CN113793757B - Flexible planar capacitor and preparation method and application thereof - Google Patents
Flexible planar capacitor and preparation method and application thereof Download PDFInfo
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- CN113793757B CN113793757B CN202111129382.4A CN202111129382A CN113793757B CN 113793757 B CN113793757 B CN 113793757B CN 202111129382 A CN202111129382 A CN 202111129382A CN 113793757 B CN113793757 B CN 113793757B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 74
- 239000007772 electrode material Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 238000000407 epitaxy Methods 0.000 claims description 4
- 239000011245 gel electrolyte Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 76
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 238000000498 ball milling Methods 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 11
- 238000007639 printing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 5
- 238000001879 gelation Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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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
- H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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 belongs to the technical field of flexible super capacitors, and mainly relates to a flexible planar capacitor and a preparation method and application thereof. The flexible planar capacitor comprises more than or equal to 1 flexible planar capacitor element; the flexible planar capacitor element comprises a flexible substrate and an electrode arranged on the surface of the flexible substrate; the electrode comprises a concentric circle structure and an epitaxial structure; the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially laminated on the surface of the flexible substrate; the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material. The structure of the flexible planar capacitor greatly shortens the transmission path of ions, is favorable for improving electrochemical performance, and the specific surface area, conductivity and porosity of the porous graphene and Mxene used have great effects on improving the specific capacitance and energy density of the planar capacitor.
Description
Technical Field
The invention belongs to the technical field of planar capacitors, and particularly relates to a flexible planar capacitor, a preparation method and application thereof.
Background
The development of intelligent clothing is very rapid, and flexible display devices are also rapidly developing. However, the power supply suitable for the portable electric power source is still mainly a hard power supply, cannot be bent to adapt to the movement of a human body, has large volume and inconvenient carrying, often adopts a traditional lithium ion battery, has potential safety hazards to the human body and the like, and therefore, the research on the flexible solid-state energy source is particularly urgent.
Currently, flexible capacitors mainly include fiber supercapacitors and film-type flexible supercapacitors. The fibrous supercapacitor takes the graphene fiber as the main energy storage fiber, has the characteristics of light weight, flexibility and the like, can be directly used for weaving clothes, and has great pushing effect on developing wearable clothes. However, the mechanical properties of the super capacitor are weak, the electrochemical performance and the energy storage performance are not high, the super capacitor cannot be directly applied to the weaving with clothing at present, and the film super capacitor is mainly formed by coating active materials on a flexible substrate and forming a capacitor together with electrolyte. The structure is mainly sandwich type. The electrolyte is composed of electrode materials, a diaphragm and electrolyte solution, electrolyte ions are transmitted through the diaphragm when charging and discharging are carried out, the ion diffusion path is long, and the electrolyte is large in size and is unfavorable for being combined with miniature intelligent equipment.
Disclosure of Invention
The invention aims to provide a flexible planar capacitor, a preparation method and application thereof, wherein the flexible planar capacitor greatly shortens the transmission path of ions and is beneficial to reducing the size of the capacitor.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a flexible planar capacitor, which comprises more than or equal to 1 flexible planar capacitor element;
the flexible planar capacitor element comprises a flexible substrate and an electrode arranged on the surface of the flexible substrate;
the electrode comprises a concentric circle structure and an epitaxial structure; the concentric circle structure comprises a center circle and an opening circular ring positioned outside the center circle;
the epitaxial structure comprises a central circular epitaxial structure and an opening circular epitaxial structure;
the center circle epitaxial structure extends through the opening of the opening circular ring;
the open circular ring epitaxial structure performs reverse epitaxy along the diameter direction of the central circular epitaxial structure;
in the diameter direction of the concentric circle structure, the distance between the center circle and the opening circular ring is 2-10 mm;
the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially stacked on the surface of the flexible substrate;
the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material.
Preferably, in the diameter direction of the concentric circle structure, the distance between the center circle and the opening circular ring is 2.9-8.7 mm.
