CN113764200B - Super capacitor, diaphragm and preparation method thereof - Google Patents
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- CN113764200B CN113764200B CN202111077166.XA CN202111077166A CN113764200B CN 113764200 B CN113764200 B CN 113764200B CN 202111077166 A CN202111077166 A CN 202111077166A CN 113764200 B CN113764200 B CN 113764200B
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- 239000003990 capacitor Substances 0.000 title abstract description 34
- 241000534460 Ampullaria Species 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229920002261 Corn starch Polymers 0.000 claims abstract description 10
- 239000008120 corn starch Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000292 calcium oxide Substances 0.000 claims abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 241000570011 Pomacea canaliculata Species 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- -1 carboxyl carbon nanotube Chemical compound 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 241000237858 Gastropoda Species 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000009766 low-temperature sintering Methods 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 235000012054 meals Nutrition 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 238000012360 testing method Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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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
- H01G11/52—Separators
-
- 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
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a super capacitor, a super capacitor diaphragm and a preparation method, wherein the super capacitor diaphragm is prepared from the following raw materials in percentage by mass: 5-60% of ampullaria gigas shell powder, 12-65% of aluminium oxide, 4-8% of corn starch, 3-8% of silicon dioxide, 3-6% of potassium phosphate, 5-10% of diboron trioxide, 0.5-5% of calcium oxide and 0.5-5% of polyvinyl alcohol. According to the invention, the Pomacea canaliculata shell is used as a raw material to prepare the supercapacitor diaphragm, so that the application of the Pomacea canaliculata shell is realized, the damage of the Pomacea canaliculata to the ecological environment is reduced, the sintering temperature in the diaphragm preparation process is reduced, and the manufacturing cost is further reduced.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a super capacitor, a diaphragm and a preparation method of the super capacitor.
Background
With the rapid development of new energy vehicles, smart phones and other novel industries, higher requirements are put forward on the improvement of the performance of energy storage devices. A super capacitor (SCs for short) is a novel energy storage device, which has fast charge and discharge capacity, long cycle life and high safety, makes up for some of the defects of lithium ion batteries, and is a key development object of high-efficiency energy storage devices. Improving the stability and the service life of the super capacitor is an important research direction.
The super capacitor mainly comprises electrodes, a diaphragm, electrolyte and the like. The diaphragm is used as one of the key materials of the super capacitor, and the structure and the performance of the diaphragm directly influence the specific power, the specific capacity and the cycle life of the super capacitor. Common diaphragm materials mainly include cellulose paper diaphragms, synthetic high-molecular polymer diaphragms, electrostatic spinning diaphragms, biological diaphragms and the like. With the wide application of capacitors, how to prepare low-cost high-performance diaphragms becomes a technical problem to be solved urgently.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a super capacitor, a super capacitor diaphragm and a preparation method thereof, and aims to solve the problem of the preparation cost of the conventional super capacitor.
The invention provides a super capacitor diaphragm which is prepared from the following raw materials in percentage by mass: 5 to 60 percent of ampullaria gigas shell powder, 12 to 65 percent of aluminum oxide, 4 to 8 percent of corn starch, 3 to 8 percent of silicon dioxide, 3 to 6 percent of potassium phosphate, 5 to 10 percent of boron trioxide, 0.5 to 5 percent of calcium oxide and 0.5 to 5 percent of polyvinyl alcohol.
Further, the ampullaria gigas shell powder is 100-300 meshes.
Further, the corn starch is 100-150 meshes.
The invention utilizes numerous ampullaria gigas shells existing in nature as raw materials to prepare the supercapacitor diaphragm, thereby not only reducing the damage of the ampullaria gigas to the ecological environment, but also greatly exploiting the economic value of the ampullaria gigas, and reducing the manufacturing cost of the capacitor diaphragm.
In addition, the invention also provides a preparation method of the supercapacitor diaphragm, which comprises the following steps:
s1, mixing the ampullaria gigas shell powder, aluminum oxide, corn starch, silicon dioxide, potassium phosphate, boron trioxide and calcium oxide according to the mass percentage;
s2, adding the mixed raw materials into a nanosphere mill, and performing dry ball milling to obtain powder with the average particle size of 1-10 microns;
s3, uniformly mixing the powder with 0.5-5% of polyvinyl alcohol and drying;
and S4, pressing and molding the dried raw materials, and sintering at low temperature to obtain the supercapacitor diaphragm.
