CN113808854B - Flexible super capacitor - Google Patents
Flexible super capacitor Download PDFInfo
- Publication number
- CN113808854B CN113808854B CN202111079529.3A CN202111079529A CN113808854B CN 113808854 B CN113808854 B CN 113808854B CN 202111079529 A CN202111079529 A CN 202111079529A CN 113808854 B CN113808854 B CN 113808854B
- Authority
- CN
- China
- Prior art keywords
- film
- ionic liquid
- microcrystalline cellulose
- gel film
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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 provides a flexible supercapacitor, which is characterized in that a microcrystalline fiber anode gel film with a graphene surface and a microcrystalline fiber cathode gel film with a zinc-based surface are jointed, the graphene surface and the zinc-based surface face outwards, then the microcrystalline fiber composite current collecting gel film with the aluminum film surface is jointed in a covered edge mode, and then the jointed gel film is pressed on a protective film through a dry film laminator to obtain the flexible supercapacitor, wherein the anode gel film is obtained by organically compounding ionic liquid modified microcrystalline cellulose with hydroxylated graphene through hydrogen bond interaction.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a flexible super capacitor.
Background
In recent years, demands for wearable electronics, new energy technology, and smart devices have been increasing, and development of flexible energy storage materials has been continuously stimulated. Flexible supercapacitors are receiving a lot of attention due to their fast charge and discharge rates, high power density, long-term cycling stability and large deformation energy supply, and these flexible energy storage materials can be integrated with innovative functions such as wearable sensing, smart display and self-powered features. Supercapacitors are generally classified into double layer capacitors, pseudocapacitors and hybrid supercapacitors according to the charge storage mechanism, and the flexibility of the supercapacitor has been one of the hot spots of research.
Factors affecting the flexibility of the supercapacitor include the flexibility, foldability, of the current collector, electrolyte, electrodes, substrate, and these affect the durability of the flexible capacitor. The existing flexible super capacitor has the main defects that: (1) the existing current collector has poor flexibility; (2) the existing gel electrolyte has poor adhesion with electrode materials; (3) the preparation is complex, and the electrode material needs to be adhered to the substrate material through a complex process. Therefore, there is a need to develop a flexible supercapacitor to solve the above problems.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a flexible supercapacitor, and solves the problem that the durability of components of the supercapacitor after bending is poor.
(II) technical scheme
In order to solve the technical problems, the invention provides the following technical scheme:
a flexible supercapacitor is formed by attaching a microcrystalline fiber positive gel film with a graphene surface to a microcrystalline fiber negative gel film with a zinc-based surface, wherein the graphene surface and the zinc-based surface face outwards, then performing edge wrapping attachment on the microcrystalline fiber composite current collecting gel film with the aluminum film surface, and then pressing the attached gel film on a protective film through a dry film laminator to obtain the flexible supercapacitor, wherein the positive gel film is obtained by organically combining ionic liquid modified microcrystalline cellulose and hydroxylated graphene through hydrogen bonding, the negative gel film and the composite current collecting gel film are respectively obtained by organically combining the ionic liquid modified microcrystalline cellulose with an aluminum film and the zinc-based film through an electrodeposition mode, and the ionic liquid is 1-butyl-3-methylimidazolium diethyl phosphate.
Preferably, the protective film is a PET insulating film, the particle size of the hydroxylated graphene is 50-100nm, and the microcrystalline cellulose is any one of MCC-WJ101 and MCC-WJ 102.
