WO2020062223A1 - One-stop supercapacitor and preparation method therefor - Google Patents
One-stop supercapacitor and preparation method therefor Download PDFInfo
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- WO2020062223A1 WO2020062223A1 PCT/CN2018/109055 CN2018109055W WO2020062223A1 WO 2020062223 A1 WO2020062223 A1 WO 2020062223A1 CN 2018109055 W CN2018109055 W CN 2018109055W WO 2020062223 A1 WO2020062223 A1 WO 2020062223A1
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- electrolyte
- supercapacitor
- flour
- electrode
- weight ratio
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000013312 flour Nutrition 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 230000008439 repair process Effects 0.000 description 25
- 230000008569 process Effects 0.000 description 6
- 238000010008 shearing Methods 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000002496 gastric effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000057297 Pepsin A Human genes 0.000 description 1
- 108090000284 Pepsin A Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229940111202 pepsin Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
Definitions
- the invention relates to the technical field of capacitors, and in particular, to a one-stop supercapacitor and a preparation method thereof.
- Supercapacitors are particularly important as the basic unit of energy supply for these devices. Existing ultracapacitors will inevitably be cut accidentally or be subject to other mechanical deformation and damage during actual application. More importantly, such damage will make the ultracapacitors that can be stretched no longer be damaged. Stretching eventually leads to a sudden reduction in the performance of supercapacitors, or even to discard them, and discarded capacitors cannot be degraded, which places a heavy burden on the environment.
- the present invention provides a one-stop supercapacitor and a preparation method thereof.
- the supercapacitor also has one-stop multifunctional characteristics such as self-healing, self-healing and re-stretching and biodegradability .
- the present invention provides a method for preparing a one-stop supercapacitor, including the following steps: preparing a solution: mixing phosphoric acid, sodium chloride, and deionized water in a weight ratio of 1: 1: 5 to 6 to obtain a uniform solution. Solution; preparing electrolyte: mixing flour with a weight ratio of 4: 3 to 3.5 and mixing the solution to obtain an electrolyte; preparing electrodes: mixing the solution with a weight ratio of 5: 2.5 to 3: 1 to 1.5, activated carbon and flour The electrode is uniformly obtained; the super capacitor is prepared: the electrolyte is sandwiched between two electrodes to obtain a super capacitor.
- the weight ratio of phosphoric acid, sodium chloride and deionized water in the solution is 1: 1: 5
- the weight ratio of flour in the electrolyte and the solution is 4: 3
- the solution in the electrode The weight ratio of activated carbon and flour is 5: 3: 1.
- a mold is used to squeeze the electrolyte into a regular shape and then sandwich it between the two electrodes.
- the electrolyte is sandwiched between the two electrodes.
- the regular shape is a square plate shape or a cylindrical shape.
- the activated carbon and flour are first mixed uniformly, and then added to the solution and mixed uniformly to obtain the electrode.
- the present invention provides a one-stop supercapacitor, which includes an electrode and an electrolyte, the electrolyte is sandwiched between the two electrodes, and the electrode includes a weight ratio of 1 to 1.5: 2.5 to 3: 5. : 5:25 to 30 flour, activated carbon, phosphoric acid, sodium chloride, and deionized water, and the electrolyte includes flour, phosphoric acid, sodium chloride, and 4: 3 to 3.5: 3 to 3.5: 15 to 18 by weight. Deionized water.
- the electrode includes flour having a weight ratio of 1: 3: 5: 5: 25, activated carbon, phosphoric acid, sodium chloride, and deionized water
- the electrolyte includes flour having a weight ratio of 4: 3: 3: 15. , Phosphoric acid, sodium chloride and deionized water.
- the shape and size of the electrolyte and each of the electrodes are the same.
- the electrolyte and each of the electrodes are in a square plate shape or a cylindrical shape.
- the supercapacitor provided by the invention can perform internal and autonomous self-repair, can be stretched after self-repair, and can be biodegraded after use.
- the preparation method is simple, the required components are small, and the cost is low. Suitable for flexible and implantable electronic devices.
- FIG. 1A is a schematic diagram of preparing an electrolyte and an electrode in a first embodiment of the present invention
- FIG. 1B is a schematic diagram of a self-repair and stretch after repair of a super capacitor in the first embodiment of the present invention
- FIG. 1C is a schematic diagram of a biodegradable supercapacitor in the first embodiment of the present invention.
