CN114429866B - Planar filter electrochemical capacitor and preparation method thereof - Google Patents
Planar filter electrochemical capacitor and preparation method thereof Download PDFInfo
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- CN114429866B CN114429866B CN202210125591.XA CN202210125591A CN114429866B CN 114429866 B CN114429866 B CN 114429866B CN 202210125591 A CN202210125591 A CN 202210125591A CN 114429866 B CN114429866 B CN 114429866B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- WCSBABHZOSWARI-UHFFFAOYSA-L nickel(2+);selenate Chemical compound [Ni+2].[O-][Se]([O-])(=O)=O WCSBABHZOSWARI-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000004743 Polypropylene Substances 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 229920001155 polypropylene Polymers 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910002521 CoMn Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 5
- 229910052748 manganese Inorganic materials 0.000 claims 5
- 239000008187 granular material Substances 0.000 claims 1
- NZIHMSYSZRFUQJ-UHFFFAOYSA-N 6-chloro-1h-benzimidazole-2-carboxylic acid Chemical compound C1=C(Cl)C=C2NC(C(=O)O)=NC2=C1 NZIHMSYSZRFUQJ-UHFFFAOYSA-N 0.000 abstract description 26
- 238000001914 filtration Methods 0.000 abstract description 21
- 239000007772 electrode material Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical group [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000001566 impedance spectroscopy Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a planar filter electrochemical capacitor and a preparation method thereof. The filter electrochemical capacitor sequentially comprises an upper packaging shell, a first electrode, electrolyte, a diaphragm, a second electrode and a lower packaging shell. The first electrode and the second electrode are two identical symmetrical electrodes, each of which comprises an active material layer and a metal layer, the active material layer is preferably a compound containing nickel, cobalt and manganese, and the metal layer is preferably nickel foil; the electrolyte is preferably KOH or K 2 SO 4 An electrolyte; the separator is preferably a filter paper or a polypropylene porous membrane. The invention also provides two filtering electrochemical capacitors of cobalt-manganese co-doped nickel telluride and cobalt-manganese co-doped nickel selenate, and provides specific structural characteristics of electrode materials, a preparation method thereof and performance indexes of the corresponding filtering electrochemical capacitors. The filter electrochemical capacitor provided by the invention can obtain excellent filter performance at low frequency, and has the advantages of high specific capacitance, simple preparation method, low resistance, low cost and the like.
Description
Technical Field
The invention relates to the field of filter capacitors, in particular to a filter electrochemical capacitor used in the low-frequency field such as commercial power and the like.
Background
The filter capacitor is a common circuit energy storage device and is generally arranged at two ends of the rectifying circuit to reduce the ripple coefficient of alternating current ripple and smooth the direct current output at high efficiency. The filter capacitors are further classified into low-frequency filter capacitors and high-frequency filter capacitors according to their applications in different operating environments. The low-frequency filter capacitor mainly applies circuits with lower frequency, such as mains supply filtering and filtering after transformer rectification, and the working frequency of the low-frequency filter capacitor is consistent with that of the mains supply and is generally 50 Hz in China; the high-frequency filter capacitor is mostly used in a switch circuit, and the working frequency of the high-frequency filter capacitor can reach tens of thousands of hertz.
The filter capacitor has the characteristics of low temperature rise, low loss, high safety and the like, and simultaneously requires larger energy storage capacitance, and most of the filter capacitors currently use aluminum electrolytic capacitors. As a filter capacitor which is currently in widespread use, the capacity of an electrolytic capacitor is not sufficient, although it is already much larger than that of a conventional ceramic capacitor. In many occasions requiring large-capacity filtering, a plurality of electrolytic capacitors are required to be connected in series to meet the filtering requirement, so that the resistance of the whole circuit system can be greatly increased, a large amount of energy is lost, and a large amount of space is occupied.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a planar Filter Electrochemical Capacitor (FEC) and a preparation method thereof, wherein the Filter Electrochemical Capacitor (FEC) obtains higher energy storage through reversible chemical adsorption/desorption or Faraday redox process of active substances, has the advantages of thousands of times higher capacitance than that of the traditional electrolytic capacitor, has excellent power characteristics, high safety and the like, is applied to the field of filter capacitors, can meet the 50 Hz requirement of domestic commercial power at the working frequency, and can be used as a low-frequency filter capacitor device such as commercial power and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme.
