CN110828198B - Laminated interdigital electrochemical capacitor and preparation method thereof - Google Patents
Laminated interdigital electrochemical capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 150
- 238000004806 packaging method and process Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 17
- 239000013067 intermediate product Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 claims description 15
- 229920002799 BoPET Polymers 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 235000011151 potassium sulphates Nutrition 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
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- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- H—ELECTRICITY
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- 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
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- 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
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- 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
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a laminated interdigital electrochemical capacitor and a preparation method thereof. The capacitor is formed by alternately overlapping active self-supporting electrodes arranged in a shell and diaphragms with electrolytes on two sides, wherein the two adjacent electrodes are respectively and electrically connected with positive and negative electrode leading-out terminals in a back-to-back manner, the electrodes are MXene titanium carbide films and the like, the electrolytes are water or organic electrolytes, and the diaphragms are water or organic electrolyte diaphragms; the method comprises coating electrolyte, pasting a diaphragm and coating electrolyte on the upper surface of the electrode, then pasting the other electrode on one surface of the electrolyte of the previous electrode, then coating the electrolyte, pasting the diaphragm and coating the electrolyte on the upper surface, then repeating the above process more than zero times, pasting the other electrode on one surface of the electrolyte of the multilayer electrode, then electrically connecting the electrodes at two ends of the obtained intermediate product with the positive and negative electrode leading-out terminals respectively, and then packaging the electrodes in a shell to obtain the product. It is extremely easy to commercialize widely as an auxiliary power supply, a backup power supply, a main power supply, and an alternative power supply.
Description
Technical Field
The invention relates to an electrochemical capacitor and a preparation method thereof, in particular to a laminated interdigital electrochemical capacitor and a preparation method thereof.
Background
The electrochemical capacitor is also called as a super capacitor, and has the characteristics of high capacity, high energy density, large current charge and discharge, long cycle life and the like, and is successfully applied in the fields of national defense, aerospace, automobile industry, consumer electronics, communication, electric power, railways and the like, and the application range of the electrochemical capacitor is continuously expanded. The electrochemical capacitor can be mainly used as an auxiliary power source, a backup power source, a main power source, and an alternative power source according to the magnitude of the capacitance, the discharge time, and the discharge amount. Recently, in order to obtain electrochemical capacitors with higher performance, there have been continuous efforts, such as a super capacitor and a method for manufacturing the same, which are disclosed in the patent CN 103762088B of china in 7.7.7.2017. The super capacitor described in the patent of the invention is characterized in that a diaphragm and electrolyte are arranged between active self-supporting electrodes with one side printed with a conductive current collecting metal grid line in a packaging shell, wherein two adjacent active self-supporting electrodes are respectively oppositely connected with a positive electrode lead-out terminal and a negative electrode lead-out terminal; the preparation method comprises the steps of printing a metal grid line, connecting a leading-out electrode end, placing a diaphragm lamination, pre-packaging, injecting liquid, packaging and standing. Firstly, a conductive current collecting metal grid line needs to be printed on an active self-supporting electrode in a product, the structural complexity of the super capacitor is increased, a large amount of conductive agent and binder are used for ensuring that the active self-supporting electrode is in good contact with the conductive current collecting metal grid line, and the use of the inactive materials, namely the current collector, the conductive agent, the binder and the like occupies a large mass ratio and a large volume ratio in the whole electrochemical capacitor, so that the overall performance, namely the capacitance, the energy density and the power density of the product are reduced; secondly, the preparation method cannot obtain a product in which the active material has a higher mass ratio and volume ratio.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a laminated interdigital electrochemical capacitor with a built-in active material having higher mass ratio and volume ratio.
The invention also provides a preparation method of the laminated interdigital electrochemical capacitor.
In order to solve the technical problem of the invention, the technical scheme is that the laminated interdigital electrochemical capacitor consists of a packaging shell internally provided with an active self-supporting electrode, a diaphragm and electrolyte and an electrode leading-out terminal, and particularly comprises the following components in percentage by weight:
the active self-supporting electrode and the diaphragm with electrolytes on two sides are alternately superposed;
the two adjacent active self-supporting electrodes alternately superposed with the diaphragms with electrolytes on two sides are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal in a back-to-back manner;
the active self-supporting electrode is MXene titanium carbide (Ti)3C2Tx) A film, or an MXene carbon nanotube composite film, or an MXene graphene composite film;
the electrolyte is an aqueous electrolyte or an organic electrolyte;
the diaphragm is an aqueous electrolyte diaphragm or an organic electrolyte diaphragm.
