratio of the total molar weight of the sodium hydroxide and the ethylenediamine to the molar weight of the zinc acetate in the step (2) is 3-8: 1;
the heating reflux reaction in the step (2) is reflux reaction at 100 ℃ for 12-24 hours.
4. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
and (3) the mass concentration of the zinc oxide nano-sheets in the water solution of the zinc oxide nano-sheets in the step (3) is 0.1-5 mg/mL.
5. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
the ultrasonic dispersion in the step (4) is ultrasonic dispersion for 1-2 hours at 40-100 kHz.
6. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
the suction filtration in the step (4) is vacuum filtration by adopting a polytetrafluoroethylene microporous filter membrane, wherein the aperture of the polytetrafluoroethylene microporous filter membrane is 0.22 mu m.
7. The preparation method of the self-assembled zinc oxide/graphene composite electrode membrane material according to claim 1, characterized in that:
the high-temperature calcination in the step (5) refers to high-temperature calcination in nitrogen or in an inert atmosphere; the high-temperature calcination refers to calcination at 600-800 ℃ for 2-8 h.
8. The self-assembled zinc oxide/graphene composite electrode membrane material prepared by the method of any one of claims 1 to 7.
9. The application of the self-assembled zinc oxide/graphene composite electrode film material according to claim 8 in a supercapacitor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN106563362A (en) * | 2016-10-25 | 2017-04-19 | 江苏大学 | Preparing method and usage of low-oxidization-degree graphene/zinc oxide nanometer composite film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN106563362A (en) * | 2016-10-25 | 2017-04-19 | 江苏大学 | Preparing method and usage of low-oxidization-degree graphene/zinc oxide nanometer composite film |
Non-Patent Citations (2)
| Title |
|---|
| 哑铃状氧化锌的合成与表征;赵荣祥等;《无机化学学报》;20070910(第09期);第1609-1614页 * |
| 基于氧化石墨烯复合膜的制备及其分离性能研究;吴维富;《中国优秀硕士学位论文全文数据库工程科技I辑》;20190215;第13-27页 * |
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Address after: 400700 5th floor, 74 Yunhe Road, Beibei District, Chongqing Applicant after: ZHONGKE GUANGHUA (CHONGQING) NEW MATERIAL RESEARCH INSTITUTE Co.,Ltd. Applicant after: Zhongke Testing Technology Service (Guangzhou) Co.,Ltd. Applicant after: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Address before: 400700 5th floor, 74 Yunhe Road, Beibei District, Chongqing Applicant before: ZHONGKE GUANGHUA (CHONGQING) NEW MATERIAL RESEARCH INSTITUTE Co.,Ltd. Applicant before: GUANGZHOU CAS TESTING TECHNOLOGY SERVICE CO.,LTD. Applicant before: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES |
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