CN109755027B - Composite graphene film, high-energy supercapacitor and intelligent flexible device - Google Patents
Composite graphene film, high-energy supercapacitor and intelligent flexible device Download PDFInfo
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- CN109755027B CN109755027B CN201910022830.7A CN201910022830A CN109755027B CN 109755027 B CN109755027 B CN 109755027B CN 201910022830 A CN201910022830 A CN 201910022830A CN 109755027 B CN109755027 B CN 109755027B
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Abstract
The invention discloses a composite graphene film, a high-energy supercapacitor and an intelligent flexible device, and belongs to the technical field of electrochemical energy storage. According to the invention, the interlayer spacing of the graphene film is accurately regulated and controlled, so that the interlayer spacing is matched with the size of ions in the electrolyte, the electrochemical energy storage process is optimized, the energy stored by the capacitor is greatly improved, and an intelligent output flexible device is constructed on the basis of the film. The method has simple process and compatibility with the prior art, can be prepared in a large scale, and can greatly improve the energy storage performance of the device, thereby having great application prospect.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a composite graphene film, a high-energy super capacitor and an intelligent flexible device.
Background
The super capacitor has the advantages of quick charging, high power, long cycle life, wide working temperature range, high safety performance and the like, can be used as a high-power supply, and has wide development prospect in the fields of hybrid electric vehicles, standby power supplies, portable electronic equipment and the like. However, the lower energy density (i.e., the energy stored per unit volume) of supercapacitors compared to batteries limits their broader application. Especially in practical applications of portable intelligent devices, it is desirable to achieve more energy storage in a limited volume, i.e. to increase the volumetric energy density.
The electrode material is an important component of the super capacitor, and in recent years, the discovery and application of novel carbon materials such as graphene and carbon nanotubes brings great importance to the field of energy storageThe pushing of (2). Taking graphene material as an example, the theoretical capacity of the graphene material as a supercapacitor electrode is up to 550F g-1And has good conductivity and stability. In addition, compared with a transition metal material, the graphene material can stably work under a higher potential window, and has great application potential as a high-energy and high-power supercapacitor electrode.
At present, many works are made on how to improve the capacity of the graphene material, however, the improvement of the energy density is far from the requirement of practical application. In order to achieve an increase in the final energy density, one is indispensable for the preparation of the material from the viewpoint of the device itself. One of the important factors is the operating potential window of the supercapacitor, which is generally determined by the electrolyte chosen. Ionic liquids have a potential window as high as 4.0V, which is considered a good choice for achieving high energy density supercapacitors. However, it is still a great challenge to prepare an electrode material that can be matched with different electrolytes (i.e. the porosity of the electrode material can be controlled), so as to optimize the performance. And the flexibility of the prepared supercapacitor is also essential in portable and wearable electronic applications. In addition, in order to meet different output requirements, whether a single device can realize the function of selective output through intelligent design still needs to be solved.
Disclosure of Invention
The invention aims to provide a composite graphene film, a high-energy super capacitor and an intelligent flexible device. Firstly, the pore structure of the electrode material is adjusted and controlled to be matched with the size of ions in the electrolyte, so that the high-energy-density output of the whole device is realized, the level of a lead-acid battery is reached, and the lead-acid battery has higher power density; based on the method, the all-solid-state flexible device capable of intelligently outputting is constructed, so that the method has wide market application prospect.
The technical scheme adopted by the invention is as follows:
a composite graphene film is prepared by the following steps: adding graphite oxide and thermal expansion reduced graphene into water according to a certain proportion, and performing ultrasonic dispersion to obtain a uniform suspension; then carrying out vacuum filtration on the uniform suspension to obtain a film and airing the film; after the dried film is subjected to hydrogen iodide steam reduction to improve the conductivity of the film, the composite graphene film is obtained; in the composite graphene film, the content of the thermal expansion reduced graphene is 40-60 wt.%.
The thickness of the composite graphene film is 10-200 microns.
The composite graphene film is composed of graphite oxide and thermal expansion reduced graphene, and thermal expansion reduced graphene sheets are uniformly dispersed in the graphite oxide; the interlayer spacing of the graphene can be adjusted by adjusting the ratio between the graphite oxide and the thermal expansion reduced graphene (namely adjusting the stacking mode of graphene interlayers).
