CN108962626B - A composite material with pn junction structure for supercapacitor - Google Patents
A composite material with pn junction structure for supercapacitor Download PDFInfo
- Publication number
- CN108962626B CN108962626B CN201810923104.8A CN201810923104A CN108962626B CN 108962626 B CN108962626 B CN 108962626B CN 201810923104 A CN201810923104 A CN 201810923104A CN 108962626 B CN108962626 B CN 108962626B
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- type
- mno
- powder
- type semiconductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000003990 capacitor Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 41
- 150000004706 metal oxides Chemical class 0.000 claims description 41
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 25
- 239000007772 electrode material Substances 0.000 claims description 22
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910002113 barium titanate Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- -1 MgFe2O4 Inorganic materials 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910002929 BaSnO3 Inorganic materials 0.000 claims description 5
- 229910004774 CaSnO3 Inorganic materials 0.000 claims description 5
- 229910002971 CaTiO3 Inorganic materials 0.000 claims description 5
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 5
- 229910016516 CuFe2O4 Inorganic materials 0.000 claims description 5
- 229910017163 MnFe2O4 Inorganic materials 0.000 claims description 5
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims description 5
- 229910004410 SrSnO3 Inorganic materials 0.000 claims description 5
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 5
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 claims description 5
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims description 5
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 5
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 4
- 229910002969 CaMnO3 Inorganic materials 0.000 claims description 4
- 229910002328 LaMnO3 Inorganic materials 0.000 claims description 4
- 229910003387 SrMnO3 Inorganic materials 0.000 claims description 4
- 229910003097 YBa2Cu3O7−δ Inorganic materials 0.000 claims description 4
- 238000004026 adhesive bonding Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910004416 SrxMnO3 Inorganic materials 0.000 claims 2
- 238000004146 energy storage Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 229910010252 TiO3 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- 229910008651 TiZr Inorganic materials 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910006364 δ-MnO2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- H01G11/24—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
- H01G11/46—Metal oxides
-
- 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)
Abstract
The invention relates to a super capacitorThe method is that p-type semi-conductive oxide powder and n-type semi-conductive oxide powder are physically or chemically processed to form pn junctions between p-type oxide particles and n-type oxide particles, and the oxide particles with the pn junctions can improve the resistance value of the super capacitor material and simultaneously rapidly compensate inserted charges in the charging/discharging process through the pn junctions, so that the problem of great reduction of the resistance value caused by introduction of carbon related materials or metal powder is avoided, the working voltage is greatly improved, and the energy storage density is increased. The composite material obtained by the method of the invention and the original p-type oxide (such as MnO)2) In comparison, the specific capacitance can be increased in addition to the operating voltage.
Description
Technical Field
The invention relates to a composite material with a pn junction structure for a super capacitor, a super capacitor electrode material and a preparation method thereof, and belongs to the technical field of material preparation.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery. The super capacitor can be divided into two categories, namely an electric double layer capacitor and a Faraday pseudo capacitor according to different energy storage mechanisms. The electric double layer capacitor generates stored energy by mainly carrying out adsorption on the surface of an electrode through pure electrostatic charges. The Faraday pseudocapacitor is mainly characterized in that reversible redox reaction is carried out on the surface and the vicinity of the surface of a Faraday pseudocapacitor active electrode material (such as transition metal oxide) to generate Faraday pseudocapacitor, so that energy storage and conversion are realized. In general, the Faraday pseudocapacitance is generated not only on the surface of the electrode but also in the entire interior of the electrode, and thus a capacitance higher than that of the electric double layer can be obtainedHigh capacitance and energy density. Under the condition of the same electrode area, the Faraday pseudocapacitance can be 10-100 times of the electric capacity of the electric double layer. In particular MnO2The material is a typical material, has very high specific capacitance theoretically due to low price, is a star material of a super capacitor, and is widely researched.
At present, a super capacitor has a wide application background in an intelligent start-stop control system (light hybrid power system) of an automobile, and particularly shows more prominently on a plug-in hybrid power automobile. Medium and micro supercapacitors have found widespread use in small mechanical devices such as computer memory systems, cameras, audio equipment and auxiliary equipment for intermittent power usage. And the large-size cylindrical super capacitor is mostly used in the automobile field and natural energy collection.