Preferably, when the flexible planar capacitor element is equal to or more than 2, the flexible planar capacitor elements are connected in parallel or in series.
Preferably, the irradiation dose of the irradiation treatment is 5-60 kGy.
Preferably, the MXene material is Ti 3 C 2 ；
The mass ratio of the graphene to the MXene material is (10-20): 1.
preferably, the material of the electrode material layer further comprises PVDF and acetylene black;
the mass ratio of the graphene subjected to irradiation treatment to PVDF to acetylene black is 8:2:1;
the electrolyte in the electrolyte layer is PVA-sulfuric acid gel electrolyte.
Preferably, the material of the first current collector layer is silver;
the first current collector layer fills the whole concentric circle structure and the epitaxial structure; the second current collector layer is made of copper sheets;
the copper sheets are respectively adhered to the surface of the epitaxial structure.
The invention provides a preparation method of the flexible planar capacitor, which comprises the following steps:
according to the structure of the flexible planar capacitor element, which is disclosed by the technical scheme, after a first current collector layer and an electrode material layer are sequentially printed on the surface of a flexible substrate, an electrolyte layer is coated, and finally, a second current collector is respectively bonded on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure, so that the flexible planar capacitor is obtained;
the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material.
The invention also provides the application of the flexible planar capacitor in the technical scheme or the flexible planar capacitor prepared by the preparation method in the technical scheme in the intelligent clothing field.
The invention provides a flexible planar capacitor, which comprises more than or equal to 1 flexible planar capacitor element; the flexible planar capacitor element comprises a flexible substrate and an electrode arranged on the surface of the flexible substrate; the electrode comprises a concentric circle structure and an epitaxial structure; the concentric circle structure comprises a center circle and an opening circular ring positioned outside the center circle; the epitaxial structure comprises a central circular epitaxial structure and an opening circular epitaxial structure; the center circle epitaxial structure extends through the opening of the opening circular ring; the open circular ring epitaxial structure performs reverse epitaxy along the diameter direction of the central circular epitaxial structure; in the diameter direction of the concentric circle structure, the distance between the center circle and the opening circular ring is 2-10 mm; the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially stacked on the surface of the flexible substrate; the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material. The concentric circle structure of the invention can greatly shorten the transmission path of ions, greatly reduce the size of the capacitor, is beneficial to tending to microminiaturization and can supply power for more microchips. Meanwhile, the defect structure is introduced into the graphene by adopting the graphene subjected to irradiation treatment, so that the capacitance of the graphene at the Fermi level can be improved, the conductivity of the graphene is improved, and the overall electrochemical performance of the flexible planar capacitor is improved; meanwhile, the structure of the Mxene is similar to that of graphene, belongs to a lamellar structure, has high electronic conductivity, and can obviously improve the conductivity of the planar flexible capacitor.
Drawings
FIG. 1 is a schematic view of the structure of an electrode in a flexible planar capacitor according to the present invention;
FIG. 2 is a Raman spectrum diagram of graphene not subjected to irradiation treatment and graphene subjected to irradiation treatment as described in example 1;
FIG. 3 is an SEM image of untreated graphene and irradiated graphene (FZ 2) described in example 1;
fig. 4 is a conductivity bar graph of the flexible planar capacitor prepared in examples 2 and 8 and comparative example 1;
FIG. 5 is a CV plot of the flexible planar capacitor prepared in example 3 at different scan rates;
FIG. 6 is a CV plot of flexible planar capacitors prepared in examples 3-7 at a scan rate of 100 mV/s;
FIG. 7 is a CV plot of flexible planar capacitors prepared in examples 2, 8-9 at a scan rate of 100 mV/s;
FIG. 8 is a schematic diagram of a parallel structure of flexible planar capacitors in the flexible planar capacitor according to the present invention;
fig. 9 is a schematic diagram of a series structure of flexible planar capacitors in the flexible planar capacitor according to the present invention.