The composite graphene film is used as an electrode active material, and can be directly used as a working electrode without using an additional current collector due to the self-supporting structural characteristic. The high-energy supercapacitor is constructed by utilizing the composite graphene film, and the following two modes can be adopted:
the first mode is as follows: the composite graphene film is directly used as a working electrode, and is assembled according to the sequence of electrode-diaphragm-electrode, and is injected with ionic liquid as electrolyte to assemble the high-energy-density super capacitor; the diaphragm is a polypropylene-polyethylene-polypropylene composite diaphragm, a single-layer polypropylene film, a single-layer polyethylene film, a glass fiber diaphragm or a cellulose diaphragm with a three-layer structure;
the second way is: the composite graphene film is directly used as a working electrode, a diaphragm is not needed, a solid electrolyte is adopted, the electrode-solid electrolyte-electrode assembly is carried out according to the sequence, and then the electrode-solid electrolyte-electrode assembly is packaged by a packaging material, so that the all-solid-state flexible supercapacitor with the high-potential window is manufactured; wherein: the packaging material is polyethylene glycol terephthalate, polydimethylsiloxane, ethylene-vinyl acetate copolymer or polyvinyl butyral resin; the assembled all-solid-state flexible supercapacitor with the high-potential window can be bent at any angle of 0-180 degrees.
The invention further utilizes the composite graphene film to construct an intelligent flexible device, which specifically comprises the following steps: the composite graphene film is directly used as a working electrode, and a solid electrolyte is adopted to assemble an electrode-solid electrolyte-electrode structure; the electrode-solid electrolyte-electrode structure is used as a unit, a plurality of units are stacked and then packaged by packaging materials, and the all-solid-state intelligent flexible capacitor device with adjustable output is obtained.
In the process of constructing the high-energy supercapacitor and the intelligent flexible device, the solid electrolyte is a gel electrolyte which takes ionic liquid as a conductive medium and takes polyvinylidene fluoride-hexafluoropropylene copolymer as a matrix, and is specifically obtained by curing a mixed material of the ionic liquid, acetone and the polyvinylidene fluoride-hexafluoropropylene copolymer.
The ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate or 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
In the process of constructing the high-energy supercapacitor and the intelligent flexible device, the graphene interlayer spacing in the composite graphene film is matched with the size of the used ionic liquid, namely the graphene interlayer spacing in the composite graphene film has a pore structure matched with the target ionic liquid. The interlayer spacing refers to the spacing between graphene sheets in the film, and the matching refers to the fact that the interlayer spacing is equal to or close to the ion size, and the difference between the graphene interlayer spacing and the ion size of the ionic liquid is less than 0.1 nm.
The manufactured all-solid-state intelligent capacitor device can realize different output requirements according to different connection modes, namely when an external circuit is connected with two structural units in series, the purpose of increasing the output of a potential window can be achieved; when the external circuit is connected with the two structural units in parallel, the output purpose of increasing the capacity can be achieved.
The design principle of the invention is as follows:
the porosity of the whole electrode material is regulated and controlled by regulating and controlling the inter-lamellar spacing in the graphene film. When the pore size of the electrode material is matched to the ionic size of the electrolyte, the space utilization of the pores is optimized, thereby maximizing the volumetric energy density. In the design of the all-solid-state flexible supercapacitor, the good bending performance of the graphene film electrode material also ensures the flexibility of the whole device. In the design of the intelligent device, different output effects are realized by changing the connection mode of an external circuit according to requirements.
The invention has the following advantages and beneficial effects:
1. in the assembled supercapacitor device, the self-supporting graphene film serving as the active material can be used as a working electrode without using an additional current collector.
2. The graphene film structure with the adjustable spacing can effectively control the porosity of the material, so that the graphene film structure is matched with electrolyte, and the energy density of a device is maximized.
3. The method for realizing porosity adjustment has the advantages of simple process, strong repeatability and easy large-scale production.
4. The self-supporting interval-adjustable graphene film produced by the invention has wide application, and can be effectively used for constructing super capacitors of different electrolyte systems, such as flexible all-solid-state equipment.
5. The intelligent all-solid-state flexible device produced by the invention can change the connection mode according to the requirement so as to achieve the output purpose of increasing the potential window or increasing the capacity.
Drawings
Fig. 1 is a schematic diagram of a self-supporting graphene thin film manufactured by using graphite oxide and a thermally expanded reduced graphene precursor according to the present invention.
FIG. 2 shows the properties of films produced using precursors of different ratios, after conditioning.
Fig. 3 is a comparison of energy density and power density achieved with a symmetric supercapacitor assembled using optimized graphene films versus different types of energy storage devices.
Fig. 4 is a schematic diagram of the composition structure of the manufactured intelligent all-solid-state flexible device and a photo thereof.
Fig. 5 is a schematic diagram of different connection modes for the smart device and is accompanied by corresponding constant current charging and discharging curves.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
The preparation process of the self-supporting graphene thin film used in the following examples is shown in fig. 1: firstly, adding graphite oxide and thermal expansion reduced graphene which are prepared in advance into water according to a certain proportion, and obtaining a uniform solution through ultrasonic dispersion; then carrying out vacuum filtration to obtain a film and airing the film; then, the electrode is subjected to further hydrogen iodide vapor reduction to improve the conductivity and then is used as a working electrode.
The process of increasing the conductivity by hydrogen iodide vapor reduction can be referred to in reference 1 (reference 1: Direct reduction of graphene oxide films in high purity and flexible film by hydrogen acids, Carbon,2010,48, 4466-.
The Thermal expansion Reduced Graphene is obtained by taking Graphene oxide as a raw material and carrying out high-temperature deoxidation and rapid expansion, and can be referred to in references 2-3 (reference 2: a simulation of Graphene/polyaniline composite paper in a single-anode electrochemical polymerization for high-performance flexible electrode, ACS Nano2009,3, 1745-1752; reference 3: J.Mater.chem.A,2017,5, 24686-24694).
The solid electrolyte is electrolyte gel obtained by solidifying acetone dispersion of polyvinylidene fluoride-hexafluoropropylene copolymer dissolved with ionic liquid.
Comparative example 1
In the preparation process of the graphene film, the following dispersion liquids are respectively used: (1) pure graphite oxide; (2) graphite oxide-thermally expanded graphene (25 wt.% thermally expanded graphene); (3) graphite oxide-thermally expanded graphene (75 wt.% thermally expanded graphene). And assembling the obtained film in 1-ethyl-3-methylimidazolium tetrafluoroborate electrolyte to obtain a symmetrical supercapacitor, and carrying out charge and discharge tests on the symmetrical supercapacitor. The results are shown in fig. 2, and none of the 3 samples achieved the maximum volumetric capacitance, indicating that the optimal pore space utilization was not achieved during the energy storage process.
Example 1
In the preparation process of the graphene film, a dispersion of graphite oxide-thermal expansion graphene (50 wt.% of thermal expansion graphene) is used, and the obtained film is assembled in 1-ethyl-3-methylimidazolium tetrafluoroborate electrolyte to obtain a symmetrical supercapacitor, and a charge and discharge test is performed. As a result, as shown in fig. 2, it can be found that the graphene thin film prepared in this ratio exhibits higher volume specific capacitance than the 3 samples in comparative example 1 described above, indicating that it has optimized pore space utilization in the same kind of samples during energy storage.
Example 2
The self-supporting graphene film with the most excellent performance in the example 1 is taken as a working electrode, and the loading capacity per unit area is adjusted to 10mg cm of the commercial standard in a mode of adding more dispersion liquid during vacuum filtration-2And assembling the two layers in 1-ethyl-3-methylimidazole tetrafluoroborate electrolyte to obtain a symmetrical supercapacitor, and calculating the integral volume energy density of the obtained device. As shown in FIG. 3, the energy density of the super capacitor prepared by the method can reach 90.1Wh L-1Not only far higher than the traditional commercial super capacitor (5-8Wh L)-1) Even reaching the level of lead-acid batteries (50-90Wh L)-1) And simultaneously has more than two orders of magnitude higher power density. The energy storage performance of the produced device can be greatly improved through the method.
Example 3
An all-solid-state intelligent flexible device was fabricated with the configuration shown in fig. 4(a) using the graphene film prepared in example 1 as a working electrode, a polyvinylidene fluoride-hexafluoropropylene copolymer dissolved with an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) as a solid electrolyte, and polyethylene terephthalate as an encapsulating material, and a physical image photograph of the device obtained can be seen in fig. 4 (b). The all-solid-state intelligent flexible device can meet different input requirements by changing the connection mode. As shown in fig. 5(a), due to different connection modes, the device sequentially achieves the effects of series output and parallel output, and achieves the purposes of increasing the potential window and increasing the capacity (as shown by the charging and discharging curves in fig. 5 (b)).
Claims (10)
1. A composite graphene film is characterized in that: the preparation process of the composite graphene film comprises the following steps: adding graphite oxide and thermal expansion reduced graphene into water according to a certain proportion, and performing ultrasonic dispersion to obtain a uniform suspension; then carrying out vacuum filtration on the uniform suspension to obtain a film and airing the film; after the dried film is subjected to hydrogen iodide steam reduction to improve the conductivity of the film, the composite graphene film is obtained; in the composite graphene film, the content of the thermal expansion reduced graphene is 40-60 wt.%.
2. The composite graphene film according to claim 1, wherein: the thickness of the composite graphene film is 10-200 microns.
3. A high-energy supercapacitor containing the composite graphene thin film according to claim 2, wherein: the composite graphene film is directly used as a working electrode and assembled into a high-energy super capacitor in the following two ways;
the first mode is as follows: assembling according to the sequence of electrode-diaphragm-electrode, and injecting ionic liquid as electrolyte to assemble the super capacitor with high energy density;
the second way is: the method is characterized in that a diaphragm is not needed, solid electrolyte is adopted, the electrode-solid electrolyte-electrode assembly is carried out in the sequence, and then packaging materials are used for packaging, so that the all-solid-state flexible supercapacitor with the high-potential window is manufactured; wherein: the solid electrolyte is a gel electrolyte which takes ionic liquid as a conductive medium and takes polyvinylidene fluoride-hexafluoropropylene copolymer as a matrix;
in the first and second modes, the graphene interlayer spacing in the composite graphene thin film is matched with the ion size of the electrolyte used.
4. The high energy ultracapacitor of claim 3, wherein: the diaphragm is a polypropylene-polyethylene-polypropylene composite diaphragm, a single-layer polypropylene film, a single-layer polyethylene film, a glass fiber diaphragm or a cellulose diaphragm with a three-layer structure.
5. The high energy ultracapacitor of claim 3, wherein: the packaging material is polyethylene glycol terephthalate, polydimethylsiloxane, ethylene-vinyl acetate copolymer or polyvinyl butyral resin.
6. The high energy ultracapacitor of claim 3, wherein: the all-solid-state flexible supercapacitor with the high-potential window assembled in the second mode can be bent at any angle of 0-180 degrees.
7. The high energy ultracapacitor of claim 3, wherein: the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate or 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
8. An intelligent flexible device constructed by using the composite graphene thin film of claim 2, wherein: the composite graphene film is directly used as a working electrode, and a solid electrolyte is adopted to assemble an electrode-solid electrolyte-electrode structure; the electrode-solid electrolyte-electrode structure is used as a unit, a plurality of units are stacked and then packaged by packaging materials, and the all-solid-state intelligent flexible capacitor device with adjustable output is obtained.
9. The intelligent flexible device of claim 8, wherein: the solid electrolyte is a gel electrolyte which takes ionic liquid as a conductive medium and takes polyvinylidene fluoride-hexafluoropropylene copolymer as a matrix, and the composite graphene film has a pore structure matched with the ionic liquid.
10. The intelligent flexible device of claim 8, wherein: the manufactured all-solid-state intelligent capacitor device can realize different output requirements according to different connection modes, namely when an external circuit is connected with two structural units in series, the purpose of increasing the output of a potential window can be achieved; when the external circuit is connected with the two structural units in parallel, the output purpose of increasing the capacity can be achieved.
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| CN110828197B (en) * | 2019-11-05 | 2022-03-08 | 中国科学院合肥物质科学研究院 | Solid laminated interdigital electrochemical capacitor and preparation method thereof |
| CN110828198B (en) * | 2019-11-05 | 2022-03-08 | 中国科学院合肥物质科学研究院 | Laminated interdigital electrochemical capacitor and preparation method thereof |
| CN112542329B (en) * | 2020-11-17 | 2022-07-19 | 伊诺福科光学技术有限公司 | High energy density super capacitor |
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