The preparation method of the flexible supercapacitor comprises the following steps:
(1) Adding tributyl phosphate into a reaction bottle, stirring and heating, keeping the temperature, adding N-methylimidazole dropwise into the tributyl phosphate, keeping the temperature and stirring for 2-4h to obtain ionic liquid, dissolving microcrystalline cellulose into the ionic liquid, keeping the temperature and stirring for 4-5h to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, carrying out constant-current electrolytic electrodeposition on an aluminum film, and drying to obtain a microcrystalline fiber composite current-collecting gel film with an aluminum film surface;
(3) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding zinc chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, performing constant-current electrolytic electrodeposition on zinc, and drying to obtain a microcrystalline fiber negative electrode gel film with a zinc-based surface;
(4) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing through ultrasonic treatment, pouring a mixed solution into a flat-bottom tray container, standing for 1h after treatment through a horizontal oscillator, and drying to obtain a microcrystalline fiber positive gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber anode gel film with the graphene surface and the microcrystalline fiber cathode gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface face outwards, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a covered edge manner, and then pressing the attached gel film on the protective film through a dry film pressing machine to obtain the flexible supercapacitor.
Preferably, the mass ratio of tributyl phosphate, N-methylimidazole and microcrystalline cellulose in step (1) is 25-28.
Preferably, the mass ratio of the ionic liquid modified microcrystalline cellulose to the aluminum chloride in the step (2) is 1.
Preferably, the constant current electrolytic electrodeposition in the step (2) and the step (3) adopts a CHI760D type electrochemical workstation, magnetic stirring is adopted during electrolysis, a constant stirring speed is kept at 400r/min, the current density is 10mA/cm, the deposition is carried out for 4 hours at 80 ℃, and the drying conditions in the steps (2), (3) and (4) are all drying for 24 to 36 hours in a vacuum oven at 140 ℃.
Preferably, the mass ratio of the ionic liquid modified microcrystalline cellulose to the zinc chloride in the step (3) is 1.
Preferably, the drying conditions in the step (2) and the step (3) are drying for 24-36h in a vacuum oven at 140 ℃.
Preferably, the mass ratio of the ionic liquid modified microcrystalline cellulose to the hydroxylated graphene in the step (4) is 1.
Preferably, the time of the oscillation treatment in the step (4) is 20-30min, and the running speed of the PCB laminator in the step (5) is 2m/min.
The beneficial effects of the invention are:
(1) According to the flexible supercapacitor provided by the invention, phosphate anions in the ionic liquid can effectively interact with hydroxyl of microcrystalline cellulose to dissolve the microcrystalline cellulose, the C-6 hydroxyl of the microcrystalline cellulose is phosphorylated, and the microcrystalline cellulose obtains good conductivity by cooperating with the imidazole group, can be used as a gel electrolyte and is organically combined with an electrode, so that the problem of poor adhesion is solved.
(2) According to the flexible supercapacitor provided by the invention, aluminum and zinc are respectively deposited to the bottom of the ionic liquid modified microcrystalline cellulose to form a film in an electrodeposition mode, the ionic liquid modified microcrystalline cellulose and hydroxylated graphene are mutually attracted through hydrogen bond interaction, part of loose graphene is deposited at the bottom of the ionic liquid modified microcrystalline cellulose to form a film through horizontal oscillation, a gel film is obtained after drying, the gel film is used as an anode, and the anode, the cathode and a current collector are bonded and then are compressed by a film presser to obtain the flexible supercapacitor.
(3) According to the flexible supercapacitor provided by the invention, due to the fact that the microcrystalline cellulose has high viscosity, the microcrystalline cellulose can be used as a binder and a colloid electrolyte after being modified by the ionic liquid, and can be used as a composite base material of the positive electrode, the negative electrode and the current collector, and the positive electrode, the negative electrode and the current collector are endowed with good bending performance, so that the folding performance and the durability of the supercapacitor are improved.
Detailed Description
The invention is further illustrated by the following examples, which are intended to illustrate, but not to limit the invention further. The technical means used in the following examples are conventional means well known to those skilled in the art, and all raw materials are general-purpose materials.