However, the relatively high cost and energy density of supercapacitors compared to lithium batteries has made them vulnerable to cooling in many areas and in practice they have always been replaced by batteries. If the super capacitor is broken through once technically, the super capacitor can generate great driving force for the development of new energy industry.
In order to increase the energy storage density of supercapacitors, most research has focused on increasing the specific capacitance. Since the improvement of the electron transport speed, that is, the reduction of the internal resistance is quite effective for improving the specific capacitance of the oxide faradaic supercapacitor material, many research ideas are to mix high-conductivity substances such as C powder, silver powder and even graphene into the oxide. Although the specific capacitance can be increased, the operating voltage is also greatly reduced due to a large reduction in the internal resistance. And the amount of stored energy of the capacitor is proportional to the square of the operating voltage, e.g.
Reducing the internal resistance is not favorable for improving the energy storage density of the super capacitor.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems of the prior art, the present invention provides a composite material having a pn junction structure for a supercapacitor, a supercapacitor electrode material, and a method for preparing the same.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a composite material for a supercapacitor, which has a pn junction structure formed by a p-type semiconductive metal oxide and an n-type semiconductive metal oxide.
Further, the p-type semiconducting metal oxide is MnO2、RuO2、Mn3O4、 MnO、CaMnO3、SrMnO3、LaMnO3、La1-xSrxMnO3NiO, CoO, FeO, CuO, Cu (where x is 0 to 0.7)2O、YBa2Cu3O7－δAnd Bi2Sr2Ca2Cu3O10－δAt least one of;
the n-type semiconductive metal oxide is Fe3O4、ZnFe2O4、CuFe2O4、CoFe2O4、 NiFe2O4、MnFe2O4、(NiCuZn)Fe2O4(NiCuZn ferrite), MgFe2O4、 ZnO、TiO2、CaTiO3、BaTiO3、SrTiO3、(SrBa)TiO3(BST)、Ba(TiZr) O3(BZT)、SnO2、CaSnO3、BaSnO3、SrSnO3And BiFeO3At least one of (1).
Further, the molar ratio of the metal atoms in the p-type semiconductive metal oxide to the n-type semiconductive metal oxide is 1-9: 9 to 1.
A preparation method of a supercapacitor electrode material comprises the following steps:
s1, treating the metal oxide powder capable of realizing n-type semi-conduction in a reducing atmosphere or making the metal oxide powder semi-conductive by a donor doping method;
s2, growing or combining an n-type semi-conductive metal oxide powder or the n-type semi-conductive metal oxide powder obtained in the step S1 on the surface or the interface of the n-type semi-conductive metal oxide powder by a physical or chemical method to form a powder of a pn junction;
and S3, gluing and pressing the powder with the pn junction obtained in the S2 to form the electrode material of the supercapacitor.
In the above-described production method, preferably, in step S1, the n-type semiconductive metal oxide includes Fe3O4、ZnFe2O4、CuFe2O4、CoFe2O4、NiFe2O4、MnFe2O4、 (NiCuZn)Fe2O4(NiCuZn ferrite), MgFe2O4、ZnO、TiO2、CaTiO3、 BaTiO3、SrTiO3、(SrBa)TiO3(BST)、Ba(TiZr)O3(BZT)、SnO2、 CaSnO3、BaSnO3、SrSnO3、BiFeO3At least one of (1).
In step S1, some of the oxide powders need not be processed, and the synthesized oxide powders are semiconducting metal oxides, and the process proceeds to the next step. Such as Fe3O4、ZnFe2O4、CuFe2O4、CoFe2O4、 NiFe2O4、MnFe2O4、(NiCuZn)Fe2O4(NiCuZn ferrite), MgFe2O4And the like.
And TiO is required to be treated in a reducing atmosphere2、CaTiO3、BaTiO3、SrTiO3、(SrBa) TiO3(BST)、Ba(TiZr)O3(BZT)、SnO2、CaSnO3、BaSnO3、SrSnO3ZnO, etc., and the reducing atmosphere refers to a method of doping a donor in an atmosphere of hydrogen, CO, etc., and refers to BaTiO3、SrTiO3、(SrBa)TiO3(BST)、Ba(TiZr)O3(BZT)、SnO2Etc. by doping with high-valent ionsSuch as Sb5+、Nb5+And Bi3+And rare earth ions (the latter two classes are not used for SnO2) And carrying out high-temperature treatment at 800-1350 ℃ to make the semiconductor.
