CN110858523B - Manufacturing method of super capacitor - Google Patents
Manufacturing method of super capacitor Download PDFInfo
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- CN110858523B CN110858523B CN201810963513.0A CN201810963513A CN110858523B CN 110858523 B CN110858523 B CN 110858523B CN 201810963513 A CN201810963513 A CN 201810963513A CN 110858523 B CN110858523 B CN 110858523B
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- 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
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- 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
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- 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 discloses a manufacturing method of a super capacitor, which comprises the following steps: s1, providing a high polymer, a nano material, a three-dimensional porous structure material and a curing agent; s2, preparing a first composite material by using the nano material and the three-dimensional porous structure material; s3, mixing the high polymer and the curing agent according to a preset mass ratio, and respectively injecting the mixture into the first composite material and the three-dimensional porous structure material to obtain a second composite material and a third composite material; s4, removing the three-dimensional porous structure materials in the second composite material and the third composite material to obtain a three-dimensional porous electrode and a porous high polymer diaphragm; s5, packaging the three-dimensional porous electrode and the porous high polymer diaphragm; wherein the nano-materials in the three-dimensional porous electrode simultaneously serve as a current collector and an active substance of the supercapacitor.
Description
Technical Field
The invention relates to the field of super capacitors, in particular to a manufacturing method of a super capacitor.
Background
The super capacitor has the characteristics of high power density, quick charge and discharge and long cycle life. In particular to a super capacitor which can be stretched and twisted and is very suitable for supplying energy to a wearable device.
In the prior art, the tensile and torsional super capacitor is mainly prepared by three methods. The first method is to mix active materials, conductive additives and gel electrolyte to prepare a stretchable film or fiber, and then prepare the super capacitor. However, the super capacitor prepared by the method has poor mechanical stability, and the gel electrolyte in the super capacitor can generate a short circuit condition in the twisting and stretching process. The second is to coat the active material onto a stretchable current collector to prepare a stretchable electrode, thereby preparing a supercapacitor. However, the supercapacitor prepared by the method has poor mechanical stability, and the active substances are easy to fall off from the current collector in the twisting and stretching process. The third method is to mix active materials and stretchable polymers such as silica gel to prepare a stretchable electrode, and then the super capacitor is prepared. However, the active material in the super capacitor prepared by the method is mostly wrapped in high polymer, the capacity is very low, and the electrode conductivity is poor, such as stretchable and Twistable 1000 times disclosed in twist and convertible woven structured fibers and supercapacitors (Nano Lett.2016, 16, 7677-The capacity of the carbon nano tube/silica gel fiber capacitor is only 0.1mF cm-2。
Moreover, the working voltage of the conventional stretchable and twistable supercapacitor is generally less than 1V, the energy density is low, and the conventional stretchable and twistable supercapacitor cannot be used under the conditions of twisting and stretching for a long time.
Disclosure of Invention
In order to solve at least one aspect of the above problems, an embodiment of the present invention provides a method of manufacturing a supercapacitor, including the steps of:
s1, providing a high polymer, a nano material, a three-dimensional porous structure material and a curing agent;
s2, preparing a first composite material by using the nano material and the three-dimensional porous structure material;
s3, mixing the high polymer and the curing agent according to a preset mass ratio, and respectively injecting the mixture into the first composite material and the three-dimensional porous structure material to obtain a second composite material and a third composite material;
s4, removing the three-dimensional porous structure materials in the second composite material and the third composite material to obtain a three-dimensional porous electrode and a porous high polymer diaphragm;
s5, packaging the three-dimensional porous electrode and the porous high polymer diaphragm;
wherein the nano-materials in the three-dimensional porous electrode simultaneously serve as a current collector and an active substance of the supercapacitor.
Further, the step S2 further includes:
preparing ethanol solution or water solution of the nano material;
and dropwise adding the ethanol solution or the water solution containing the nano material to the three-dimensional porous structure material to prepare the first composite material.
Further, in step S3, the first composite material and the three-dimensional porous structure material injected with the high polymer and the curing agent are respectively subjected to vacuum treatment, curing treatment and surface high polymer removal by using an emission spectrometer, chemical or mechanical.