Example 1
A preparation method of a flexible supercapacitor comprises the following steps:
(1) Firstly, adding 25g of tributyl phosphate into a reaction bottle, stirring and heating to 140 ℃, keeping the temperature, dripping 8g of N-methylimidazole into the tributyl phosphate, continuously keeping the temperature and stirring for 2 hours to obtain ionic liquid, dissolving 10g of microcrystalline cellulose into the ionic liquid, continuously keeping the temperature and stirring for 4 hours to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 20g of aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic electrodeposition of aluminum by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, depositing for 4h at 80 ℃, and drying for 24h in a vacuum oven at 140 ℃ to obtain a microcrystalline fiber composite current collecting gel film with an aluminum film surface;
(3) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 22g of zinc chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic zinc electrodeposition by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, depositing for 4h at 80 ℃, and drying for 24h in a vacuum oven at 140 ℃ to obtain a microcrystalline fiber negative electrode gel film with a zinc-based surface;
(4) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 6g of hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, carrying out ultrasonic treatment for 30min, uniformly mixing, pouring the mixed solution into a flat-bottom tray container, oscillating for 20min by using a horizontal oscillator, standing for 1h, and drying in a vacuum oven at 140 ℃ for 24h to obtain a microcrystalline fiber anode gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber anode gel film with the graphene surface and the microcrystalline fiber cathode gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface face outwards, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a covered manner, wherein the aluminum film surface faces inwards, and then pressing the attached gel film on the protective film at the speed of 2m/min through a PCB film pressing machine to obtain the flexible supercapacitor.
Example 2
A preparation method of a flexible supercapacitor comprises the following steps:
(1) Firstly, adding 26g of tributyl phosphate into a reaction bottle, stirring and heating to 145 ℃, keeping the temperature, dripping 9g of N-methylimidazole into the tributyl phosphate, continuously keeping the temperature and stirring for 3 hours to obtain ionic liquid, dissolving 12g of microcrystalline cellulose into the ionic liquid, continuously keeping the temperature and stirring for 5 hours to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 20g of aluminum chloride in batches under continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, carrying out constant current electrolytic electrodeposition on aluminum by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping a constant stirring speed at 400r/min and a current density at 10mA/cm, depositing for 4h at 80 ℃, and drying for 30h in a vacuum oven at 140 ℃ to obtain a microcrystalline fiber composite afflux gel film with an aluminum film surface;
(3) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 23g of zinc chloride in batches under continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, carrying out constant current electrolytic electrodeposition on zinc by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping a constant stirring speed at 400r/min, a current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is that after drying is carried out in a vacuum oven at 140 ℃ for 30h, the microcrystalline fiber negative electrode gel film with the zinc-based surface is obtained;
(4) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 7g of hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, carrying out ultrasonic treatment for 35min, uniformly mixing, pouring the mixed solution into a flat-bottom tray container, oscillating for 24min by using a horizontal oscillator, standing for 1h, and drying in a vacuum oven at 140 ℃ for 30h to obtain a microcrystalline fiber anode gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber anode gel film with the graphene surface and the microcrystalline fiber cathode gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface are outward, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a wrapping manner, the aluminum film surface is inward, and then pressing the attached gel film on the protective film at the speed of 2m/min through a PCB film pressing machine to obtain the flexible supercapacitor.
Example 3
A preparation method of a flexible supercapacitor comprises the following steps:
(1) Firstly, adding 27g of tributyl phosphate into a reaction bottle, stirring and heating to 148 ℃, keeping the temperature, adding 9.5g of N-methylimidazole dropwise into the tributyl phosphate, continuously keeping the temperature, stirring for 3.5 hours to obtain ionic liquid, dissolving 13g of microcrystalline cellulose into the ionic liquid, continuously keeping the temperature, stirring for 4.5 hours to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 20g of aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic electrodeposition on aluminum by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is that the microcrystalline fiber composite afflux gel film with the aluminum film surface is obtained after drying for 36h in a vacuum oven at 140 ℃;
(3) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 23g of zinc chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic zinc electrodeposition by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is that the microcrystalline fiber negative electrode gel film with the zinc-based surface is obtained after drying for 36h in a vacuum oven at 140 ℃;
(4) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 7.5g of hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, carrying out ultrasonic treatment for 35min, uniformly mixing, pouring the mixed solution into a flat-bottom tray container, oscillating for 30min by using a horizontal oscillator, standing for 1h, and drying in a vacuum oven at 140 ℃ for 36h to obtain a microcrystalline fiber positive gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber anode gel film with the graphene surface and the microcrystalline fiber cathode gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface are outward, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a wrapping manner, the aluminum film surface is inward, and then pressing the attached gel film on the protective film at the speed of 2m/min through a PCB film pressing machine to obtain the flexible supercapacitor.