As a further improvement of the stacked interdigitated electrochemical capacitor:
preferably, the number of active self-supporting electrodes in the separator in which the active self-supporting electrodes and the electrolyte are alternately stacked is 3 or more.
Preferably, the conductivity of the active self-supporting electrode is more than or equal to 2000S/cm, and the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer.
Preferably, the aqueous electrolyte is sulfuric acid, or phosphoric acid, or potassium hydroxide, or sodium hydroxide, or magnesium sulfate, or potassium sulfate, or sodium sulfate, and the organic electrolyte is lithium bistrifluoromethanesulfonylimide, or tetraethylammonium Tetrafluoroborate (TEABF)4) Or triethylmethylammonium Tetrafluoroborate (TEMABF)4) Or bispyrrolidine tetrafluoroborate (SBPBF)4)。
Preferably, the water system electrolyte membrane is a Japanese NKK-MPF30AC-100 membrane, and the organic system electrolyte membrane is a Japanese NKK TF4535 cellulose membrane, or an NKK TF4530 cellulose membrane, or an NKK TF4050 cellulose membrane.
In order to solve another technical problem of the present invention, another technical solution is adopted in that the method for manufacturing the stacked interdigital electrochemical capacitor comprises the steps of arranging and packaging an active self-supporting electrode, a diaphragm, an electrolyte and an electrode lead-out terminal, and particularly comprises the following main steps:
step 1, firstly coating electrolyte on the upper surface of an active self-supporting electrode, then pasting a diaphragm on the electrolyte to keep the two immersed, and then coating the electrolyte on the diaphragm to obtain the active self-supporting electrode with the upper surface immersed and coated with the electrolyte, the diaphragm and the electrolyte in sequence;
and 3, repeating the process of the step 2 for more than zero times, attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product, electrically connecting the active self-supporting electrodes at two ends of the intermediate product with the positive electrode lead-out terminal and the negative electrode lead-out terminal respectively, and packaging the active self-supporting electrodes in a packaging shell to obtain the laminated interdigital electrochemical capacitor.
As a further improvement of the preparation method of the laminated interdigital electrochemical capacitor:
preferably, the conductivity of the active self-supporting electrode is more than or equal to 2000S/cm, and the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer.
Preferably, the aqueous electrolyte is sulfuric acid, or phosphoric acid, or potassium hydroxide, or sodium hydroxide, or magnesium sulfate, or potassium sulfate, or sodium sulfate, and the organic electrolyte is lithium bistrifluoromethanesulfonylimide, or tetraethylammonium tetrafluoroborate, or triethylmethylammonium tetrafluoroborate, or bispyrrolidinium tetrafluoroborate.
Preferably, the water system electrolyte membrane is a Japanese NKK-MPF30AC-100 membrane, and the organic system electrolyte membrane is a Japanese NKK TF4535 cellulose membrane, or an NKK TF4530 cellulose membrane, or an NKK TF4050 cellulose membrane.
Preferably, the package shell is a PET film package shell or an aluminum plastic film package shell.
Compared with the prior art, the beneficial effects are that:
first, with such a structure, the capacitor of the present invention has the following advantages:
(1) as the active self-supporting electrode adopts the MXene titanium carbide film or the MXene carbon nanotube composite film or the MXene graphene composite film, and the conductive current-collecting metal grid line is not required to be printed on the active self-supporting electrode, the use of a conductive agent and a binder is avoided, the volume ratio and the mass ratio of the active material are greatly increased, the manufacturing cost is greatly reduced, and the miniaturization of a target product is greatly facilitated;
(2) preferred electrolytes and separators laminated between the active self-supporting electrodes not only separate adjacent active self-supporting electrodes but also enable necessary charge transport;
(3) the active self-supporting electrode and the diaphragm with electrolytes on two sides are arranged into a laminated interdigital structure, so that the relative area between the electrodes is increased, the ion transport path is shortened, high power output is obtained, the single target product realizes the ultrahigh mass load of the active material, the ultrahigh performance, namely the surface specific capacitance, the surface energy density and the surface power density, is realized, and the electrode active material keeps the excellent body performance, namely the body specific capacitance, the body energy density and the body power density under the ultrahigh mass load;
(4) the mass load of the electrode active material can be controlled by the number of the electrode units, so that the capacitance capacity of a single target product can be controlled, and the performance of the electrode active material, namely the capacitance, the energy density and the bulk power density, is not influenced;
secondly, the performance of the target product is tested for multiple times and multiple batches by using an electrochemical workstation, and the result shows that the parameter indexes of the electrochemical workstation are superior to those of the prior art.
Thirdly, the preparation method of the invention is simple, scientific and efficient:
the stacked interdigital electrochemical capacitor which is a target product with a built-in active material and higher mass ratio and volume ratio is prepared, and the stacked interdigital electrochemical capacitor has the characteristics of less raw materials, convenience in preparation, low production cost and easiness in industrial scale production; thereby making the desired product extremely susceptible to widespread commercial use as an auxiliary power source, a backup power source, a main power source, and an alternative power source.
Drawings
FIG. 1 shows the electrochemical work of the German Zahner Im6ex model for the preparation of the desired productThe station performs one of the results of the characterization. Wherein the single-electrode mass load of the active self-supporting electrode used in the target product is 6.4mg/cm2The mass load of the half electrode (the outermost active self-supporting electrode) is 3.2mg/cm2The concentration of the electrolyte was 3 mol/L.
Graph a in FIG. 1 is a cyclic voltammogram of the desired product at a scan rate of 2-100mV/s, and it can be seen from graph a that the desired product has good capacitance performance even at a high scan rate of 100 mV/s;
b is the load of the active self-supporting electrode in the target product is 27.2mg/cm2(Mass Loading of Positive electrode active Material or negative electrode active Material) was measured, and it was found that the objective product obtained 5.3F/cm2The ultra-high surface capacitance;
c is a constant current charge and discharge curve chart of the target product, which is at 0.1A/cm2Has a voltage drop of only 0.07V at high current densities;
the Nyquist plot of the target product is shown as d, and it is understood that the equivalent series resistance of the target product is only 0.32 Ω.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
the self-supporting electrode comprises an MXene titanium carbide film, an MXene carbon nanotube composite film and an MXene graphene composite film which are used as active self-supporting electrodes, wherein the conductivity of the active self-supporting electrodes is more than or equal to 2000S/cm;
aqueous electrolytes and organic electrolytes as electrolytes, wherein the aqueous electrolytes are sulfuric acid, phosphoric acid, potassium hydroxide, sodium hydroxide, magnesium sulfate, potassium sulfate and sodium sulfate, and the organic electrolytes are lithium bistrifluoromethanesulfonylimide, tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate and dipyrrolidine tetrafluoroborate;
an aqueous electrolyte membrane and an organic electrolyte membrane as membranes, wherein the aqueous electrolyte membrane is a Japanese NKK-MPF30AC-100 membrane, and the organic electrolyte membrane is a Japanese NKK TF4535 cellulose membrane, a Japanese NKK TF4530 cellulose membrane, or a Japanese NKK TF4050 cellulose membrane;
a PET film packaging shell and an aluminum plastic film packaging shell which are used as packaging shells; wherein, the packaging shell using the water system electrolyte is a PET film packaging shell, and the packaging shell using the organic system electrolyte is an aluminum plastic film packaging shell.
Then:
example 1
The preparation method comprises the following specific steps:
step 1, coating electrolyte on the upper surface of an active self-supporting electrode; wherein the active self-supporting electrode is MXene titanium carbide film, and the electrolyte is sulfuric acid in water-based electrolyte. Then the diaphragm is pasted on the electrolyte to keep the two substances soaked, and then the electrolyte is coated on the diaphragm; wherein the diaphragm is an NKK-MPF30AC-100 diaphragm produced in Japan in an aqueous electrolyte diaphragm, and an active self-supporting electrode with the upper surface being sequentially soaked and coated with an electrolyte, the diaphragm and the electrolyte is obtained.
And 2, firstly, attaching the other active self-supporting electrode to the surface of the last active self-supporting electrode covered with the electrolyte so as to keep the two electrodes soaked, and then coating the electrolyte on the surface of the two electrodes. And then the diaphragm is attached to the electrolyte to keep the electrolyte and the diaphragm to be soaked, and then the electrolyte is coated on the diaphragm to obtain the multilayer active self-supporting electrode with the upper surface sequentially soaked and coated with the electrolyte, the diaphragm and the electrolyte.
Step 3, sticking another active self-supporting electrode on one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product; wherein the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer. And then, after the active self-supporting electrodes at two ends of the intermediate product are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal, the active self-supporting electrodes are packaged in a PET film packaging shell to obtain the laminated interdigital electrochemical capacitor similar to the curve shown in figure 1.
Example 2
The preparation method comprises the following specific steps:
step 1, coating electrolyte on the upper surface of an active self-supporting electrode; wherein the active self-supporting electrode is MXene titanium carbide film, and the electrolyte is sulfuric acid in water-based electrolyte. Then the diaphragm is pasted on the electrolyte to keep the two substances soaked, and then the electrolyte is coated on the diaphragm; wherein the diaphragm is an NKK-MPF30AC-100 diaphragm produced in Japan in an aqueous electrolyte diaphragm, and an active self-supporting electrode with the upper surface being sequentially soaked and coated with an electrolyte, the diaphragm and the electrolyte is obtained.
And 2, firstly, attaching the other active self-supporting electrode to the surface of the last active self-supporting electrode covered with the electrolyte so as to keep the two electrodes soaked, and then coating the electrolyte on the surface of the two electrodes. And then the diaphragm is attached to the electrolyte to keep the electrolyte and the diaphragm to be soaked, and then the electrolyte is coated on the diaphragm to obtain the multilayer active self-supporting electrode with the upper surface sequentially soaked and coated with the electrolyte, the diaphragm and the electrolyte.
Step 3, repeating the process of the step 2 for 3 times, and then attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product; wherein the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer. And then, after the active self-supporting electrodes at two ends of the intermediate product are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal, the active self-supporting electrodes are packaged in a PET film packaging shell to obtain the laminated interdigital electrochemical capacitor similar to the curve shown in figure 1.
Example 3
The preparation method comprises the following specific steps:
step 1, coating electrolyte on the upper surface of an active self-supporting electrode; wherein the active self-supporting electrode is MXene titanium carbide film, and the electrolyte is sulfuric acid in water-based electrolyte. Then the diaphragm is pasted on the electrolyte to keep the two substances soaked, and then the electrolyte is coated on the diaphragm; wherein the diaphragm is an NKK-MPF30AC-100 diaphragm produced in Japan in an aqueous electrolyte diaphragm, and an active self-supporting electrode with the upper surface being sequentially soaked and coated with an electrolyte, the diaphragm and the electrolyte is obtained.
And 2, firstly, attaching the other active self-supporting electrode to the surface of the last active self-supporting electrode covered with the electrolyte so as to keep the two electrodes soaked, and then coating the electrolyte on the surface of the two electrodes. And then the diaphragm is attached to the electrolyte to keep the electrolyte and the diaphragm to be soaked, and then the electrolyte is coated on the diaphragm to obtain the multilayer active self-supporting electrode with the upper surface sequentially soaked and coated with the electrolyte, the diaphragm and the electrolyte.
Step 3, repeating the process of the step 2 for 6 times, and then attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product; wherein the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer. And then, after the active self-supporting electrodes at two ends of the intermediate product are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal, the active self-supporting electrodes are packaged in a PET film packaging shell to obtain the laminated interdigital electrochemical capacitor shown by the curve in figure 1.
Example 4
The preparation method comprises the following specific steps:
step 1, coating electrolyte on the upper surface of an active self-supporting electrode; wherein the active self-supporting electrode is MXene titanium carbide film, and the electrolyte is sulfuric acid in water-based electrolyte. Then the diaphragm is pasted on the electrolyte to keep the two substances soaked, and then the electrolyte is coated on the diaphragm; wherein the diaphragm is an NKK-MPF30AC-100 diaphragm produced in Japan in an aqueous electrolyte diaphragm, and an active self-supporting electrode with the upper surface being sequentially soaked and coated with an electrolyte, the diaphragm and the electrolyte is obtained.
And 2, firstly, attaching the other active self-supporting electrode to the surface of the last active self-supporting electrode covered with the electrolyte so as to keep the two electrodes soaked, and then coating the electrolyte on the surface of the two electrodes. And then the diaphragm is attached to the electrolyte to keep the electrolyte and the diaphragm to be soaked, and then the electrolyte is coated on the diaphragm to obtain the multilayer active self-supporting electrode with the upper surface sequentially soaked and coated with the electrolyte, the diaphragm and the electrolyte.
Step 3, repeating the process of the step 2 for 9 times, and then attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product; wherein the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer. And then, after the active self-supporting electrodes at two ends of the intermediate product are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal, the active self-supporting electrodes are packaged in a PET film packaging shell to obtain the laminated interdigital electrochemical capacitor similar to the curve shown in figure 1.
Example 5
The preparation method comprises the following specific steps:
step 1, coating electrolyte on the upper surface of an active self-supporting electrode; wherein the active self-supporting electrode is MXene titanium carbide film, and the electrolyte is sulfuric acid in water-based electrolyte. Then the diaphragm is pasted on the electrolyte to keep the two substances soaked, and then the electrolyte is coated on the diaphragm; wherein the diaphragm is an NKK-MPF30AC-100 diaphragm produced in Japan in an aqueous electrolyte diaphragm, and an active self-supporting electrode with the upper surface being sequentially soaked and coated with an electrolyte, the diaphragm and the electrolyte is obtained.
And 2, firstly, attaching the other active self-supporting electrode to the surface of the last active self-supporting electrode covered with the electrolyte so as to keep the two electrodes soaked, and then coating the electrolyte on the surface of the two electrodes. And then the diaphragm is attached to the electrolyte to keep the electrolyte and the diaphragm to be soaked, and then the electrolyte is coated on the diaphragm to obtain the multilayer active self-supporting electrode with the upper surface sequentially soaked and coated with the electrolyte, the diaphragm and the electrolyte.
Step 3, repeating the process of the step 2 for 12 times, and then attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product; wherein the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the inner layer. And then, after the active self-supporting electrodes at two ends of the intermediate product are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal, the active self-supporting electrodes are packaged in a PET film packaging shell to obtain the laminated interdigital electrochemical capacitor similar to the curve shown in figure 1.
Then respectively selecting an MXene titanium carbide film or an MXene carbon nanotube composite film or an MXene graphene composite film as an active self-supporting electrode, an aqueous electrolyte and an organic electrolyte as electrolytes, wherein the aqueous electrolyte is sulfuric acid or phosphoric acid or potassium hydroxide or sodium hydroxide or magnesium sulfate or potassium sulfate or sodium sulfate, the organic electrolyte is bis (trifluoromethanesulfonyl) imide lithium or tetraethylammonium tetrafluoroborate or triethylmethylammonium tetrafluoroborate or bis (pyrrolidino) tetrafluoroborate, the aqueous electrolyte membrane and the organic electrolyte membrane are taken as membranes, the aqueous electrolyte membrane is an NKK-MPF30AC-100 membrane produced in Japan, the organic electrolyte membrane is an NKK TF4535 cellulose membrane produced in Japan or an NKK 4530 cellulose membrane or an NKK TF4050 cellulose membrane, and the PET film packaging shell or a PET film packaging shell as a packaging shell, the above examples 1-5 were repeated to also produce stacked interdigitated electrochemical capacitors as shown or approximated by the curves in figure 1.
It will be apparent to those skilled in the art that various modifications and variations can be made in the stacked interdigitated electrochemical capacitor of the present invention and its method of fabrication without departing from the spirit or scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (5)
1. A laminated interdigital electrochemical capacitor is composed of a packaging shell internally provided with an active self-supporting electrode, a diaphragm and electrolyte and an electrode leading-out terminal, and is characterized in that:
the active self-supporting electrode and the diaphragm with electrolytes on two sides are alternately superposed;
the two adjacent active self-supporting electrodes alternately superposed with the diaphragms with electrolytes on two sides are respectively and electrically connected with the positive electrode lead-out terminal and the negative electrode lead-out terminal in a back-to-back manner;
the active self-supporting electrode is an MXene titanium carbide film, an MXene carbon nanotube composite film or an MXene graphene composite film;
the electrolyte is an aqueous electrolyte or an organic electrolyte;
the diaphragm is an aqueous electrolyte diaphragm or an organic electrolyte diaphragm;
the preparation method of the laminated interdigital electrochemical capacitor mainly comprises the following steps:
step 1, firstly coating electrolyte on the upper surface of an active self-supporting electrode, then pasting a diaphragm on the electrolyte to keep the two immersed, and then coating the electrolyte on the diaphragm to obtain the active self-supporting electrode with the upper surface immersed and coated with the electrolyte, the diaphragm and the electrolyte in sequence;
step 2, firstly, attaching another active self-supporting electrode to one surface of the previous active self-supporting electrode, which is covered with the electrolyte, so that the two active self-supporting electrodes are kept wet, coating the electrolyte on the surface of the previous active self-supporting electrode, then attaching a diaphragm to the electrolyte, so that the two active self-supporting electrodes are kept wet, and coating the electrolyte on the diaphragm, so as to obtain a multilayer active self-supporting electrode, the upper surface of which is sequentially wetted and covered with the electrolyte, the diaphragm and the electrolyte;
step 3, repeating the process of the step 2 for more than zero times, then attaching another active self-supporting electrode to one surface of the multilayer active self-supporting electrode covered with the electrolyte to keep the two surfaces soaked to obtain an intermediate product, then electrically connecting the active self-supporting electrodes at two ends of the intermediate product with the positive electrode lead-out terminal and the negative electrode lead-out terminal respectively, and then packaging the active self-supporting electrodes in a packaging shell to obtain the laminated interdigital electrochemical capacitor;
the conductivity of the active self-supporting electrode is more than or equal to 2000S/cm, and the mass load per unit area and the thickness of the active self-supporting electrode at the outermost layer are half of those of the active self-supporting electrode at the inner layer.
2. The stacked interdigitated electrochemical capacitor of claim 1 wherein the number of active self-supporting electrodes in the alternating stack of active self-supporting electrodes and separator with electrolyte on both sides is 3 or more.
3. The stacked interdigital electrochemical capacitor of claim 2, wherein the conductivity of the active self-supporting electrode is equal to or greater than 2000S/cm, and the mass loading per unit area and the thickness of the outermost active self-supporting electrode are half of those of the inner layer.
4. The stacked interdigitated electrochemical capacitor of claim 3 wherein the aqueous electrolyte is sulfuric acid, or phosphoric acid, or potassium hydroxide, or sodium hydroxide, or magnesium sulfate, or potassium sulfate, or sodium sulfate, and the organic electrolyte is lithium bistrifluoromethanesulfonylimide, or tetraethylammonium tetrafluoroborate, or triethylmethylammonium tetrafluoroborate, or bispyrrolidinium tetrafluoroborate.
5. The method for preparing a laminated interdigital electrochemical capacitor of claim 1, wherein the package casing is a PET film package casing or an aluminum plastic film package casing.
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| CN103762088A (en) * | 2013-12-31 | 2014-04-30 | 昆明纳太能源科技有限公司 | Novel super capacitor and manufacturing method thereof |
| CN108257791A (en) * | 2018-01-22 | 2018-07-06 | 西南交通大学 | A kind of MXene paper electrodes and preparation method thereof and micro super capacitor and preparation method thereof |
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| CN103762088A (en) * | 2013-12-31 | 2014-04-30 | 昆明纳太能源科技有限公司 | Novel super capacitor and manufacturing method thereof |
| CN108257791A (en) * | 2018-01-22 | 2018-07-06 | 西南交通大学 | A kind of MXene paper electrodes and preparation method thereof and micro super capacitor and preparation method thereof |
| CN109755027A (en) * | 2019-01-10 | 2019-05-14 | 中国科学院金属研究所 | Composite graphite alkene film, high-energy ultracapacitor and intelligent flexible device |
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