- FIG. 2Ai shows the tensile behavior of the electrolyte in the first embodiment of the present invention
- 2Aii shows the behavior of the electrolyte in the first embodiment of the present invention undergoing continuous shaping, shearing, repairing, reshaping to the original state and stretching;
- FIG. 2Bi shows the stretching behavior of the electrode in the first embodiment of the present invention
- FIG. 2Bii shows the behavior of the electrode in the first embodiment of the present invention undergoing continuous shaping, cutting, repairing, reshaping to the original state and stretching;
- 2C shows a SEM image of an electrode containing activated carbon and flour in the first embodiment of the present invention
- 2D shows a Raman spectrum chart of activated carbon and flour in the first embodiment of the present invention
- FIG. 3A shows each CV curve of the super capacitor in the first embodiment of the present invention at multiple scan rates between 10 mVs -1 and 1000 mVs -1 ;
- 3B shows the GCD curves of the super capacitor in the first embodiment of the present invention under a plurality of charge / discharge currents between 5 ⁇ A and 20 ⁇ A;
- 4a is a function relationship between the specific capacitance of the supercapacitor and the scan rate between 10 mVs -1 and 1000 mVs -1 in the first embodiment of the present invention
- 4b is a function relationship between the specific capacitance of the ultracapacitor and the current between 5 ⁇ A and 20 ⁇ A in the first embodiment of the present invention
- 5A shows a plurality of CV curves of the supercapacitor from the 0th repair to the 40th repair in the first embodiment of the present invention
- FIG. 5B shows the repair efficiency of the super capacitor in the first embodiment of the present invention from the 0th repair to the 40th repair;
- FIG. 6 shows a plurality of GCD curves of the supercapacitor from the 0th repair to the 40th repair in the first embodiment of the present invention
- FIG. 7A shows the GCD curves of 0% to 50% stretching of the supercapacitor after self-repair in the first embodiment of the present invention
- FIG. 7B shows a function relationship between capacitance retention and tensile strain of the ultracapacitor in the first embodiment of the present invention
- FIG. 8 shows the CV curves of the supercapacitor stretched from 0% to 50% after self-repair in the first embodiment of the present invention
- FIG. 10A shows the biodegradation process of the supercapacitor in the simulated gastric fluid environment in the first embodiment of the present invention
- FIG. 10B shows the biodegradation process in the supercapacitor nutrient soil in the first embodiment of the present invention.
- This embodiment provides a one-stop supercapacitor, which includes an electrode and an electrolyte, the electrolyte is sandwiched between the two electrodes, wherein the electrode includes flour and activated carbon with a weight ratio of 1: 3: 5: 5: 25 , Phosphoric acid, sodium chloride, and deionized water, the electrolyte includes flour, phosphoric acid, sodium chloride, and deionized water in a weight ratio of 4: 3: 3: 15.
- the shape of the electrolyte and each of the electrodes is a rectangular plate shape, and the sizes are also the same.
- the preparation method of the super capacitor includes the following steps:
- S1 prepare a solution: 20 g of phosphoric acid, 20 g of sodium chloride and 100 g of deionized water are mixed to obtain a solution.
- FIG. 1A it is a schematic diagram of preparing an electrolyte and an electrode.
- a supercapacitor is obtained by sandwiching the electrolyte between two electrodes.
- the electrolyte and the two electrodes are first extruded into a rectangular plate shape by using the same mold, and then the electrolyte is sandwiched between the two electrodes.
- the electrolyte and the two electrodes may be extruded into a cylindrical shape.
- the flour is used as the main material of the electrolyte and the electrode to ensure the excellent flexibility and self-healing properties of the supercapacitor.
- Phosphoric acid and sodium chloride are used as the ion source to improve the ion conductivity.
- the combination of activated carbon and flour is used to improve The electronic conductivity of the electrode fully guarantees the electrochemical performance of the supercapacitor.
- the prepared supercapacitors through the hydrogen bonds formed between the electrolyte, the flour in the electrodes, and the water molecules, enable the supercapacitors to perform intrinsic and autonomous self-treatment after undergoing mechanical damage such as cutting. It can be repaired, and it can also be stretched after the self-repair. After using the super capacitor, it can be biodegraded.
- the method for preparing supercapacitors is not only simple to prepare, but also requires fewer components and has low cost.
- Figure 2Ai shows the tensile behavior of the electrolyte. From this figure, it can be seen that the electrolyte can be shaped into any shape and can be stretched with high strength; Figure 2Aii shows that the electrolyte undergoes continuous shaping, shearing, repair, and reshaping to The original state and stretching behavior can be seen from the figure, the electrolyte can repair itself after being cut, and can be arbitrarily kneaded to completely restore the original shape. More importantly, comparing Figure 2 in Figure 2Ai and Figure 6 in Figure 2Aii, it can be found that the electrolyte after self-repair can be stretched to the same length as the original electrolyte.
- the electrodes also show good flexibility, stretchability, and self-healing properties.
- the electrode's tensile behavior is shown in Figure 2Bi, and the electrode shown in Figure 2Bii undergoes continuous shaping, shearing, repair, and Forming to the original state and drawing behavior.