Further, in step S3, the high polymer and the curing agent mixed in a predetermined mass ratio are subjected to a vacuum bubble removal process.
Further, the method comprises the steps of:
a polymer substrate is manufactured.
Further, the three-dimensional porous electrode and the porous polymer separator are encapsulated with the polymer substrate.
Further, the method further comprises:
and injecting an electrolyte into the three-dimensional porous electrode and the porous high polymer diaphragm after packaging.
Further, after the electrolyte is injected, the injection port is sealed with the high polymer and a sealing film.
Further, the preset mass ratio is 8: 1-16: 1.
Further, the high polymer is polydimethylsiloxane or silica gel.
Further, the nano material is a carbon nano tube.
Further, the three-dimensional porous structure material is a three-dimensional metal, a metal compound, a porous sugar or a porous salt.
Further, the method comprises the steps of: and pretreating the three-dimensional metal.
Compared with the prior art, the invention has one of the following advantages:
(1) the nanometer material in the three-dimensional porous electrode is simultaneously used as the current collector and the active substance of the super capacitor, the super capacitor has a super-stable structure, and the three-dimensional porous electrode can effectively protect the active substance in the twisting and stretching process.
(2) The porous high polymer diaphragm ensures that the super capacitor does not have the short circuit problem in the stretching and twisting process.
(3) Gel electrolyte is mostly used in the conventional stretchable super capacitor, and the voltage is lower, the super capacitor provided by the invention uses organic or ionic liquid electrolyte to increase the working voltage, and the energy density is improved, for example, the working voltage of the twistable stretchable super capacitor provided by the invention is 3V.
(4) The stretchable and twistable supercapacitor prepared by the method has super-stable mechanical properties, and can still maintain the original electrochemical properties after being twisted and stretched for hundreds of thousands of cycles.
Drawings
Other objects and advantages of the present invention will become apparent from the following description of the invention which refers to the accompanying drawings, and will assist in a comprehensive understanding of the invention.
Fig. 1 is a flowchart of a method for manufacturing a super capacitor according to an embodiment of the present invention;
FIG. 2 is a process for fabricating a 3D CNT/PDMS electrode according to embodiment 1 of the present invention;
FIGS. 3-12 are schematic diagrams of the mechanical and electrochemical performance of supercapacitors provided in examples 1-5 of the present invention; and
fig. 13-17 are schematic diagrams of the performance of the supercapacitor provided in embodiment 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention. It should be apparent that the described embodiment is one embodiment of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Some embodiments of the invention are described in detail below with reference to the accompanying drawings. The embodiments and features of the embodiments described below can be combined with each other without conflict.
As shown in fig. 1, a method for manufacturing a super capacitor according to an embodiment of the present invention may include:
s1, providing high polymer, nanometer material, three-dimensional porous structure material and curing agent.
The high polymer can be polydimethylsiloxane or silica gel, and can also be other flexible and stretchable high polymers. The nanomaterial may be a carbon nanotube. The three-dimensional porous structure material can be three-dimensional metal, metal compound, porous sugar or porous salt, for example, the three-dimensional metal can be three-dimensional foam copper and three-dimensional foam nickel, and the metal compound can be 3D CuO and 3D NiO. It should be noted that, when the three-dimensional porous structure material is three-dimensional foam copper or three-dimensional foam nickel, it is necessary to perform a pretreatment such as cutting, rolling, calcining, etc. The metal compound can be obtained by pretreating three-dimensional metal, such as three-dimensional copper foam or nickel foam by high-temperature calcination to obtain three-dimensional copper oxide and three-dimensional nickel oxide, or can be directly prepared from the existing metal oxide. Specific pretreatment procedures are described in detail below with reference to specific examples.
And S2, preparing a first composite material by using the nanometer material and the three-dimensional porous structure material.
Specifically, the first composite material may be prepared by preparing an ethanol solution or an aqueous solution containing the nanomaterial, and then adding the ethanol solution or the aqueous solution containing the nanomaterial dropwise to the three-dimensional porous structure material several times.