Example 4
A preparation method of a flexible supercapacitor comprises the following steps:
(1) Firstly, adding 28g of tributyl phosphate into a reaction bottle, stirring and heating to 150 ℃, keeping the temperature, dripping 10g of N-methylimidazole into the tributyl phosphate, keeping the temperature and stirring for 4 hours to obtain ionic liquid, dissolving 15g of microcrystalline cellulose into the ionic liquid, keeping the temperature and stirring for 5 hours to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 20g of aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic electrodeposition on aluminum by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is that the microcrystalline fiber composite afflux gel film with the aluminum film surface is obtained after drying for 34h in a vacuum oven at 140 ℃;
(3) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 24g of zinc chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic zinc electrodeposition by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping a constant stirring speed at 400r/min and a current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is that the microcrystalline fiber negative electrode gel film with a zinc-based surface is obtained after drying for 34h in a vacuum oven at 140 ℃;
(4) Taking 10g of the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding 6g of hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, carrying out ultrasonic treatment for 30min, uniformly mixing, pouring the mixed solution into a flat-bottom tray container, oscillating for 30min by using a horizontal oscillator, standing for 1h, and drying in a vacuum oven at 140 ℃ for 34h to obtain a microcrystalline fiber anode gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber anode gel film with the graphene surface and the microcrystalline fiber cathode gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface are outward, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a wrapping manner, the aluminum film surface is inward, and then pressing the attached gel film on the protective film at the speed of 2m/min through a PCB film pressing machine to obtain the flexible supercapacitor.
Comparative example 1
A preparation method of a flexible supercapacitor comprises the following steps:
(1) Firstly, adding 25g of tributyl phosphate into a reaction bottle, stirring and heating to 150 ℃, keeping the temperature, dropwise adding 8g of N-methylimidazole into the tributyl phosphate, keeping the temperature and stirring for 5 hours to obtain ionic liquid;
(2) Taking 10g of the ionic liquid prepared in the step (1) into a reaction bottle, adding 20g of aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice-water bath, carrying out constant-current electrolytic electrodeposition on aluminum by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping the constant stirring speed at 400r/min and the current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is drying for 24h in a vacuum oven at 140 ℃ to obtain an aluminum film;
(3) Putting 10g of the ionic liquid prepared in the step (1) into a reaction bottle, adding 22g of zinc chloride in batches under continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, carrying out constant-current electrolytic zinc electrodeposition by using a CHI760D type electrochemical workstation, stirring by using magnetic force during electrolysis, keeping a constant stirring speed at 400r/min and a current density at 10mA/cm, and depositing for 4h at 80 ℃, wherein the drying condition is drying in a vacuum oven at 140 ℃ for 24h to obtain a zinc film;
(4) Attaching the obtained graphene as a positive electrode and the zinc film as a negative electrode to two sides of an organic gel electrolyte (propylene carbonate-tetraethylammonium tetrafluoroborate, the concentration of conductive salt is 0.65M), attaching the three by using the aluminum film, and then pressing the attached gel film onto the protective film by using a PCB film pressing machine at the speed of 2M/min to obtain the flexible supercapacitor.
1) The test method comprises the following steps: in order to evaluate the energy storage capacity of the flexible supercapacitor prepared according to the present invention, the supercapacitors of examples 1-4 and comparative example 1 were subjected to electrochemical performance evaluation by cyclic voltammetry and galvanostatic charge/discharge measurements, and their specific capacitances at different current densities, and the results of the measurements are shown in table 1.