The invention provides a planar filter electrochemical capacitor and a preparation method thereof. The filter electrochemical capacitor sequentially comprises an upper packaging shell, a first electrode, electrolyte, a diaphragm, a second electrode and a lower packaging shell; after the encapsulation is completed, standing is carried out for not less than 24 hours at room temperature, then the mixture is placed in a heat treatment furnace, and static heating is carried out for 3 to 5 hours at the temperature of 50 to 70 ℃ in the atmosphere.
In the filtering electrochemical capacitor, the first electrode and the second electrode are two identical symmetrical electrodes, each of which comprises an active material layer and a metal layer, and the active material layer is coated on the metal layer; the active material layer is preferably a nickel cobalt manganese containing compound; the metal layer is preferably a nickel foil.
In the above filter electrochemical capacitor, the electrolyte is preferably KOH or K 2 SO 4 The electrolyte and the separator are preferably filter paper or polypropylene porous membrane.
In the filter electrochemical capacitor, the nickel-cobalt-manganese-containing compound is preferably cobalt-manganese co-doped nickel telluride (NiTe 2 CoMn) or cobalt manganese co-doped nickel selenate (NiSeO 3 :CoMn)。
The cobalt-manganese co-doped nickel telluride (NiTe 2 CoMn) in the shape of nanocube, nmThe side length of the nanocube is 500-900 nm, the surface of the nanocube is of a two-level nanosheet structure, and the nanosheets are crisscrossed to form a network structure of a three-dimensional nanowall, which is expressed as a porous nanomaterial; in NiTe 2 In CoMn, the atomic percent of Ni to Co to Mn is about 80:10:10. The morphology is very favorable for the infiltration and permeation of electrolyte and also favorable for the rapid diffusion and transfer of ions and electrons, thereby being favorable for the rapid response of filtering performance.
Said NiTe 2 The typical preparation process of the CoMn nanomaterial is as follows: weighing 0.8mmol of nickel nitrate, 0.1mmol of cobalt nitrate, 0.1mmol of manganese nitrate, 2.0mmol of Te powder and 3.0mL of hydrazine hydrate (80%), dissolving in 40mL of deionized water to form a solution, transferring into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and magnetically stirring for 12-17 minutes to form a suspension; heating to 180 ℃ in an oven for 12 hours; after the reaction is finished, taking out the autoclave, naturally cooling to room temperature to obtain reaction products, and respectively flushing the reaction products with deionized water and ethanol for 3 times; drying in a drying oven at 60 deg.C for 5-7 hr to obtain NiTe 2 CoMn nanomaterial.
The cobalt-manganese co-doped nickel selenate (NiSeO) 3 CoMn) is a particulate material having a particle size of 9 to 15 μm, each of the microparticles being composed of NiSeO 3 The CoMn two-dimensional sheet layer is formed by stacking layers with the thickness of 30-70 nm, and the gaps between the layers are uniform and are of a two-dimensional lamellar structure; in NiSeO 3 In CoMn, the atomic percent of Ni to Co to Mn is about 90:5:5. The abundant two-dimensional lamellar structure enables the electrolyte to have high specific surface area, can fully contact and infiltrate the material, provides a large number of active sites for ion adsorption/desorption and intercalation/deintercalation, and is also beneficial to rapid diffusion and transfer of ions and electrons, thereby being beneficial to rapid response of filtering performance.
The cobalt-manganese co-doped nickel selenate (NiSeO) 3 CoMn), which is typically prepared by: weighing 0.9mmol of nickel acetate, 0.05mmol of cobalt acetate, 0.05mmol of manganese acetate, 1.0mmol of selenium dioxide and 0.50g of PVP, and dissolving in 40mL of deionized water to form a solution; transferring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and magnetically stirring the mixture for 13 to 18 minutes; high pressure is reversedPlacing the reaction kettle into an oven, heating to 190 ℃ and reacting for 14-16 hours; taking out the autoclave after the reaction is finished, and naturally cooling to room temperature; pouring out supernatant, transferring the turbid solid at the bottom layer into a centrifuge tube, and centrifugally washing for 3 times by using deionized water and ethanol as solvents respectively; the obtained precipitate is dried for 5 to 7 hours at the temperature of 50 to 70 ℃ to obtain the nickel selenate powder.
The beneficial results of the invention are as follows:
1) The filter electrochemical capacitor provided by the invention adopts the symmetrical electrodes, has a simple structure, small volume, low production cost and low equipment investment, is compatible with the existing industrial system, and is suitable for large-scale industrial production.