Wherein, the content of the nanometer material in the ethanol solution or the water solution can be 1mg/ml-6mg/ml, the length can be 5-100 μm, and the diameter can be 2-500 nm. The ethanol solution or the water solution containing the nanomaterial may be added dropwise to the three-dimensional porous structure material in 10 times, 20 times, or 30 times. The density of the nanomaterial in the first composite material produced may be 3mg/cm2、4mg/cm2Or 5mg/cm2。
And S3, mixing the high polymer and the curing agent according to a preset mass ratio, and respectively injecting the mixture into the first composite material and the three-dimensional porous structure material to obtain a second composite material and a third composite material.
Specifically, the high polymer and the curing agent may be mixed in a mass ratio of 8: 1 to 16: 1, and after mixing, the mixture may be subjected to a vacuum bubble removal treatment. And then injecting the mixture into the first composite material and the three-dimensional porous structure material respectively, and then performing vacuum treatment, curing treatment and surface polymer removal by using an emission spectrometer (ICP) and chemical or mechanical methods on the first composite material and the three-dimensional porous structure material injected with the mixture respectively, wherein the specific treatment process is described in detail below by combining specific embodiments.
S4, removing the three-dimensional porous structure material in the second composite material and the third composite material to obtain a three-dimensional porous electrode and a porous high polymer diaphragm.
Specifically, the three-dimensional porous structure material in the second composite material and the third composite material may be removed by using water or 5% diluted hydrochloric acid. And the prepared nano material in the three-dimensional porous electrode can be used as a current collector and an active substance of the supercapacitor at the same time.
S5, packaging the three-dimensional porous electrode and the porous high polymer diaphragm.
Specifically, a polymer substrate may be manufactured first, and then the three-dimensional porous electrode and the porous polymer separator may be encapsulated by the polymer substrate.
In addition, the electrolyte can be injected into the encapsulated structure by a syringe, with which the injection port can be reduced. In order to encapsulate the injection port, the injection port may be sealed with the high polymer and a sealing film after the injection of the electrolyte. The electrolyte may be LiCl or 1-ethyl-3-methyltetrafluoroborylimidazole.
In this example, a 1mm thick polymer was spin-coated on a mixture obtained using a polymer and a curing agent, and then cured to obtain a polymer substrate.
How to prepare the super capacitor is described in detail below with reference to specific examples.
Example 1
In this embodiment, three-dimensional copper foam is used as the three-dimensional porous structure material, Carbon Nanotubes (CNTs) are used as the nano material, Polydimethylsiloxane (PDMS) is used as the high polymer, and 1-ethyl-3-methyltetrafluoroboryl imidazole is used as the electrolyte. The specific process for fabricating the supercapacitor is as follows.
FIG. 2 shows the preparation process of 3D CNT/PDMS electrode, in this example, firstly, the copper foam is cut into 1cm wide and 10cm long, and rolled to 1mm thick to obtain 3D Cu (three-dimensional porous structure) with ideal thickness and size, then after washing with absolute ethyl alcohol, 5% diluted hydrochloric acid, and deionized water, copper hydroxide nanowires are grown in a mixed solution of 3mol/L sodium hydroxide and 0.1mol/L ammonium persulfate, and then dried for 48h under vacuum at 80 ℃ to obtain 3D Cu/Cu (OH)2. Then 3D Cu/Cu (OH)2Putting the mixture into a tube furnace, and calcining the mixture in air at 600 ℃ for 6 hours to obtain 3D CuO. Then preparing 2mg/ml CNTs ethanol solution by using CNTs with the length of 10-30 mu m and the diameter of 2-500nm, and dripping the solution on the 3D CuO for 20 times to obtain 5mg/cm 23D CNT/CuO. Then, mixing PDMS and a curing agent well according to the mass ratio of 10: 1, removing bubbles under a vacuum condition, filling the mixture into 3D CNT/CuO and 3D CuO, and respectively performing vacuum treatment on the obtained products for 10 hours and curing the products at 80 ℃ for 10 hours to finally obtain 3D CuO/CNT/PDMS and CuO/PDMS. And then etching and removing PDMS on the surfaces of the 3D CuO/CNT/PDMS and the 3D CuO/PDMS by utilizing ICP (SENTECH/SI 500, Germany), and removing the 3D CuO of the two by utilizing 5% diluted hydrochloric acid to finally obtain the 3D CNT/PDMS electrode and the porous PDMS membrane. Next, a PDMS substrate was prepared. The preparation method comprises the following steps of preparing PDMS and a curing agent according to the mass ratio of 10: 1, removing air bubbles under a vacuum condition, spin-coating PDMS with the thickness of 1mm on the obtained product, and finally curing at the temperature of 80 ℃ for 10 hours to obtain the PDMS substrate. And finally, packaging the 3D CNT/PDMS electrode and the porous PDMS membrane by using a PDMS substrate, injecting 1-ethyl-3-methyltetrafluoro boron imidazole into the sealed capacitor by using an injector, and sealing the injection port by using PDMS and a sealing tape to obtain the stretchable and twistable supercapacitor.