TABLE 1
According to table 1, the charging and discharging time of the flexible capacitors prepared in examples 1 to 4 is longer than that of comparative example 1, and the specific capacitance examples 1 to 4 are superior to that of comparative example 1 under different current densities, which shows that the flexible capacitors prepared by the invention have higher specific capacitance and excellent discharging time, are beneficial to the application of the flexible capacitors in various occasions, and have wide application prospects.
2) In order to evaluate the flexibility and durability of the flexible supercapacitor prepared according to the present invention, the flexible supercapacitors prepared according to examples 1-4 and comparative example 1 were bent by 90 °, 75 °, 60 °, 45 ° and unbent, wherein the degree of bending is the degree of the included angle formed between the flexible supercapacitors, the electrochemical properties thereof were measured by cyclic voltammetry at a current density of 1A/g, and the coulombic efficiencies thereof after 500, 1000, 2000 cycles were recorded, and the measurement results are shown in table 2.
Table 2:
and (4) analyzing results: as can be seen from examples 1 to 4, the coulombic efficiency of the flexible capacitor decreased with the number of cycles, but the coulombic efficiency of the flexible capacitor bent to different angles did not greatly differ, while the coulombic efficiency of the flexible capacitor of comparative example 1 gradually decreased with the decrease of the bending angle, and the main difference between comparative example 1 and the examples was that it was not compounded with microcrystalline cellulose, thereby showing that the flexible capacitor prepared according to the present invention enhanced the flexibility and durability of the current collector, the electrode and the electrolyte by compounding of microcrystalline cellulose, thereby improving the flexibility and durability of the flexible capacitor as a whole.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The flexible supercapacitor is characterized in that a microcrystalline fiber positive gel film with a graphene surface and a microcrystalline fiber negative gel film with a zinc-based surface are attached, the graphene surface and the zinc-based surface face outwards, then the microcrystalline fiber composite current collecting gel film with the aluminum film surface is attached in a wrapped mode, then the attached gel film is pressed on a protective film through a dry film pressing machine, the positive gel film is obtained by organically combining ionic liquid modified microcrystalline cellulose and hydroxylated graphene through a hydrogen bond, the negative gel film and the composite current collecting gel film are respectively obtained by organically combining the ionic liquid modified microcrystalline cellulose with the aluminum film and the zinc-based film through an electrodeposition mode, and the ionic liquid is 1-butyl-3-methylimidazolium diethyl phosphate.
2. The flexible supercapacitor according to claim 1, wherein the protective film is a PET insulating film, the hydroxylated graphene has a particle size of 50-100nm, and the microcrystalline cellulose is any one of MCC-WJ101 and MCC-WJ 102.
3. A method for preparing a flexible supercapacitor according to any one of claims 1 and 2, comprising the following steps:
(1) Adding tributyl phosphate into a reaction bottle, stirring and heating, keeping the temperature, adding N-methylimidazole dropwise into the tributyl phosphate, keeping the temperature and stirring for 2-4h to obtain ionic liquid, dissolving microcrystalline cellulose into the ionic liquid, keeping the temperature and stirring for 4-5h to obtain ionic liquid modified microcrystalline cellulose for later use;
(2) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding aluminum chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, carrying out constant-current electrolytic electrodeposition on an aluminum film, and drying to obtain a microcrystalline fiber composite current-collecting gel film with an aluminum film surface;
(3) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding zinc chloride in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing, cooling by using an ice water bath, performing constant-current electrolytic electrodeposition on zinc, and drying to obtain a microcrystalline fiber negative electrode gel film with a zinc-based surface;
(4) Putting the ionic liquid modified microcrystalline cellulose prepared in the step (1) into a reaction bottle, adding hydroxylated graphene into the ionic liquid modified microcrystalline cellulose in batches under the condition of continuous stirring in a nitrogen atmosphere, uniformly mixing through ultrasonic treatment, pouring a mixed solution into a flat-bottom tray container, standing for 1h after treatment through a horizontal oscillator, and drying to obtain a microcrystalline fiber positive gel film with a graphene surface;
(5) And (3) attaching the obtained microcrystalline fiber positive gel film with the graphene surface and the microcrystalline fiber negative gel film with the zinc-based surface, wherein the graphene surface and the zinc-based surface face outwards, then attaching the microcrystalline fiber composite current collecting gel film with the aluminum film surface in a covered edge manner, and then pressing the attached gel film on the protective film through a dry film pressing machine to obtain the flexible supercapacitor.