The production method as described above, preferably, in step S2, the p-type semiconductive metal oxide includes MnO2、RuO2、Mn3O4、MnO、CaMnO3、SrMnO3、LaMnO3、 La1-xSrxMnO3(wherein x is 0 to 0.7), NiO, CoO, FeO, CuO, Cu2O、YBa2Cu3O7－δ、Bi2Sr2Ca2Cu3O10－δAt least one of (1).
Preferably, in step S2, the n-type semiconductive metal oxide and the p-type semiconductive metal oxide are used in an amount such that the molar ratio of metal atoms in the n-type semiconductive metal oxide to the p-type semiconductive metal oxide is 1 to 9: 9-1.
The preparation method as described above, preferably, in step S2, the physical or chemical method includes: evaporation, hydrothermal method, chemical liquid phase precipitation, sol-gel method, and the like.
The vapor deposition is to evaporate a target material by means of high temperature, laser, plasma, etc., and then condense the target material at a specific position, so that a heterojunction (such as a pn junction), a metal electrode, etc. can be obtained by the method.
The hydrothermal method is a method which mainly uses an aqueous solution as a reaction medium, and heats reactants containing a liquid phase (such as water, an organic solvent and the like) in a closed reaction container to enable the temperature in a system to exceed the boiling point of the contained liquid phase so as to generate a certain pressure in the system, so that substances perform a series of chemical reactions in the liquid phase to prepare the required product.
The chemical liquid phase precipitation method is that different soluble metal salts are mixed in a solution state, then a precipitant is added into the solution, and the solution reacts under certain temperature and other conditions to form a precipitate, wherein the precipitate can be a desired product or a precursor thereof, and if the precipitate is the precursor, the precursor needs to be further thermally treated, so that the desired substance is obtained. Since the process is simple to carry out, especially if the product is precipitated directly without heat treatment. The latter preferred embodiment therefore predominates over this method.
Specifically, it comprises the following steps: metal oxide powder capable of n-type semi-conduction (such as BaTiO)3、Ba0.9Sr0.1TiO3Etc.) heat-treating in a reducing atmosphere to make it semiconductive; adding the semiconducting n-type semiconducting metal oxide into a soluble metal salt solution capable of generating a precipitate as the p-type semiconducting metal oxide, adding a precipitator at a certain temperature of 60-80 ℃, and stirring to obtain the precipitate, namely the ultrahigh dielectric constant composite material with the pn junction.
Further, the molar ratio of metal atoms of the n-type semiconductive metal oxide to the p-type semiconductive metal oxide is preferably 1 to 3: 3 to 1.
The sol-gel method is a method in which an organic or inorganic compound is solidified by solution, sol, or gel, and then heat-treated at a high temperature to form an oxide or other compound solid.
In the above production method, preferably, in step S3, the pressing condition is 1MPa to 100 MPa.
A supercapacitor electrode material obtained by compounding a composite material prepared by the above method with an electrolyte and an electrode (e.g., foamed Ni) by gluing, pressing, and the like.
Further, the composite method may be a press molding method, a coating method, or a film-forming lamination method.
(III) advantageous effects
The invention has the beneficial effects that:
the invention can form pn junctions between the p-type oxide particles and the n-type oxide particles, the oxide particles with the pn junctions can improve the resistance value of the material of the super capacitor, and simultaneously, the pn junctions quickly compensate the inserted charges in the process of charging/discharging, thereby greatly improving the working voltage and increasing the energy storage density. Therefore, the problem of great reduction of resistance caused by introduction of a large amount of carbon-related materials or metal powder is avoided, the specific capacitance is improved, the working voltage is not limited by the energy storage material and is close to the decomposition voltage of the electrolyte, and the energy storage density is greatly increased.
The method has simple preparation and low cost, and is easy for large-scale industrial production. The capacitor prepared by the method has high specific capacitance.
The super capacitor electrode material prepared by the invention is characterized in that insertion charges in the process of flushing/discharging are quickly compensated through a pn junction, and the resistance of the energy storage material is increased, so that the working voltage is greatly increased, the working voltage can be close to the decomposition voltage of an electrolyte without being limited by the energy storage material, and the energy storage density is increased. The working voltage of the conventional common super capacitor is 3V, because a large amount of carbon powder or metal powder or even graphene is added, the resistance of the material is reduced too much, so that the super capacitor cannot work under higher voltage, otherwise, the current is too large to cause the damage of a device.