Further, the ampullaria gigas shell powder is prepared by the following method:
s01, putting the ampullaria gigas shells into a 2-5% sodium dodecyl sulfate aqueous solution for cleaning and drying to obtain clean shells;
s02, crushing the clean snail shells into shell powder by a crusher, and sieving the shell powder by a 100-mesh and 300-mesh sieve to obtain the ampullaria gigas shell powder.
Further, the molding in step S4 is specifically: pressing and molding by a press under the pressure of 10-30MPa, wherein the thickness is about 1.2 mm.
Further, the low-temperature sintering in step S4 specifically includes: sintering at 350-580 deg.C for 0.5-5 h.
The main component of the ampullaria gigas shell is aragonite calcium carbonate, the characteristics of the ampullaria gigas shell are utilized, and the ampullaria gigas shell is cooperated with other components to act together, so that the temperature of a sintering stage can be greatly reduced when the supercapacitor diaphragm is prepared, the sintering is carried out only in the air atmosphere of 350-580 ℃ at low temperature for 0.5-5h, the reduction of the sintering temperature means the reduction of energy consumption, and the manufacturing cost of the capacitor diaphragm is further reduced.
Meanwhile, the invention also provides a super capacitor, which comprises the diaphragm prepared by the preparation method.
Furthermore, the positive electrode and the negative electrode of the super capacitor both adopt carboxyl carbon nanotube electrodes with foamed nickel as a substrate.
Further, the preparation method of the carboxyl carbon nanotube electrode comprises the following steps: weighing 5-30mg of carboxyl carbon nano tube, dissolving with 200-500 mu L of tetrahydrofuran, taking 100 mu L of solution, dropping 1-10mg of acetylene black into the solution, ultrasonically dispersing, adding 0.01-0.06mol/L of glue prepared from 10-50 mu L of polytetrafluoroethylene emulsion, uniformly stirring to prepare paste, and then pressing on a foam nickel sheet for vacuum drying to obtain the nano-tube.
The supercapacitor diaphragm prepared from the ampullaria gigas shell has good insulating property, controllable pore structure appearance, stable chemical property and higher mechanical strength, and after the supercapacitor diaphragm is applied to a supercapacitor device, the supercapacitor diaphragm is verified by tests such as cyclic voltammetry, constant-current charging and discharging and the like, has good energy storage performance stability and long service life, and the performance is still good after 2 ten thousand cyclic tests.
Drawings
FIG. 1 is a flow chart of a method for making a supercapacitor separator according to one embodiment of the invention;
FIG. 2 is a flow chart of a method for preparing Pomacea canaliculata shell powder according to an embodiment of the present invention;
FIG. 3 is a graph of CV for different scan rates for an ultracapacitor according to one embodiment of the present invention;
FIG. 4 is a graph showing the dependence of the specific capacitance of a super capacitor on the scan rate according to an embodiment of the present invention;
FIG. 5 is a constant current charging and discharging curve diagram of an ultracapacitor at different current densities according to an embodiment of the present invention;
FIG. 6 is a graph illustrating the dependence of the specific capacitance of a super capacitor on the current density according to an embodiment of the present invention;
FIG. 7 is a graph showing the dependence of the capacity retention ratio of a supercapacitor on the number of cycles (current density: 3.60A g-1) according to one embodiment of the present invention;
fig. 8 is an electrochemical ac impedance spectrum before and after 2 ten thousand cycle life tests of the supercapacitor at room temperature in an embodiment of the invention.
Detailed Description
The invention provides a super capacitor diaphragm, a preparation method thereof and a super capacitor, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a super capacitor diaphragm which is prepared from the following raw materials in percentage by mass: 5 to 60 percent of ampullaria gigas shell powder, 12 to 65 percent of aluminum oxide, 4 to 8 percent of corn starch, 3 to 8 percent of silicon dioxide, 3 to 6 percent of potassium phosphate, 5 to 10 percent of boron trioxide, 0.5 to 5 percent of calcium oxide and 0.5 to 5 percent of polyvinyl alcohol.
Preferably, the ampullaria gigas shell powder is 100-300 meshes.
Preferably, the corn starch is 100-150 mesh.
As shown in fig. 1, the invention also provides a preparation method of the supercapacitor separator, which comprises the following steps:
s1, mixing the ampullaria gigas shell powder, aluminum oxide, corn starch, silicon dioxide, potassium phosphate, boron trioxide and calcium oxide according to the mass percentage;
s2, adding the mixed raw materials into a nanosphere mill, and performing dry ball milling to obtain powder with the average particle size of 1-10 microns;
s3, uniformly mixing the powder with 0.5-5% of polyvinyl alcohol and drying;
and S4, pressing and molding the dried raw materials, and sintering at low temperature to obtain the supercapacitor diaphragm.