4. The method for preparing the flexible supercapacitor according to claim 3, wherein the mass ratio of tributyl phosphate, N-methylimidazole and microcrystalline cellulose in the step (1) is 25-28.
5. The method for preparing the flexible supercapacitor according to claim 3, wherein the mass ratio of the ionic liquid modified microcrystalline cellulose to the aluminum chloride in the step (2) is 1.
6. The method for preparing a flexible supercapacitor according to claim 3, wherein the constant current electrolytic electrodeposition in the step (2) and the step (3) adopts a CHI760D electrochemical workstation, the electrolysis is carried out by using magnetic stirring and maintaining a constant stirring speed of 400r/min, the current density is 10mA/cm, the deposition is carried out for 4h at 80 ℃, and the drying conditions in the steps (2), (3) and (4) are drying for 24-36h in a vacuum oven at 140 ℃.
7. The preparation method of the flexible supercapacitor according to claim 3, wherein the mass ratio of the ionic liquid modified microcrystalline cellulose to the zinc chloride in the step (3) is 1.
8. The method for preparing the flexible supercapacitor according to claim 3, wherein the drying conditions in the step (2) and the step (3) are drying for 24-36h in a vacuum oven at 140 ℃.
9. The method for preparing the flexible supercapacitor according to claim 3, wherein in the step (4), the mass ratio of the ionic liquid modified microcrystalline cellulose to the hydroxylated graphene is 1.
10. The method for preparing a flexible supercapacitor according to claim 3, wherein the oscillation time in step (4) is 20-30min, and the running speed of the PCB laminator in step (5) is 2m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079529.3A CN113808854B (en) | 2021-09-15 | 2021-09-15 | Flexible super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079529.3A CN113808854B (en) | 2021-09-15 | 2021-09-15 | Flexible super capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113808854A CN113808854A (en) | 2021-12-17 |
| CN113808854B true CN113808854B (en) | 2022-11-11 |
Family
ID=78941005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111079529.3A Active CN113808854B (en) | 2021-09-15 | 2021-09-15 | Flexible super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113808854B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034939A1 (en) * | 2006-09-04 | 2008-03-27 | Natucell Ay | Functionalized cellulose - carbon nanotube nanocomposites and hybride materials |
| CN102382870A (en) * | 2011-08-10 | 2012-03-21 | 中国科学院西双版纳热带植物园 | Method for pretreating and hydrolyzing microcrystalline cellulose |
| CN105210165A (en) * | 2013-04-10 | 2015-12-30 | 泰勒斯公司 | Electrode-gel electrolyte assembly comprising a porous carbon material and obtained by radical polymerisation |
| JP2016222780A (en) * | 2015-05-28 | 2016-12-28 | 公立大学法人兵庫県立大学 | Proton conductivity polymer gel electrolyte |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN112820553A (en) * | 2021-02-11 | 2021-05-18 | 贵州大学 | Preparation method and application of cellulose proton type ionic liquid composite gel electrolyte |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130189589A1 (en) * | 2012-01-23 | 2013-07-25 | Masdar Institute Of Science And Technology | Fabrication of cellulose polymer composites and their application as solid electrolytes |
-
2021
- 2021-09-15 CN CN202111079529.3A patent/CN113808854B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034939A1 (en) * | 2006-09-04 | 2008-03-27 | Natucell Ay | Functionalized cellulose - carbon nanotube nanocomposites and hybride materials |
| CN102382870A (en) * | 2011-08-10 | 2012-03-21 | 中国科学院西双版纳热带植物园 | Method for pretreating and hydrolyzing microcrystalline cellulose |
| CN105210165A (en) * | 2013-04-10 | 2015-12-30 | 泰勒斯公司 | Electrode-gel electrolyte assembly comprising a porous carbon material and obtained by radical polymerisation |