- the unique properties of this electrolyte and electrode make the final supercapacitor also have excellent mechanical stability, that is, it can not only intrinsically and autonomously repair itself, but also perform intrinsic stretching after self-repairing.
- Figure 2C shows an SEM image of an electrode containing activated carbon and flour.
- the scale bar is 10um. Micron spherical activated carbon and nanosphere flour can be seen from the figure. This can be verified from Figure 2D.
- Figure 2D shows the activated carbon and flour.
- FIG. 3A shows each CV curve of the super capacitor at multiple scan rates between 10 mVs -1 and 1000 mVs -1
- FIG. 3B shows each GCD curve of the super capacitor at multiple charge / discharge currents between 5 ⁇ A and 20 ⁇ A.
- Each electrochemical test is performed at room temperature.
- FIG. 3A and FIG. 3B show the fast and reversible electrochemical properties of the supercapacitor, which shows that the supercapacitor prepared by the method has good conductivity and effective electrochemical dynamic process.
- the CV curve gradually deviates from the rectangular shape, which is mainly caused by the diffusion-controlled ion transmission with higher ion transfer resistance at higher rates. As shown in FIGS.
- the specific capacitances of the supercapacitors are calculated from the CV curves of FIG. 3A and the GCD curves of FIG. 3B.
- Figure 4a shows the relationship between the specific capacitance of the supercapacitor and the scan rate between 10mVs -1 and 1000mVs -1 .
- the calculated capacitance decreases as the scan rate increases.
- Figure 4b shows the specific capacitance of the supercapacitor as a function of the current between 5 ⁇ A and 20 ⁇ A.
- the calculated capacitance decreases as the current increases.
- the formula for calculating capacitance based on CV curve and GCD curve is as follows:
- I is the discharge current of the GCD
- t is the discharge time of the GCD
- U is the voltage range
- U U + -U -
- s is the area of one of the electrodes
- v is the scan rate of the CV curve
- FIG. 5A shows the multiple CV curves of the super capacitor from the 0th repair to the 40th repair
- FIG. 5B shows the multiple repair efficiency of the super capacitor from the 0th repair to the 40th repair
- FIG. 6 shows the super capacitor from 0th repair.
- Fig. 7A shows the GCD curves of 0% to 50% stretching after supercapacitor self-repair
- Fig. 7B shows the relationship between the capacitance retention and tensile strain of the supercapacitor
- Fig. 8 shows 0% to 10% stretch after supercapacitor self-repair.
- Each CV curve was stretched by 50%. It can be seen from Figures 7A and 8 that even after stretching to 50% after self-repair, the GCD curve and CV curve are similar to the curve before repair; and from Figure 7B, it can be seen that even after pulling When it reaches 50%, its capacitance remains at about 80%. Although the capacitance decreases slightly with the increase of tensile strain in the figure, it is caused by the slight weakening of the conductivity of the electrode, which is unavoidable. .
- Figure 9 is a photo of different tensile strains of the supercapacitor after repair and repair. It can be further verified from the photos that after the supercapacitor is cut, the hydrogen bond can reach a new balance through the contact of the cut surface under the environmental conditions and slight pressure, so that the supercapacitor repairs itself to its original state. And even if it was further stretched to 50%, the supercapacitor did not break and showed strong self-healing and stretchability after self-healing, which had never been achieved before.
- FIG. 10A shows the biodegradation process of supercapacitors in a simulated gastric fluid environment
- FIG. 10B shows the biodegradation process of supercapacitors in a nutrient soil.
- Black blocks are supercapacitors, and bright blocks are plastics used as a control.
- the raw materials used in the super capacitor in this embodiment are non-toxic and environmentally friendly, especially most of them are biodegradable flour, which makes the super capacitor in this embodiment very environmentally friendly and biodegradable.
- the supercapacitor was still a whole at first, but after a few days, it was broken down into small pieces, and only carbon powder was left. This is due to the simulation of pepsin in gastric juice to protein in flour. Caused by decomposition.
- step S1 when preparing a super capacitor, the solution in step S1 is prepared by mixing 20g phosphoric acid, 20g sodium chloride and 120g deionized water.
- the electrolyte is prepared by mixing 40g of flour and 35g of the solution, and in step S3, the electrode is prepared by mixing 50g of the solution, 25g of activated carbon, and 15g of flour.
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Abstract
Description
Claims (10)
- 一站式超级电容器的制备方法,其特征在于,包括以下步骤:The method for preparing a one-stop supercapacitor is characterized in that it includes the following steps:制备溶液:将重量比为1:1:5~6的磷酸、氯化钠和去离子水混合均匀得一溶液;Preparation of solution: phosphoric acid, sodium chloride and deionized water in a weight ratio of 1: 1: 5 to 6 are mixed uniformly to obtain a solution;制备电解质:将重量比为4:3~3.5的面粉、所述溶液混合均匀得电解质;Preparing electrolyte: mixing flour with a weight ratio of 4: 3 to 3.5 and the solution to obtain an electrolyte;制备电极:将重量比为5:2.5~3:1~1.5的所述溶液、活性炭和面粉混合均匀得电极;Preparing an electrode: mixing the solution, activated carbon and flour in a weight ratio of 5: 2.5 to 3: 1 to 1.5 to obtain an electrode;制备超级电容器:将所述电解质夹在两个所述电极之间得超级电容器。Preparation of a super capacitor: a super capacitor is obtained by sandwiching the electrolyte between two electrodes.
- 根据权利要求1所述的制备方法,其特征在于,所述溶液中磷酸、氯化钠和去离子水的重量比为1:1:5,所述电解质中面粉和所述溶液的重量比为4:3,所述电极中所述溶液、活性炭和面粉的重量比为5:3:1。The preparation method according to claim 1, wherein a weight ratio of phosphoric acid, sodium chloride and deionized water in the solution is 1: 1: 5, and a weight ratio of flour in the electrolyte to the solution is 4: 3, the weight ratio of the solution, activated carbon and flour in the electrode is 5: 3: 1.
- 根据权利要求1所述的制备方法,其特征在于,采用一模具将所述电解质挤压成规则形状后再夹在两个所述电极之间。The method according to claim 1, wherein the electrolyte is extruded into a regular shape by a mold and then sandwiched between the two electrodes.
- 根据权利要求3所述的制备方法,其特征在于,采用所述模具将所述电极挤压成所述规则形状后,再将所述电解质夹在两个所述电极之间。The method according to claim 3, wherein after the electrode is extruded into the regular shape by using the mold, the electrolyte is sandwiched between the two electrodes.
- 根据权利要求3或4所述的制备方法,其特征在于,所述规则形状为方形板状或者圆筒状。The preparation method according to claim 3 or 4, wherein the regular shape is a square plate shape or a cylindrical shape.
- 根据权利要求1至4中任一项所述的制备方法,其特征在于,制备电极时,先将所述活性炭和面粉混合均匀后,再加入所述溶液中混合均匀得所述电极。The preparation method according to any one of claims 1 to 4, characterized in that, when preparing an electrode, the activated carbon and flour are first mixed uniformly, and then added to the solution and mixed to obtain the electrode.
- 一站式超级电容器,包括电极和电解质,所述电解质夹在两个所述电极之间,其特征在于,所述电极包括重量比为1~1.5:2.5~3:5:5:25~30的面粉、活性炭、磷酸、氯化钠和去离子水,所述电解质包括重量比为4:3~3.5:3~3.5:15~18的面粉、磷酸、氯化钠和去离子水。The one-stop supercapacitor includes an electrode and an electrolyte, and the electrolyte is sandwiched between the two electrodes, wherein the electrode includes a weight ratio of 1 to 1.5: 2.5 to 3: 5: 5: 25 to 30 Flour, activated carbon, phosphoric acid, sodium chloride, and deionized water, the electrolyte includes flour, phosphoric acid, sodium chloride, and deionized water in a weight ratio of 4: 3 to 3.5: 3 to 3.5: 15 to 18.
- 根据权利要求7所述的一站式超级电容器,其特征在于,所述电极包括重量比为1:3:5:5:25的面粉、活性炭、磷酸、氯化钠和去离子水,所述电解质包括重量比为4:3:3:15的面粉、磷酸、氯化钠和去离子水。The one-stop supercapacitor according to claim 7, wherein the electrode comprises flour, activated carbon, phosphoric acid, sodium chloride, and deionized water in a weight ratio of 1: 3: 5: 5: 25, and The electrolyte includes flour, phosphoric acid, sodium chloride, and deionized water in a weight ratio of 4: 3: 3: 15.
- 根据权利要求7所述的一站式超级电容器,其特征在于,所述电解质和每个所述电极的形状、尺寸均一样。The one-stop supercapacitor according to claim 7, wherein the shape and size of the electrolyte and each of the electrodes are the same.
- 根据权利要求7至9中任一项所述的一站式超级电容器,其特征在于,所述电解质和每个所述电极均呈方形板状或者圆筒状。The one-stop supercapacitor according to any one of claims 7 to 9, wherein the electrolyte and each of the electrodes are in a square plate shape or a cylindrical shape.
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- 2018-09-30 WO PCT/CN2018/109055 patent/WO2020062223A1/en active Application Filing
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US20080003166A1 (en) * | 2004-07-15 | 2008-01-03 | Yurii Maletin | Methods of forming nanoporous carbon material and electrodes and electrochemical double layer capacitors therefrom |
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