Detailed Description
The invention provides a flexible planar capacitor, which comprises more than or equal to 1 flexible planar capacitor element;
the flexible planar capacitor element comprises a flexible substrate and an electrode arranged on the surface of the flexible substrate;
the electrode comprises a concentric circle structure and an epitaxial structure; the concentric circle structure comprises a center circle and an opening circular ring positioned outside the center circle;
the epitaxial structure comprises a central circular epitaxial structure and an opening circular epitaxial structure;
the center circle epitaxial structure extends through the opening of the opening circular ring;
the open circular ring epitaxial structure performs reverse epitaxy along the diameter direction of the central circular epitaxial structure;
in the diameter direction of the concentric circle structure, the distance between the center circle and the opening circular ring is 2-10 mm;
the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially stacked on the surface of the flexible substrate;
the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material.
In the present invention, the flexible planar capacitor element includes a flexible substrate and an electrode disposed on a surface of the flexible substrate. The kind and thickness of the flexible substrate are not particularly limited in the present invention, and those known to those skilled in the art may be used.
In the present invention, the electrode includes a concentric circle structure and an epitaxial structure; the concentric circle structure comprises a center circle and an opening circular ring positioned outside the center circle. The diameter of the center circle is 10.9mm; the width of the opening circular ring is 3.1mm; the distance between the center circle and the open circular ring in the diameter direction of the concentric circle structure is preferably 2 to 10mm, more preferably 2.9 to 8.7mm, further preferably 4.4 to 7.3mm, and most preferably 5.8mm. In the present invention, the opening width of the opening ring is preferably 2 to 10mm, more preferably 2.9 to 8.7mm.
In the invention, when the center circle is used as the positive electrode of the electrode, the open circular ring is used as the negative electrode of the electrode; when the center circle is used as the negative electrode of the electrode, the opening circular ring is used as the positive electrode of the electrode.
In the invention, the epitaxial structure comprises a central circular epitaxial structure and an open circular epitaxial structure; the center circle epitaxial structure extends through the opening of the opening circular ring; in the invention, the width of the central circle epitaxial structure is 4.5mm. And the open circular ring epitaxial structure is reversely epitaxial along the diameter direction of the central circular epitaxial structure. In the invention, the width of the open circular ring epitaxial structure is 4.5mm.
In the invention, the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially stacked on the surface of the flexible substrate.
In the present invention, the thickness of the first current collector layer is preferably 0.01 to 0.1mm, more preferably 0.06 to 0.08mm. In the present invention, the material of the first current collector layer is preferably silver. The first current collector layer preferably fills the entire concentric circle structure and the epitaxial structure in the present invention.
In the invention, the material of the electrode material layer comprises graphene subjected to irradiation treatment. In the present invention, the irradiation dose of the irradiation treatment is preferably 5 to 60kGy, more preferably 30kGy. In the present invention, the light source used for the irradiation treatment is preferably Co60 gamma rays.
In the invention, the thickness of the slice layer of the graphene subjected to the irradiation treatment is less than or equal to 100nm.
In the invention, the irradiation treatment is controlled under the irradiation intensity, so that the two-dimensional graphene can be assembled into the graphene with a three-dimensional porous structure, and the graphene has a higher specific surface area; meanwhile, through irradiation treatment, the surface of the graphene can be subjected to defect treatment, a defect structure is introduced, and the electrochemical performance of the graphene is improved.
In the invention, the material of the electrode material layer comprises graphene and MXene material; the MXene material is preferably Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the graphene to the MXene material is preferably (10-20): 1.
in the present invention, the material of the electrode material layer preferably further includes PVDF and acetylene black; the mass ratio of the graphene subjected to irradiation treatment to PVDF and acetylene black is preferably 8:2:1.
In the present invention, the thickness of the electrode material layer is preferably 0.1 to 0.5mm, more preferably 0.1 to 0.3mm, and most preferably 0.2mm.
In the present invention, the electrolyte in the electrolyte layer is preferably a PVA-sulfuric acid gel electrolyte; the thickness of the electrolyte layer is preferably 0.1 to 0.5mm, more preferably 0.2 to 0.4mm.
In the present invention, the material of the second current collector layer is preferably a copper sheet; the copper sheets are preferably adhered to the surface of the epitaxial structure respectively. In the present invention, the thickness of the second fluid layer is preferably 0.04mm.
In the invention, the flexible planar capacitor comprises more than or equal to 1 flexible planar capacitor element, and when the flexible planar capacitor element is more than or equal to 2, the flexible planar capacitor elements are preferably connected in parallel (the structure is shown in fig. 8) or in series (the structure is shown in fig. 9).
The invention provides a preparation method of the flexible planar capacitor, which comprises the following steps:
according to the structure of the flexible planar capacitor element, which is disclosed by the technical scheme, after a first current collector layer and an electrode material layer are sequentially printed on the surface of a flexible substrate, an electrolyte layer is coated, and finally, a second current collector is respectively bonded on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure, so that the flexible planar capacitor is obtained;
the electrode material layer comprises graphene subjected to irradiation treatment.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, the first current collector layer is preferably prepared by printing conductive silver paste on the surface of the flexible substrate. The composition of the conductive silver paste is not particularly limited, and may be any composition known to those skilled in the art. In the present invention, the printing is preferably screen printing; the screen printing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the preparation process of the electrode material layer preferably includes the steps of:
adding N-methyl pyrrolidone into the material of the electrode material layer, and performing ball milling to obtain electrode slurry;
and printing the electrode slurry on the surface of the first current collector layer to obtain an electrode material layer.
According to the invention, after graphene, PVDF and acetylene black subjected to irradiation treatment are mixed, N-methyl pyrrolidone is added, and ball milling is performed to obtain electrode slurry.
The amount of the N-methylpyrrolidone used in the present invention is not particularly limited, and may be any known amount known to those skilled in the art.
In the present invention, the ball milling is preferably performed by alternately ball milling clockwise and counterclockwise, and the time of the ball milling is preferably 6 to 10 hours, more preferably 8 hours. The rotational speed of the ball milling is not limited in any particular way, and graphene, PVDF and acetylene black subjected to irradiation treatment are uniformly mixed by adopting the rotational speed which is well known to a person skilled in the art.
After electrode slurry is obtained, the electrode slurry is printed on the surface of the first current collector layer, and an electrode material layer is obtained. The printing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the preparation process of the electrolyte layer preferably includes the steps of:
adding concentrated sulfuric acid into PVA solution, and then gelling to obtain electrolyte gel;
and coating the electrolyte gel on the surface of the electrode material layer to obtain an electrolyte layer.
In the invention, concentrated sulfuric acid is added into PVA solution, and gelation is carried out to obtain electrolyte gel.
In the present invention, the PVA solution is preferably an aqueous solution of PVA; the concentration of PVA in the PVA solution is preferably 0.1g/mL; the mass concentration of the concentrated sulfuric acid is preferably 98%.
In the invention, the mass ratio of PVA to concentrated sulfuric acid in the PVA solution is preferably 1:1.
In the present invention, the process of adding concentrated sulfuric acid to the PVA solution, to which concentrated sulfuric acid is added dropwise, is preferably performed under stirring.
In the present invention, the gelation is preferably performed under constant temperature and stirring, and the temperature of the gelation is preferably 85 ℃ and the time is preferably 2 hours. The stirring speed is not particularly limited, and a speed well known to those skilled in the art may be used.
After the gelation is completed, the present invention also preferably includes a process of removing bubbles, which is preferably performed under vacuum.
After the electrolyte gel is obtained, the electrolyte gel is coated on the surface of the electrode material layer to obtain the electrolyte layer.
The process of the coating is not particularly limited, and may be performed by a process well known to those skilled in the art.
The invention also provides the application of the flexible planar capacitor in the technical scheme or the flexible planar capacitor prepared by the preparation method in the technical scheme in the intelligent clothing field. The method of the present invention is not particularly limited, and may be carried out by a process well known to those skilled in the art.
The flexible planar capacitor, the method of manufacturing the same, and the use thereof are described in detail with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Carrying out irradiation treatment on the graphene by adopting Co60 gamma rays, wherein the intensity of the irradiation treatment is 5kGy, 30kGy and 60kGy respectively, so as to obtain the graphene (sequentially marked as FZ1, FZ2 and FZ 3) after the irradiation treatment;
carrying out Raman spectrum test on the graphene which is not subjected to irradiation treatment and the graphene which is subjected to irradiation treatment, wherein the test result is shown in figure 2, and as can be seen from figure 2, the stone which is not subjected to irradiation treatmentThe graphene has no defect peak, and the 2G peak is lower, which indicates that the graphene is multilayer graphene; after irradiation treatment, the graphene is 2726.89cm -1 A 2D peak appears and 1385.8cm -1 A defect peak D-peak appears at the position, and the defect peak intensity is continuously enhanced. The occurrence of the D peak shows that Co60 gamma rays introduce defects into graphene, which is beneficial to the application of graphene in electrochemistry. Meanwhile, co60 gamma rays can further strip graphene, so that the conductivity of the graphene is improved, and the electrochemical performance is improved. Wherein, the ID/IG of FZ1, FZ2 and FZ3 are respectively 0.138, 0.092 and 0.168.
SEM test is carried out on the graphene which is not subjected to irradiation treatment and the graphene (FZ 2) which is subjected to irradiation treatment, and a test result is shown as a figure 3, wherein a is an integral SEM image of the graphene which is not subjected to irradiation treatment, b is an integral SEM image of single-layer graphene which is not subjected to irradiation treatment, c is an integral SEM image of FZ2, d is the thickness of the single-layer graphene in FZ2, as shown in figure 3, after irradiation treatment, the layered structure becomes loose, the hole structure is increased, the thickness of the non-irradiated graphene sheet is larger, the thickness of the non-irradiated graphene sheet belongs to multiple layers, the thickness of the non-irradiated graphene sheet is in a micron level, and after irradiation, the thickness of the graphene sheet after irradiation treatment is less than 10nm, so that the specific surface area of the graphene per unit volume is increased, more active sites are provided for electrochemical reaction, the graphene sheet is in contact with electrolyte, and the ion transmission rate is increased;
example 2
According to the structure shown in fig. 1, the diameter of the center circle is 10.9mm, the width of the open circular ring is 3.1mm, the distance between the center circle and the open circular ring is 2.9mm, the opening width of the open circular ring is 6.9mm, the width of the center circular epitaxial structure is 4.5mm, and the width of the open circular ring epitaxial structure is 4.5mm;
printing conductive silver paste on the surface of the TPU flexible substrate through screen printing to obtain a silver current collector layer (the thickness is 0.08 mm);
mixing the graphene (FZ 1, FZ2 and FZ 3) subjected to irradiation treatment prepared in the embodiment 1 with PVDF and acetylene black according to the mass ratio of 8:2:1, adding N-methylpyrrolidone, and performing ball milling for 8 hours in a clockwise and anticlockwise alternate ball milling mode to obtain electrode slurry;
printing the electrode slurry on the surface of the silver current collector layer to obtain an electrode material layer (with the thickness of 0.17 mm);
mixing 1g of PVA with 10mL of distilled water to obtain a PVA solution, dropwise adding 1g of concentrated sulfuric acid with the mass concentration of 98% under the condition of stirring, gelatinizing for 2 hours under the condition of constant temperature (85 ℃) and stirring, removing bubbles under the condition of vacuum, and standing for two days to obtain electrolyte gel;
coating the electrolyte gel on the surface of the electrode material layer to obtain an electrolyte layer (thickness of 0.15 mm);
and respectively bonding copper sheets on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure to obtain the flexible planar capacitor.
Comparative example 1
Referring to example 2, only the difference is that the irradiation treatment of graphene is not performed.
Example 3
According to the structure shown in fig. 1, the diameter of the center circle is 10.9mm, the width of the open circular ring is 3.1mm, the distance between the center circle and the open circular ring is 2.9mm, the opening width of the open circular ring is 6.9mm, the width of the center circular epitaxial structure is 4.5mm, and the width of the open circular ring epitaxial structure is 4.5mm;
printing conductive silver paste on the surface of the TPU flexible substrate through screen printing to obtain a silver current collector layer (the thickness is 0.06 mm);
mixing the graphene (FZ 2) subjected to irradiation treatment prepared in the embodiment 1 with PVDF and acetylene black according to the mass ratio of 8:2:1, adding N-methylpyrrolidone, and performing ball milling for 8 hours in a clockwise and anticlockwise alternative ball milling mode to obtain electrode slurry;
printing the electrode slurry on the surface of the silver current collector layer to obtain an electrode material layer (the thickness is 0.18 mm);
mixing 1g of PVA with 10mL of distilled water to obtain a PVA solution, dropwise adding 1g of concentrated sulfuric acid with the mass concentration of 98% under the condition of stirring, gelatinizing for 2 hours under the condition of constant temperature (85 ℃) and stirring, removing bubbles under the condition of vacuum, and standing for two days to obtain electrolyte gel;
coating the electrolyte gel on the surface of the electrode material layer to obtain an electrolyte layer (with the thickness of 0.23 mm);
and respectively bonding copper sheets on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure to obtain the flexible planar capacitor.
Example 4
Reference to example 3 differs only in that: the diameter of the center circle is 10.9mm, the width of the opening ring is 3.1mm, the distance between the center circle and the opening ring is 4.4mm, the opening width of the opening ring is 6.9mm, the width of the center circle epitaxial structure is 4.5mm, and the width of the opening ring epitaxial structure is 4.5mm.
Example 5
Reference to example 3 differs only in that: the diameter of the center circle is 10.9mm, the width of the opening ring is 3.1mm, the distance between the center circle and the opening ring is 5.8mm, the opening width of the opening ring is 6.9mm, the width of the center circle epitaxial structure is 4.5mm, and the width of the opening ring epitaxial structure is 4.5mm.
Example 6
Reference to example 3 differs only in that: the diameter of the center circle is 10.9mm, the width of the opening ring is 3.1mm, the distance between the center circle and the opening ring is 7.3mm, the opening width of the opening ring is 6.9mm, the width of the center circle epitaxial structure is 4.5mm, and the width of the opening ring epitaxial structure is 4.5mm.
Example 7
Reference to example 3 differs only in that: the diameter of the center circle is 10.9mm, the width of the opening ring is 3.1mm, the distance between the center circle and the opening ring is 8.7mm, the opening width of the opening ring is 6.9mm, the width of the center circle epitaxial structure is 4.5mm, and the width of the opening ring epitaxial structure is 4.5mm.