The mechanical and mechanical properties of the supercapacitor of example 1 tested by a tensile machine, and the electrochemical properties tested by an electrochemical workstation are described below with reference to fig. 3-12.
Fig. 3 shows a scanning electron micrograph of 3D CNT/PDMS from which it can be seen that CNTs are uniformly embedded in the porous PDMS electrode.
Figure 4 shows a face scan of 3D CNT/PDMS. The uniform distribution of Si, C and O can be seen from the figure, which shows that PDMS is uniformly wrapped on the surface of CNT.
FIG. 5 shows a transmission electron micrograph of 3D CNT/PDMS. It can be seen that the CNT surface is coated with a layer of polymer.
Figure 6 shows the XRD pattern of 3D CNT/PDMS. From the figure, it can be seen that the prepared 3D CNT/PDMS contains XRD peaks of CNTs without other impurities.
Figure 7 shows a graph of the resistance and resistivity of 3D CNT/PDMS at different tensile lengths. It can be seen from the figure that the resistance and resistivity of the 3D CNT/PDMS remained stable during the stretching of the 3D CNT/PDMS to 100%.
Fig. 8 shows a tensile-tensile graph of the 3D CNT/PDMS electrode, the supercapacitor, the porous PDMS membrane, and the PDMS substrate. It can be seen from the figure that the 3D CNT/PDMS electrode can be stretched to 180%, the supercapacitor device can be stretched to 130%, the porous PDMS membrane can be stretched to 165%, and the PDMS substrate can be stretched to 220%.
Fig. 9 shows a charge-discharge curve of a supercapacitor using an electrolyte of an ionic liquid. From the figure, it can be seen that the super capacitor has better performance in charging and discharging under different current densities.
Fig. 10 shows the capacity retention curves at 60% stretch and at 180 ° twist and 40% stretch when the supercapacitor uses an electrolyte of an ionic liquid. It can be seen from the figure that the supercapacitor can maintain good stability in both the stretched and twisted states.
Fig. 11 shows CV curves in different tensile states when the supercapacitor uses an ionic liquid electrolyte. It can be seen from the figure that the supercapacitor is relatively stable under different tensile and torsional conditions. It should be noted that the supercapacitor has no change in performance under other conditions of stretching and twisting except for 100% stretching, and the curves coincide.
Fig. 12 shows impedance curves for a supercapacitor using an electrolyte of an ionic liquid. It can be seen from the figure that the supercapacitor can have a smaller internal resistance.
Example 2
In this embodiment, three-dimensional copper foam is used as the three-dimensional porous structure material, Carbon Nanotubes (CNTs) are used as the nano material, Polydimethylsiloxane (PDMS) is used as the high polymer, and LiCl is used as the electrolyte. The difference between this embodiment and embodiment 1 is only that different electrolytes are used, and other manufacturing processes are the same, and will not be described herein again. The mechanical and electrochemical performance test results are presented in fig. 3-12.
The performance of the supercapacitor provided by the present embodiment is explained below with reference to fig. 13 to 17.
Figure 13 shows the resistance of a 3D CNT/PDMS electrode at 120000 stretches 40% and twists 180 ° each time. It can be seen from the figure that the resistance change of the 3D CNT/PDMS is small under long-time stretching and twisting conditions. It is to be noted that fig. 13 is a graph showing the results of simultaneous testing of two electrodes, each of which is a resistance change tested under the condition of simultaneous twisting by 180 ° and stretching by 40%.
Fig. 14 shows CV curves of a 3D CNT/PDMS electrode after 40% stretching and 180 ° twisting for a total of 120000 times. It can be seen that the CVs have similar shapes at different scan speeds, indicating that the 3D CNT/PDMS has better rate performance.
Fig. 15 shows a schematic of the results of 3D CNT/PDMS electrodes recharged 5000 times after being stretched 40% and twisted 180 ° for a total of 120000 times. It can be seen from the figure that the cycling performance of 3D CNT/PDMS is still stable after long time twist-draw.
Fig. 16(a) shows a photograph of an LED lamp lit with four supercapacitors, numbered sequentially from left to right as device 1, device 2, device 3 and device 4, using a lithium chloride electrolyte. Fig. 16(b) shows CV curves for four supercapacitors using lithium chloride electrolyte after series connection at different scan speeds. Fig. 16(c) shows a schematic of the voltage over time when different numbers of supercapacitors are connected in series-parallel. It can be seen from the figure that when four super capacitors are connected in series, the voltage peak value is maximum, and the voltage change curve with time after the device 1 and the device 2 are connected in parallel is basically coincided with the voltage change curve with time after the device 3 and the device 4 are connected in parallel, the voltage change curves with time of the four super capacitors are basically coincided, and the voltage peak values of the 2 super capacitors connected in parallel are similar to the voltage peak value of a single super capacitor. It can be seen that the super capacitor can be used in series-parallel applications.
Fig. 17(a) shows a photograph of four supercapacitors in series, worn on the hand, using lithium chloride electrolyte. Fig. 17(b) shows a photograph of four supercapacitors connected in series and worn on a hand to illuminate an LED lamp. Fig. 17(c) shows a photograph when the object is normally picked up. And when an object is picked up, the performance of the supercapacitor is tested through the electrochemical workstation, and the performance of the supercapacitor is not changed, so that the supercapacitor provided by the embodiment of the invention can be used for a wearable device, and the stable electrochemical performance is maintained.
Example 3
In this embodiment, three-dimensional foam nickel is used as the three-dimensional porous structure material, Carbon Nanotubes (CNTs) are used as the nano material, Polydimethylsiloxane (PDMS) is used as the high polymer, and 1-ethyl-3-methyltetrafluoroboryl imidazole is used as the electrolyte. The specific process for fabricating the supercapacitor is as follows.
In this example, the nickel foam was first cut into 2cm wide and 20cm long and rolled to 2mm thick to obtain 3D Ni (three dimensional porous structure) of desired thickness and size and calcined in air at 800 ℃ for 6h to obtain 3D NiO. Then, CNTs with the length of 10-30 mu m and the diameter of 2-500nm are utilized to prepare 3mg/ml ethanol solution of the CNTs, and the ethanol solution is dripped on the 3D NiO for 20 times to obtain 4mg/cm 23D CNT/NiO. And then mixing PDMS and a curing agent according to the mass ratio of 10: 1, removing bubbles under a vacuum condition, filling the mixture into 3D CNT/NiO and 3D NiO, and respectively performing vacuum treatment on the obtained products for 10 hours and curing the products at 80 ℃ for 10 hours to finally obtain 3D NiO/CNT/PDMS and NiO/PDMS. And then etching and removing PDMS on the surfaces of the 3D NiO/CNT/PDMS and the 3D NiO/PDMS by utilizing ICP (SENTECH/SI 500, Germany), and removing the 3D NiO by utilizing 5% dilute hydrochloric acid, thereby finally obtaining the 3D CNT/PDMS electrode and the porous PDMS membrane. Next, a PDMS substrate was prepared. Mixing PDMS and a curing agent according to the massThe mass ratio is 10: 1, then bubbles are removed under the vacuum condition, the obtained product is spin-coated with PDMS with the thickness of 1mm, and finally the PDMS substrate is prepared after curing for 10h at the temperature of 80 ℃. And finally, packaging the 3D CNT/PDMS electrode and the porous PDMS membrane by using a PDMS substrate, injecting 1-ethyl-3-methyltetrafluoro boron imidazole into the sealed capacitor by using an injector, and sealing the injection port by using PDMS and a sealing tape to obtain the stretchable and twistable supercapacitor. The mechanical and electrochemical performance test results are shown in fig. 3-12.
Example 4
In this embodiment, porous sugar is used as the three-dimensional porous structure material, Carbon Nanotubes (CNTs) are used as the nano material, Polydimethylsiloxane (PDMS) is used as the high polymer, and LiCl is used as the electrolyte. The specific process for fabricating the supercapacitor is as follows.
Preparing 1mg/ml ethanol solution of CNTs with length of 5-10 μm and diameter of 2-500nm, and dripping the solution on porous sugar by 30 times to obtain 3mg/cm 23D CNT/sugar of (1). Then, mixing PDMS and a curing agent according to a mass ratio of 10: 1, removing bubbles under a vacuum condition, filling the mixture into 3D CNT/sugar, and curing the obtained product at 80 ℃ for 10h under a vacuum treatment to finally obtain the 3D sugar/CNT/PDMS. Then, the PDMS on the surface of the 3D sugar/CNT/PDMS is removed by ICP (SENTECH/SI 500, Germany) etching, and the 3D sugar is removed by water, so that the 3D CNT/PDMS electrode is finally obtained. Next, the porous PDMS membrane and the PDMS substrate were prepared by the method provided in example 1, and finally, the 3D CNT/PDMS electrode and the porous PDMS membrane were encapsulated by the PDMS substrate, and an LiCl aqueous solution was injected into the encapsulated capacitor by an injector, and then the injection port was sealed by the PDMS and the sealing tape, so that the tensile and torsional supercapacitor was obtained. The mechanical and electrochemical performance test results are shown in fig. 3-12.
Example 5
In this embodiment, the three-dimensional porous structure material is porous salt, the nano material is Carbon Nanotubes (CNTs), the high polymer is Polydimethylsiloxane (PDMS), and the electrolyte is LiCl. The specific process for fabricating the supercapacitor is as follows.
By lengthCNTs having a diameter of 2nm to 500nm for 20 to 100 μm, a 6mg/ml ethanol solution of CNTs is prepared and dropped on porous salts (e.g., lithium chloride, sodium chloride, etc.) in 10 times to obtain 3mg/cm 23D CNT/salt of (a). Then, mixing PDMS and a curing agent according to a mass ratio of 10: 1, removing air bubbles under a vacuum condition, filling the mixture into 3D CNT/salt, and curing the obtained product at 80 ℃ for 10h under a vacuum treatment to finally obtain the 3D salt/CNT/PDMS. And then etching and removing PDMS on the surface of the 3D salt/CNT/PDMS by utilizing ICP (SENTECH/SI 500, Germany), and removing the 3D salt by utilizing water to finally obtain the 3D CNT/PDMS electrode. Next, the porous PDMS membrane and the PDMS substrate were prepared by the method provided in example 1, and finally, the 3D CNT/PDMS electrode and the porous PDMS membrane were encapsulated by the PDMS substrate, and an LiCl aqueous solution was injected into the encapsulated capacitor by an injector, and then the injection port was sealed by the PDMS and the sealing tape, so that the tensile and torsional supercapacitor was obtained. The mechanical and electrochemical performance test results are shown in fig. 3-12.