| JP2016222780A (en) * | 2015-05-28 | 2016-12-28 | 公立大学法人兵庫県立大学 | Proton conductivity polymer gel electrolyte |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN112820553A (en) * | 2021-02-11 | 2021-05-18 | 贵州大学 | Preparation method and application of cellulose proton type ionic liquid composite gel electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| A monolithic functional film of nanotubes/cellulose/ionic liquid for high performance supercapacitors;LuciaBasiricò et al;《Journal of Power Sources》;20141220;第271卷;全文 * |
| Highly conducting, extremely durable, phosphorylated cellulose-based ionogels for renewable flexible supercapacitors;Harpalsinh H. Rana et al;《Energy Storage Materials》;20200331;第25卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113808854A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111508724B (en) | MOFs composite electrode material for supercapacitor, preparation method and working electrode | |
| Cheng et al. | Preparation of flexible supercapacitor with RGO/Ni-MOF film on Ni-coated polyester fabric | |
| CN104817085B (en) | A kind of preparation method and its usage of two-dimensional nano silicon chip | |
| CN108232161A (en) | A kind of full battery of sodium ion | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| CN103730645A (en) | Silicon-coated carbon fiber nano composite material and preparation method and application thereof | |
| CN107086322A (en) | A kind of copper selenium compound can discharge and recharge aluminium ion battery for positive pole | |
| Zeng et al. | In situ synthesis of binded, thick and porous carbon nanoparticle dye sensitized solar cell counter electrode with nickel gel as catalyst source | |
| CN109216045A (en) | CC@ZIF-67/8-PPY composite material and preparation method and application based on carbon cloth growth in situ | |
| CN108630449B (en) | Flexible asymmetric super capacitor with ultrahigh energy density and preparation method thereof | |
| Aghazadeh et al. | High performance electrode material for supercapacitors based on α-Co (OH) 2 nano-sheets prepared through pulse current cathodic electro-deposition (PC-CED) | |
| CN109546082A (en) | A kind of cathode pole piece and preparation method thereof and lithium ion battery | |
| CN111689523A (en) | Chromium metal doped-MnO2Preparation method of nanosheet | |
| Zhang et al. | LiNO3 and TMP enabled high voltage room-temperature solid-state lithium metal battery | |
| Wang et al. | Continuous preparation of high performance flexible asymmetric supercapacitor with a very fast, low-cost, simple and scalable electrochemical co-deposition method | |
| Xu et al. | Structural engineering for high energy and voltage output supercapacitors | |
| Wang et al. | Rational design and in-situ synthesis of ultra-thin β-Ni (OH) 2 nanoplates for high performance all-solid-state flexible supercapacitors | |
| Zhang et al. | A study of the electrochemical performance of strip supercapacitors under bending conditions | |
| CN107742746A (en) | A kind of manufacture method of composite graphite alkene lithium ion battery and composite graphite alkene electrode | |
| CN113808854B (en) | Flexible super capacitor | |
| Liu et al. | Porous current collector enables carbon superior electrochemical performance for K-ion capacitors | |
| Medagedara et al. | Triethylammonium thiocyanate ionic liquid electrolyte-based supercapacitor fabricated using coconut shell-derived electronically conducting activated charcoal electrode material | |
| CN105118683B (en) | A kind of preparation method of cobalt molybdate composite manganese dioxide electrode material | |
| CN109830379A (en) | A kind of supercapacitor and preparation method thereof | |
| CN109935813A (en) | A kind of preparation method and application of novel cathode material for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |