CN113808854B - Flexible super capacitor - Google Patents
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- 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
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- 239000003990 capacitor Substances 0.000 title description 15
- 108010025899 gelatin film Proteins 0.000 claims abstract description 64
- 239000002608 ionic liquid Substances 0.000 claims abstract description 63
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 62
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 62
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 62
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 62
- 238000001035 drying Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 238000004070 electrodeposition Methods 0.000 claims description 19
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 16
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 3
- IGPWLYINMURFNR-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;diethyl phosphate Chemical compound CCOP([O-])(=O)OCC.CCCC[N+]=1C=CN(C)C=1 IGPWLYINMURFNR-UHFFFAOYSA-M 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 4
- -1 electrodes Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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.
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