Drawings
FIG. 1 is an XRD pattern of the composite material prepared in example 1;
FIG. 2 is an electron micrograph of the composite prepared in example 1;
FIG. 3 shows a composite material prepared in each example and comparative example MnO2Cyclic voltammetry characteristics of (a);
FIG. 4 is an XRD pattern of the composite material prepared in example 2;
FIG. 5 is an electron micrograph of the composite prepared in example 2;
FIG. 6 is an XRD pattern of the composite material prepared in example 3;
FIG. 7 is an electron micrograph of the composite prepared in example 3.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
MnO in this embodiment2According to the chemical reaction equation:
MnSO4+H2O2+2NaOH＝MnO2+2H2O+Na2SO4
to complete.
Firstly, 4.66g of BaTiO3Powder is in H2Heat treatment is carried out for 8 hours at 900 ℃ in air.
The composite material with the pn junction is obtained by adopting an in-situ synthesis method. Weighing 1.6g NaOH, putting into a beaker, adding 200ml deionized water for dissolving, and carrying out semi-conducting treatment on the BaTiO3The powder is transferred into a prepared NaOH solution, stirred vigorously and heated to 60 ℃ to be used as a base solution. Weigh 3.38gMn (SO)4)·H2O, put into a small beaker, add 50ml of H2O and 5ml of 30% H2O2The resulting solution was dissolved to form a titration solution. Dropwise adding the titration solution into the base solution, maintaining at 60 deg.C and stirring vigorously to obtain black brown precipitate, filtering, oven drying, and subjecting the obtained composite powder to X-ray diffraction (XRD) with diffraction pattern shown in figure 1, wherein the powder has delta-MnO2And BaTiO3Two phases. Scanning the obtained composite powder by an electron microscope, and obtaining an SEM shown in figure 2. From the figure, the lamellar delta-MnO can be seen2Has been completely fragmented, is mixed with BaTiO3The powder particles are tightly bound together to form fine particle aggregates forming a pn junction structure. The large blocky particles beside the BaTiO are individual large particles3。
And mixing the obtained composite powder with 75%, 20% and 5% of acetylene black and polytetrafluoroethylene glue by mass ratio, coating the mixture on a 10 x 10mm foam Ni square piece, and applying 2MPa pressure to further and tightly combine the powder and the piece so as to prepare the electrode material of the super capacitor. After the supercapacitor electrode material is soaked in 1mol/L sodium sulfate electrolyte for 12 hours, cyclic voltammetry characteristics are tested, as shown in FIG. 3. High performance MnO is also given in FIG. 32For comparison. MnO2The specific capacitance of (a) is 120F/g, and the composite material with a pn junction structure reaches 560F/g. Illustrating MnO having pn junction structure prepared by the present invention2With BaTiO3The composite material can effectively improve the specific capacitance.
Example 2
MnO in this embodiment2According to the chemical reaction equation:
MnSO4+H2O2+2NaOH＝MnO2+2H2O+Na2SO4
to complete.
The specific operation is as follows:
(1) firstly 0.0226gY2O3(yttria) and 4.46g Ba0.9Sr0.1TiO3(BST) powder was uniformly mixed and ground for 1 hour with an agate mortar, and then briquetted under 1MPa and sintered for 1 hour at 1280 ℃ in air to be semiconductive. The cooled porcelain body is crushed and sieved by a 300-mesh sieve. The powder appeared light blue.
(2) The composite material with the pn junction is obtained by adopting an in-situ synthesis method. Weighing 1.6g of NaOH, putting into a beaker, and adding 200ml of deionized water for dissolving; and (2) transferring the BST powder subjected to the semi-conducting treatment in the step (1) into a prepared NaOH solution, violently stirring and heating to 80 ℃ to be used as a base solution. Weighing 3.38g of MnSO4·H2O, put into a small beaker, add 50ml of H2O and 5ml of 30% H2O2The resulting solution was dissolved to form a titration solution. Dropwise adding the titration solution into the base solution, maintaining at 80 deg.C and stirring vigorously to obtain black brown precipitate, filtering, oven drying, and subjecting the obtained composite powder to X-ray diffraction (XRD) with diffraction pattern shown in FIG. 4, wherein the powder has delta-MnO2And BST two phases. Scanning the obtained composite powder by an electron microscope to obtain SEM shown in figure 5. From the figure, the lamellar delta-MnO can be seen2Has been completely fragmented and tightly bonded with BST powder particles to form fine particle aggregates to form a pn junction structure.