Example 8
According to the structure shown in fig. 1, the diameter of the center circle is 10.9mm, the width of the open circular ring is 3.1mm, the distance between the center circle and the open circular ring is 2.9mm, the opening width of the open circular ring is 6.9mm, the width of the center circular epitaxial structure is 4.5mm, and the width of the open circular ring epitaxial structure is 4.5mm;
printing conductive silver paste on the surface of the TPU flexible substrate through screen printing to obtain a silver current collector layer (the thickness is 0.06 mm);
graphene and MXene Ti are mixed according to the mass ratio of 20:1 3 C 2 Mixing to obtain an electrode material;
mixing the electrode material, PVDF and acetylene black according to the mass ratio of 8:2:1, adding N-methyl pyrrolidone, and performing ball milling for 8 hours in a clockwise and anticlockwise alternative ball milling mode to obtain electrode slurry;
printing the electrode slurry on the surface of the silver current collector layer to obtain an electrode material layer (with the thickness of 0.17 mm);
mixing 1g of PVA with 10mL of distilled water to obtain a PVA solution, dropwise adding 1g of concentrated sulfuric acid with the mass concentration of 98% under the condition of stirring, gelatinizing for 2 hours under the condition of constant temperature (85 ℃) and stirring, removing bubbles under the condition of vacuum, and standing for two days to obtain electrolyte gel;
coating the electrolyte gel on the surface of the electrode material layer to obtain an electrolyte layer (thickness of 0.21 mm);
copper sheets are respectively bonded on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure, so that a flexible planar capacitor is obtained;
the flexible planar capacitors prepared in examples 2 and 8 and comparative example 1 were tested for electrical conductivity using a four-probe tester, and the test results are shown in FIG. 4. As can be seen from FIG. 4, the electrical conductivities of the flexible planar capacitors all reached 10 4 The level, the conductivity of the graphene electrode after irradiation treatment is higher than that of the graphene electrode without irradiation treatment, wherein the irradiation intensity of 30kGy is improved to the maximum, and the irradiation treatment proves that the irradiation treatment increases the aperture of the nano lamellar of the graphene and accelerates the transmission of ions and electrons, but the increase of the irradiation intensity also causes larger damage to the structure of the graphene and further leads to the reduction of the conductivity. As same asIn this case, the conductivity of the flexible planar capacitor of example 8 is higher than that of the flexible planar capacitor of example 2, because Mxene itself has a structure similar to graphene, belongs to a lamellar structure, has high electron conductivity, and can significantly improve the conductivity of the planar flexible capacitor.
Example 9
Reference example 8 differs only in graphene and MXene Ti 3 C 2 The mass ratio of (2) is 10:1.
Test case
The flexible planar capacitor prepared in example 3 was subjected to cyclic voltammetry at scan rates of 10mV/s, 50mV/s and 100mV/s. As shown in fig. 5, the CV curve is smooth, has no oxidation-reduction peak, shows a distinct rectangular-like curve, is relatively symmetrical, is typical of an electric double layer capacitor, and increases in current density of the curve as the scanning speed increases, increases in integral area, and shows good rate performance, while the shape of the cyclic voltammogram remains almost unchanged. By the formulaWherein ≡i (V) dV represents the integrated area size of CV curve, s represents the mass of active material or the area of electrode, V represents the scanning rate at CV test, deltaV represents the potential window at test, and the specific capacitance of the flexible planar capacitor described in example 3 was 0.2125mF/cm at scanning rates of 10mV/s, 50mV/s and 100mV/s, respectively, was calculated -2 、0.1422mF/cm -2 And 0.1253mF/cm -2 ；
The flexible planar capacitors prepared in examples 3 to 7 were subjected to CV scanning at a scanning rate of 100mV/s, and the test results are shown in FIG. 6, in which examples 1# correspond to example 3,2# correspond to example 4,3# correspond to example 5,4# correspond to example 6,5# correspond to example 7. As can be seen from FIG. 6, the electrode pitches of 1#, 2#, 3#, 4# and 5# are 2.9mm, 4.4mm, 5.8mm, 7.3mm and 8.7mm, respectively, and their specific capacitances are 0.1253mF/cm, respectively -2 、0.059mF/cm -2 、0.1522mF/cm -2 、0.2289mF/cm -2 And 0.05565mF/cm -2 It is explained that the distance between the positive electrode and the negative electrode has an important influence on the overall performance of the capacitor, and for a planar flexible capacitor, the smaller the distance between the positive electrode and the negative electrode is, the smaller the ion transmission distance is, and the better the electrochemical performance of the capacitor is.
CV scanning is carried out on the flexible planar capacitor prepared in the embodiments 2, 8-9 at a scanning rate of 100mV/s, and a test result is shown in figure 7, wherein 1# corresponds to the flexible planar capacitor prepared by FZ1, 2# corresponds to the flexible planar capacitor prepared by FZ2, and 3# corresponds to the flexible planar capacitor prepared by FZ 3; as can be seen from FIG. 7, doping of graphene with MXene greatly increases the specific capacitance of the flexible planar capacitor, wherein the specific capacitance of example 8 is 0.9418mF/cm -2 The specific capacitance of example 9 was 1.446mF/cm -2 。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A flexible planar capacitor is characterized in that the flexible planar capacitor comprises more than or equal to 1 flexible planar capacitor element;
the flexible planar capacitor element comprises a flexible substrate and an electrode arranged on the surface of the flexible substrate;
the electrode comprises a concentric circle structure and an epitaxial structure; the concentric circle structure comprises a center circle and an opening circular ring positioned outside the center circle;
the epitaxial structure comprises a central circular epitaxial structure and an opening circular epitaxial structure;
the center circle epitaxial structure extends through the opening of the opening circular ring;
the open circular ring epitaxial structure performs reverse epitaxy along the diameter direction of the central circular epitaxial structure;
in the diameter direction of the concentric circle structure, the distance between the center circle and the opening circular ring is 2-10 mm;
the electrode comprises a first current collector layer, an electrode material layer, an electrolyte layer and a second current collector layer which are sequentially stacked on the surface of the flexible substrate;
the material of the first current collector layer includes silver; the first current collector layer fills the whole concentric circle structure and the epitaxial structure; the second current collector layer is made of copper sheets; the copper sheets are respectively adhered to the surface of the epitaxial structure;
the electrode material layer comprises graphene subjected to irradiation treatment;
the irradiation dose of the irradiation treatment is 5-60 kGy.
2. The flexible planar capacitor of claim 1 wherein the spacing between said center circle and open circle is 2.9-8.7 mm in the diameter direction of said concentric circle structure.
3. The flexible planar capacitor of claim 1 wherein said flexible planar capacitor elements are connected in parallel or in series when said flexible planar capacitor elements are ≡2.
4. The flexible planar capacitor of claim 1 wherein the material of the electrode material layer further comprises PVDF and acetylene black;
the mass ratio of the graphene subjected to irradiation treatment to PVDF and acetylene black is 8:2:1.
5. The flexible planar capacitor of claim 1 wherein the electrolyte in the electrolyte layer is a PVA-sulfuric acid gel electrolyte.
6. The method for manufacturing a flexible planar capacitor as claimed in any one of claims 1 to 5, comprising the steps of:
the flexible planar capacitor element structure according to any one of claims 1 to 5, wherein after a first current collector layer and an electrode material layer are printed on the surface of a flexible substrate in sequence, an electrolyte layer is coated, and finally a second current collector is bonded on the surfaces of the central circular epitaxial structure and the open circular epitaxial structure respectively, so as to obtain the flexible planar capacitor;
the material of the electrode material layer comprises graphene subjected to irradiation treatment, or the material of the electrode material layer comprises graphene and an MXene material.
7. Use of the flexible planar capacitor of any one of claims 1 to 5 or the flexible planar capacitor prepared by the preparation method of claim 6 in the field of smart clothing.
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| CN109637819A (en) * | 2018-12-07 | 2019-04-16 | 中国科学院大连化学物理研究所 | A kind of integrated plane supercapacitor and preparation method thereof |
| CN112687474A (en) * | 2019-10-17 | 2021-04-20 | 北京石墨烯研究院 | Miniature super capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109637819A (en) * | 2018-12-07 | 2019-04-16 | 中国科学院大连化学物理研究所 | A kind of integrated plane supercapacitor and preparation method thereof |
| CN112687474A (en) * | 2019-10-17 | 2021-04-20 | 北京石墨烯研究院 | Miniature super capacitor |
Non-Patent Citations (2)
| Title |
|---|
| 石墨烯纤维的改性及在超级电容器中的应用;吴燕;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20210215(第2021/02期);第22页 * |
| 网版印刷制备织物型柔性储能电容器;张欣欣等;《丝网印刷》;20201231(第2020/12期);第14-16页 * |
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