It should be noted that the sodium hydroxide and ammonium persulfate in examples 1 and 2 can be replaced by potassium hydroxide and sodium persulfate, the calcination temperature in examples 1-3 can be 300-1600 deg.C, the curing temperature in examples 1-5 can be 60-200 deg.C, PDMS can be replaced by high polymer silica gel with flexible and stretchable properties, and PDMS on the surface can be removed by chemical or mechanical force. In addition, in order to improve the surface capacity of the 3D CNT/PDMS electrode, active materials such as ruthenium oxide, manganese oxide, vanadium oxide, or nickel oxide may be grown on the CNT by chemical growth or electrochemical deposition, and polymer pseudocapacitance active materials such as polyaniline and polypyrrole may also be grown. The sealing may be performed by a conventional technique, and the electrolyte may be an electrolyte used in a conventional capacitor.
Embodiments of the present invention have one or more of the following advantages over the prior art:
(1) the nanometer material in the three-dimensional porous electrode is simultaneously used as the current collector and the active substance of the super capacitor, the super capacitor has a super-stable structure, and the three-dimensional porous electrode can effectively protect the active substance in the twisting and stretching process.
(2) The porous high polymer diaphragm ensures that the short circuit problem of the super capacitor does not occur in the stretching and twisting process.
(3) Gel electrolyte is mostly used in the conventional stretchable super capacitor, and the voltage is lower, the super capacitor provided by the invention uses organic or ionic liquid electrolyte to increase the working voltage, and the energy density is improved, for example, the working voltage of the twistable stretchable super capacitor provided by the invention is 3V.
(4) The stretchable and twistable supercapacitor prepared by the method has super-stable mechanical properties, and can still maintain the original electrochemical properties after being twisted and stretched for hundreds of thousands of cycles.
It should also be noted that, in the case of the embodiments of the present invention, features of the embodiments and examples may be combined with each other to obtain a new embodiment without conflict.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method of manufacturing a supercapacitor, comprising the steps of:
s1, providing a high polymer, a nano material, a three-dimensional porous structure material and a curing agent, wherein the high polymer is polydimethylsiloxane or silica gel;
s2, preparing a first composite material by using the nano material and the three-dimensional porous structure material, wherein an ethanol solution or an aqueous solution of the nano material is prepared; dropwise adding an ethanol solution or an aqueous solution containing a nano material to the three-dimensional porous structure material to prepare the first composite material;
s3, mixing the high polymer and the curing agent according to a preset mass ratio, respectively injecting the mixture into a first composite material and a three-dimensional porous structure material, respectively carrying out vacuum treatment and curing treatment on the first composite material and the three-dimensional porous structure material which are injected with the high polymer and the curing agent, and chemically or mechanically removing the surface high polymer by using an emission spectrometer;
obtaining a second composite material and a third composite material;
s4, removing the three-dimensional porous structure materials in the second composite material and the third composite material to obtain a three-dimensional porous electrode and a porous high polymer diaphragm; the three-dimensional porous electrode and the porous high polymer diaphragm adopt organic or ionic liquid electrolyte;
s5, packaging the three-dimensional porous electrode and the porous high polymer diaphragm;
wherein the nano-materials in the three-dimensional porous electrode simultaneously serve as a current collector and an active substance of the supercapacitor.
2. The method of claim 1, wherein in step S3, the high polymer and the curing agent mixed in a preset mass ratio are subjected to a vacuum de-bubbling treatment.
3. The method of claim 1, wherein the method further comprises the steps of:
a polymer substrate is manufactured.
4. The method of claim 3, wherein the three-dimensional porous electrode and the porous polymeric separator are encapsulated with the polymeric substrate.
5. The method of any one of claims 1-4, further comprising:
and injecting an electrolyte into the three-dimensional porous electrode and the porous high polymer diaphragm after packaging.
6. The method of claim 5, wherein the injection port is sealed using the high polymer and a sealing film after the injection of the electrolyte.
7. The method according to any one of claims 1 to 4, wherein the predetermined mass ratio is from 8: 1 to 16: 1.
8. The method of any one of claims 1-4, wherein the nanomaterial is a carbon nanotube.
9. The method of any one of claims 1-4, wherein the three-dimensional porous structure material is a three-dimensional metal, a metal compound, a porous sugar, or a porous salt.
10. The method according to any one of claims 1-4, characterized in that the method further comprises the step of: and pretreating the three-dimensional porous structure material.
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