2) The filter electrochemical capacitor can provide a large specific capacitance which is 3 orders of magnitude larger than that of the traditional electrolytic capacitor, so that the application number requirement of the capacitor in the circuit can be greatly reduced, the system resistance is reduced, the energy loss is reduced, and the space occupation ratio is remarkably saved.
3) Compared with the existing electrolytic capacitor, the filter electrochemical capacitor has the advantages of more excellent filter performance, large capacity, high safety and low leakage current, and can replace the electrolytic capacitor in a circuit system with lower frequency to realize wide application.
4) The filter electrochemical capacitor is flat, two-dimensional in shape and tiny in volume, can be applied to the fields of solid-state electronics, flexible electronics, transparent electronics and other devices, is easy to combine and integrate, and is suitable for products such as miniaturization, portability, intellectualization, mobility and the like.
5) The filtering electrochemical capacitor has high specific capacitance while having filtering performance, has the advantages of filtering and energy storage, can be applied to the green energy fields of solar energy, wind energy, tidal energy and the like, provides the combined action of energy storage and filtering in an intermittent or unstable energy power generation system, and is particularly suitable for power systems requiring high-capacity filtering such as commercial power and the like.
Drawings
Fig. 1 is a schematic diagram of the internal structure of a planar filter electrochemical capacitor according to the present invention.
FIG. 2 is a cobalt-manganese co-doped nickel telluride (NiTe) obtained in example 1 2 SEM image of CoMn).
FIG. 3 is a drawing of NiTe prepared in example 1 2 CoMn filter electrochemical capacitor impedance spectrum Bode curve.
Fig. 4 is a schematic diagram of a rectifying circuit of the planar filter electrochemical capacitor in practical application.
Fig. 5 is a filter pattern formed by the application of the filter electrochemical capacitor of the invention in a rectifying circuit.
FIG. 6 is a cobalt manganese co-doped nickel selenate (NiSeO) prepared in example 2 3 SEM image of CoMn).
FIG. 7 is a NiSeO obtained in example 2 3 CoMn filter electrochemical capacitor impedance spectrum Bode curve.
Detailed Description
The following description is made with reference to examples.
Example 1
Planar cobalt manganese co-doped nickel telluride (NiTe 2 CoMn) filtering electrochemical capacitor sequentially comprises an upper packaging shell, a first electrode, electrolyte, a diaphragm, a second electrode and a lower packaging shell; after the encapsulation is completed, standing is carried out for not less than 24 hours at room temperature, then the mixture is placed in a heat treatment furnace, and static heating is carried out for 3 to 5 hours at the temperature of 50 to 70 ℃ in the atmosphere. The first electrode and the second electrode are two identical symmetrical electrodes, and the nanometer NiTe 2 Coating CoMn active substance on nickel foil metal layer, electrolyte is KOH electrolyte, and diaphragm is filter paper.
The cobalt-manganese co-doped nickel telluride (NiTe 2 CoMn), which is in the shape of a nanocube, the side length of the nanocube is 500-900 nm, the surface of the nanocube is in a secondary nanosheet structure, and the nanosheets are crisscrossed to form a network structure of a three-dimensional nanoshell, which is expressed as a porous nanomaterial; in NiTe 2 In CoMn, the atomic percent of Ni to Co to Mn is about 80:10:10. The morphology is very favorable for the infiltration and permeation of electrolyte and also favorable for the rapid diffusion and transfer of ions and electrons, thereby being favorable for the rapid response of filtering performance.
Said NiTe 2 The typical preparation process of the CoMn nanomaterial is as follows: weighing 0.8mmol of nickel nitrate, 0.1mmol of cobalt nitrate, 0.1mmol of manganese nitrate, 2.0mmol of Te powder and 3.0mL of hydrazine hydrate (80%), dissolving in 40mL of deionized water to form a solution, transferring into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and magnetically stirring for 12-17 minutes to form a suspension; heating to 180 ℃ in an oven for 12 hours; after the reaction is finished, taking out the autoclave, naturally cooling to room temperature to obtain reaction products, and respectively flushing the reaction products with deionized water and ethanol for 3 times; drying in a drying oven at 60 deg.C for 5-7 hr to obtain NiTe 2 CoMn nanomaterial.
The nickel telluride/nickel mesh electrode prepared under the above conditions has substantially uniform physicochemical properties. X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and x-ray energy scattering spectroscopy (EDX) were performed on the sample, which showed that the product was NiTe 2 The atomic percent of Ni to Co to Mn of the phase structure is about 8:1:1. Fig. 1 is a schematic structural diagram of a planar filter electrochemical capacitor. FIG. 2 shows the resulting NiTe 2 Typical SEM pictures of CoMn nanomaterial.
According to FIG. 1, a planar NiTe is assembled 2 CoMn filter electrochemical capacitor. The assembled filter electrochemical capacitor is subjected to electrochemical performance tests, including constant current charge and discharge (GCD), cyclic Voltammetry (CV) and impedance spectroscopy (EIS). Fig. 3 is a typical impedance spectrum Bode curve, derived from EIS data, at a fixed frequency, the larger the corresponding negative phase angle, the stronger the capacitance characteristic, where 45 ° is a critical boundary distinguishing the device capacitance and the resistance, and the corresponding negative phase angle of the filter electrochemical capacitor is 67.5 ° at 120hz (dual grid frequency, e.g. grid frequency of 60hz in the united states) and 70.4 ° at 100 hz (dual grid frequency, e.g. grid frequency of 50 hz in china), which means that the filter electrochemical capacitor can be fully applied to solve the filtering problem in an actual grid circuit.
The capacitance value under different alternating current frequencies can be calculated according to EIS data, and the specific area capacitance reaches 957 mu F cm under the characteristic frequency of 120Hz -2 (much larger than commercial aluminum)300 mu F cm of electrolytic capacitor -2 Is a specific area capacitance of (c). The relevant performance index is shown in the attached table 1.
Fig. 4 is a schematic diagram of a rectifying circuit in practical application. NiTe prepared in example 1 2 The CoMn filter electrochemical capacitor is arranged in a rectifying circuit shown in figure 4, a filter pattern shown in figure 5 is obtained through output voltage, a rectifying module consisting of 4 diodes converts a 60Hz bidirectional sinusoidal alternating current input signal into a 120Hz unidirectional sinusoidal alternating current signal (the signal has certain voltage loss before and after rectification due to inherent voltage drop of the diodes), and the rectified unidirectional sinusoidal alternating current signal passes through NiTe 2 The CoMn filtering electrochemical capacitor is converted into a direct current signal, and the whole alternating current-direct current conversion process is completed.
Example 2
Planar cobalt manganese co-doped nickel selenate (NiSeO) 3 CoMn) filtering electrochemical capacitor sequentially comprises an upper packaging shell, a first electrode, electrolyte, a diaphragm, a second electrode and a lower packaging shell; after the encapsulation is completed, standing is carried out for not less than 24 hours at room temperature, then the mixture is placed in a heat treatment furnace, and static heating is carried out for 3 to 5 hours at the temperature of 50 to 70 ℃ in the atmosphere. The first electrode and the second electrode are two identical symmetrical electrodes, and the nanometer NiSeO 3 Coating CoMn active substance on nickel foil metal layer, and its electrolyte is K 2 SO 4 And the electrolyte and the diaphragm are polypropylene porous films.
The cobalt-manganese co-doped nickel selenate (NiSeO) 3 CoMn) is a particulate material having a particle size of 9 to 15 μm, each of the microparticles being composed of NiSeO 3 The CoMn two-dimensional sheet layer is formed by stacking layers with the thickness of 30-70 nm, and the gaps between the layers are uniform and are of a two-dimensional lamellar structure; in NiSeO 3 In CoMn, the atomic percent of Ni to Co to Mn is about 90:5:5. The abundant two-dimensional lamellar structure enables the electrolyte to have high specific surface area, can fully contact and infiltrate the material, provides a large number of active sites for ion adsorption/desorption and intercalation/deintercalation, and is also beneficial to rapid diffusion and transfer of ions and electrons, thereby being beneficial to rapid response of filtering performance.
The cobalt-manganese alloyDoped nickel selenate (NiSeO) 3 CoMn), which is typically prepared by: weighing 0.9mmol of nickel acetate, 0.05mmol of cobalt acetate, 0.05mmol of manganese acetate, 1.0mmol of selenium dioxide and 0.50g of PVP, and dissolving in 40mL of deionized water to form a solution; transferring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and magnetically stirring the mixture for 13 to 18 minutes; putting the high-pressure reaction kettle into a baking oven, heating to 190 ℃ and reacting for 14-16 hours; taking out the autoclave after the reaction is finished, and naturally cooling to room temperature; pouring out supernatant, transferring the turbid solid at the bottom layer into a centrifuge tube, and centrifugally washing for 3 times by using deionized water and ethanol as solvents respectively; the obtained precipitate is dried for 5 to 7 hours at the temperature of 50 to 70 ℃ to obtain the nickel selenate powder.
The nickel telluride/nickel mesh electrode prepared under the above conditions has substantially uniform physicochemical properties. X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and x-ray energy scattering spectroscopy (EDX) were performed on the sample, which showed that the product was NiSeO 3 The atomic percent of Ni to Co to Mn of the phase structure is about 90:5:5. FIG. 6 is a diagram of a resulting NiSeO 3 Typical SEM pictures of CoMn nanomaterial.
According to FIG. 1, a planar NiSeO is assembled 3 CoMn filter electrochemical capacitor. The assembled filter electrochemical capacitor is subjected to electrochemical performance tests, including constant current charge and discharge (GCD), cyclic Voltammetry (CV) and impedance spectroscopy (EIS). Fig. 7 is a typical impedance spectrum Bode curve, derived from EIS data, at a fixed frequency, the larger the corresponding negative phase angle, the stronger the capacitance characteristic, where 45 ° is a critical boundary distinguishing the device capacitance and the resistance, and the corresponding negative phase angle of the filter electrochemical capacitor is 70.1 ° at 120hz (dual grid frequency, e.g., grid frequency of 60hz in the united states) and 72.9 ° at 100 hz (dual grid frequency, e.g., grid frequency of 50 hz in china), which means that the filter electrochemical capacitor can be fully applied to solve the filtering problem in an actual grid circuit.
According to EIS data, capacitance values under different alternating current frequencies can be calculated, and the specific area capacitance reaches 1215 mu F cm under the characteristic frequency of 120Hz -2 (300. Mu.F cm far greater than commercial aluminum electrolytic capacitors) -2 Specific area of electricityCapacity). The relevant performance index is shown in the attached table 1.
NiSeO obtained in example 2 3 The CoMn filter electrochemical capacitor is arranged in the rectifying circuit shown in the figure 4, and a filter pattern similar to that of the figure 5 can be obtained, so that the whole AC-DC conversion process is realized.
Claims (5)
1. A planar filter electrochemical capacitor, characterized by: the filter electrochemical capacitor sequentially comprises an upper packaging shell, a first electrode, electrolyte, a diaphragm, a second electrode and a lower packaging shell; the first electrode and the second electrode are two identical symmetrical electrodes, each of which consists of an active material layer and a metal layer, and the active material layer is coated on the metal layer; the active material layer is a compound containing nickel, cobalt and manganese; the metal layer is nickel foil;
the preparation method of the compound containing nickel, cobalt and manganese comprises the following steps: 0.9mmol of nickel acetate, 0.05mmol of
Dissolving cobalt acetate, manganese acetate 0.05mmol, selenium dioxide 1.0mmol and PVP 0.50g in deionized water 40mL to form a solution; transferring into a polytetrafluoroethylene high-pressure reaction kettle, and stirring; putting the high-pressure reaction kettle into a baking oven, heating to 190 ℃ and reacting for 14-16 hours; taking out after the reaction is finished, and naturally cooling to room temperature; pouring out supernatant, transferring the turbid solid at the bottom layer into a centrifuge tube, and centrifugally washing for a plurality of times by using deionized water and ethanol as solvents respectively; and drying the obtained precipitate at 50-70 ℃ for 5-7 hours to obtain the compound powder containing nickel, cobalt and manganese.
2. A planar filter electrochemical capacitor as claimed in claim 1, wherein: the compound containing nickel, cobalt and manganese is cobalt and manganese co-doped nickel selenate, namely NiSeO 3 :CoMn。
3. A planar filter electrochemical capacitor as claimed in claim 2, wherein: the cobalt-manganese co-doped nickel selenate is a micron granular material with the grain size of 9-15 mu m, and each micron grain is composed of NiSeO 3 CoMn two-dimensionalThe laminated layers are stacked, the thickness of the layers is 30-70 nm, the gaps among the layers are uniform, and the laminated layer is of a two-dimensional laminated structure.
4. A planar filter electrochemical capacitor as claimed in claim 3, wherein: in the cobalt-manganese Co-doped nickel selenate, the atomic percentage of Ni to Co to Mn is 90:5:5.
5. A planar filter electrochemical capacitor as claimed in claim 1, wherein: the electrolyte is KOH or K 2 SO 4 An electrolyte; the membrane is filter paper or polypropylene porous membrane.
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