Preferably, as shown in fig. 2, the ampullaria gigas shell powder is prepared by the following method:
s01, putting the ampullaria gigas shells into a 2-5% sodium dodecyl sulfate aqueous solution for cleaning and drying to obtain clean shells;
s02, crushing the clean snail shells into shell powder by a crusher, and sieving the shell powder by a 100-mesh and 300-mesh sieve to obtain the ampullaria gigas shell powder.
Preferably, the molding in step S4 is specifically: pressing and molding by a press under the pressure of 10-30MPa, wherein the thickness is about 1.2 mm.
Preferably, the low-temperature sintering in step S4 is specifically: sintering at 350-580 deg.C for 0.5-5 h.
Meanwhile, the invention also provides a super capacitor, which comprises the diaphragm prepared by the preparation method.
Preferably, the positive electrode and the negative electrode of the supercapacitor both adopt carboxyl carbon nanotube electrodes with foamed nickel as a substrate.
Preferably, the preparation method of the carboxyl carbon nanotube electrode comprises the following steps: weighing 5-30mg of carboxyl carbon nano tube, dissolving with 200-500 mu L of tetrahydrofuran, taking 100 mu L of solution, dropping 1-10mg of acetylene black into the solution, ultrasonically dispersing, adding 10-50 mu L of polytetrafluoroethylene emulsion (PTFE, 0.01 mg/L) to prepare 0.01-0.06mol/L of glue, uniformly stirring to prepare paste, and then pressing on a foam nickel sheet for vacuum drying to prepare the nano-material. Preferably, the anode and the cathode are prepared by vacuum drying at 80-130 ℃ for 1-10 h.
In order to verify the performance of the supercapacitor of the invention, in one embodiment, the positive electrode, the negative electrode and the ampullaria gigas shell are usedThe prepared capacitor diaphragm is cut into small blocks of 2cm multiplied by 2cm and soaked in 1.0 mol/L Na 2 SO 4 Wetting in a water solution, horizontally placing a glass slide, an anode, a capacitor diaphragm, a cathode and the glass slide from bottom to top in sequence, and then winding and sealing the supercapacitor with a paraffin film for sealing treatment to obtain a supercapacitor device F.
Fig. 3 is a CV graph of the device F at different scan rates, and it can be seen from the graph that the CV graphs of the device F are all rectangular or rectangle-like, indicating that the devices have good capacitance characteristics. As the scan rate increases, the area of the CV curve also increases gradually.
We calculate the specific capacitance of device F from the integrated area of FIG. 3, by the formula
The calculation results are shown in fig. 4. It can be seen from fig. 4 that as the scan rate increases from 10, 20, 50, 100 to 200 mV s-1, the specific capacitance of the device decreases as the scan rate increases. When the scanning speed is as high as 200 mV/s, the specific capacitance is 7.4F g -1 The magnification thereof was 59.2%, indicating that it had a high magnification.
Further, the charging and discharging curves of the device F under different current densities are further researched through constant current charging and discharging tests, and as shown in fig. 5, the curves show good symmetry and linear characteristics, and the excellent super-capacitor performance is reflected.
Using formulas
From the discharge curve of fig. 5, the specific capacitance values of the device F at different current densities were calculated, as shown in fig. 6. The current density was 0.07, 0.18, 0.36, 0.73, 1.80 and 3.60A g in this order -1 The specific capacitances are respectively 13.3, 12.4, 11.6, 10.6, 8.3 and 5.4F g -1 The above results indicate that the device F has superior supercapacitor performance.
In addition to being able to charge and discharge quickly, cycle life is a key parameter in capacitor performance. The results of 2 ten thousand charge and discharge cycles of the device F, which was tested for cycle life at a current density of 3.60A g-1, are shown in FIG. 7. The capacitance did not decay after 2 ten thousand cycles, indicating a long service life. In order to further study the internal resistance problem of the device F, electrochemical alternating current impedance spectroscopy (EIS) data before and after 2 ten thousand life tests are collected as shown in fig. 8, and it can be seen that two EIS curves substantially coincide, which indicates that the internal resistance is substantially unchanged before and after 2 ten thousand cycles. Specifically, the two EIS curves are a small semicircle in the high frequency region, which indicates that the device F has a very low internal resistance to charge transfer. The middle and low frequency region is an upward inclined curve, which shows that the device F has ideal capacitance behavior before and after the cycle life test.
In conclusion, the invention adopts the ampullaria gigas shell to prepare the supercapacitor diaphragm which has good insulating property, controllable pore structure appearance, stable chemical property and higher mechanical strength. After the application of the material in a super capacitor device, the electrochemical characterization such as cyclic voltammetry, constant current charging and discharging and the like shows that the current density of the device F is 0.07A g -1 When the specific capacitance is 13.3F g -1 (ii) a At 3.60A g -1 And the specific capacitance of the device F is not attenuated after the device is subjected to cycle life test for 2 ten thousand cycles, which shows that the ampullaria gigas shell porous ceramic diaphragm is a super capacitor diaphragm with excellent performance.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (6)
1. The supercapacitor is characterized by comprising a supercapacitor diaphragm prepared by the preparation method of the supercapacitor diaphragm, wherein the positive electrode and the negative electrode of the supercapacitor are carboxyl carbon nanotube electrodes with foam nickel as a substrate, and the supercapacitor diaphragm is prepared from the following raw materials in percentage by mass: 5-60% of Pomacea canaliculata shell powder, 12-65% of aluminum oxide, 4-8% of corn starch, 3-8% of silicon dioxide, 3-6% of potassium phosphate, 5-10% of boron trioxide, 0.5-5% of calcium oxide and 0.5-5% of polyvinyl alcohol;
the preparation method of the supercapacitor diaphragm comprises the following steps:
s1, mixing the ampullaria gigas shell powder, aluminum oxide, corn starch, silicon dioxide, potassium phosphate, boron trioxide and calcium oxide according to the mass percentage of the membrane;
s2, adding the mixed raw materials into a nanosphere mill, and performing dry ball milling to obtain powder with the average particle size of 1-10 microns;
s3, uniformly mixing the powder with the polyvinyl alcohol in percentage by mass, and drying;
and S4, pressing and molding the dried raw materials, and sintering at low temperature to obtain the supercapacitor diaphragm.
2. The supercapacitor according to claim 1, wherein the preparation method of the carboxyl carbon nanotube electrode comprises: weighing 5-30mg of carboxyl carbon nano tube, dissolving with 200-500 mu L of tetrahydrofuran, taking 100 mu L of solution, dropping 1-10mg of acetylene black into the solution, ultrasonically dispersing, adding 0.01-0.06mol/L of glue prepared from 10-50 mu L of polytetrafluoroethylene emulsion, uniformly stirring to prepare paste, and then pressing on a foam nickel sheet for vacuum drying to obtain the nano-tube.
3. The supercapacitor according to claim 1, wherein the ampullaria gigas shell powder is 100-300 mesh, and the corn starch is 100-150 mesh.
4. The supercapacitor according to claim 1, wherein the pressing in step S4 is specifically: pressing with a press under 10-30MPa to obtain the final product with a thickness of 1.2 mm.
5. The supercapacitor according to claim 4, wherein the low-temperature sintering in step S4 is specifically: sintering at 350-580 deg.C for 0.5-5 h.
6. The supercapacitor according to claim 1, wherein the ampullaria gigas shell meal is prepared by the following method:
s01, putting the ampullaria gigas shells into a 2-5% sodium dodecyl sulfate aqueous solution for cleaning and drying to obtain clean shells;
s02, crushing the clean snail shells into shell powder by a crusher, and sieving the shell powder by a 100-mesh and 300-mesh sieve to obtain the ampullaria gigas shell powder.
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| CN106128793A (en) * | 2016-06-24 | 2016-11-16 | 安徽江威精密制造有限公司 | The hybrid supercapacitor diaphragm material that a kind of isolation performance is good |
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| CN109755440A (en) * | 2018-12-17 | 2019-05-14 | 中国电力科学研究院有限公司 | A kind of preparation method, battery core and the lithium ion battery of low temperature resistant anodic aluminium oxide membrane type lithium ion battery |
| TW202018144A (en) * | 2018-11-14 | 2020-05-16 | 國立虎尾科技大學 | Method for making paper from waste oyster shell and finished product thereof including grinding and sintering steps to mold the oyster shell paper material |
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| US20130041420A1 (en) * | 2011-08-11 | 2013-02-14 | Gregory J. Sherwood | Sintered capacitor electrode including a 3-dimensional framework |
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