The obtained composite powder, acetylene black and polytetrafluoroethylene glue are mixed according to the mass ratio of 75%, 20% and 5% and then coated on a 10 x 10mm foam Ni square piece, 2MPa pressure is applied to enable the composite powder to be further and tightly combined to prepare a supercapacitor electrode material, and the supercapacitor electrode material is soaked in 1mol/L sodium sulfate electrolyte for 12 hours and then tested for cyclic voltammetry characteristics, as shown in figure 3. High performance MnO is also given in FIG. 32For comparison. MnO2Has a pn junction structure and a specific capacitance of 120F/g2The electrode material of the super capacitor prepared by the electrode material and the BST composite material reaches 390F/g. Illustrating MnO having pn junction structure prepared by the present invention2The composite material with BST can effectively improve the specific capacitance.
Example 3
Preparation of ultra-high dielectric constant composite materials by chemical liquid phase precipitation, wherein MnO is2According to the chemical reaction equation:
MnSO4+H2O2+2NaOH＝MnO2+2H2O+Na2SO4
to complete.
The specific operation is as follows:
(1) first 1.628g of ZnO was subjected to a heat treatment at 800 ℃ for 1h in hydrogen to make it semiconductive.
(2) The composite material with the pn junction is obtained by adopting an in-situ synthesis method. Weighing 1.6g of NaOH and putting into a beaker, and adding 500ml of deionized water for dissolving; transferring the ZnO powder subjected to the semi-conducting treatment in the step (1) into a prepared NaOH solution, violently stirring and heating to 60 ℃ to be used as a base solution. Weighing 3.38g of MnSO4·H2O, put into a small beaker, add 50ml of H2O and 5ml of 30% H2O2The resulting solution was dissolved to form a titration solution. Dropwise adding the titration solution into the base solution, maintaining at 60 deg.C and stirring vigorously to obtain black brown precipitate, filtering, oven drying, and subjecting the obtained composite powder to X-ray diffraction (XRD) with diffraction pattern shown in FIG. 6, wherein the powder has delta-MnO2And ZnO two phases. Scanning the obtained composite powder by an electron microscope to obtain SEM shown in FIG. 7. From the figure, the lamellar delta-MnO can be seen2Has been completely fragmented, and is tightly combined with ZnO powder particles to form fine particle aggregates to form a pn junction structure.
Mixing the obtained composite powder with 75%, 20% and 5% of acetylene black and polytetrafluoroethylene glue by mass ratio, coating the mixture on a 10 x 10mm foam Ni square sheet, and applying 2MPa pressure to further tightly combine the powder and the foam Ni square sheet to prepare the electrode material of the super capacitor, wherein the thickness of the electrode material is 1mAfter being soaked in an ol/L sodium sulfate electrolyte for 12 hours, the cyclic voltammetry characteristic, MnO, is tested2Has a pn junction structure and a specific capacitance of 120F/g2The electrode material of the super capacitor made of the ZnO composite material reaches 370F/g. Illustrating MnO having pn junction structure prepared by the present invention2The composite material with ZnO can effectively improve the specific capacitance.
Comparative example
In this comparative example, MnO2According to the chemical reaction equation:
MnSO4+H2O2+2NaOH＝MnO2+2H2O+Na2SO4
to complete.
The specific operation is as follows:
weighing 1.6g of NaOH, putting into a beaker, and adding 200ml of deionized water for dissolving; vigorously stirred and heated to 60 ℃ as a base liquid. Weighing 3.38g of MnSO4·H2O, put into a small beaker, and 50ml of H is added2O and 5ml of 30% H2O2The resulting solution was dissolved to form a titration solution. Dropwise adding the titration solution into the base solution, maintaining the temperature at 60 ℃ and stirring vigorously to obtain a dark brown precipitate, namely MnO2After filtering and drying, the obtained dark brown precipitate, acetylene black and polytetrafluoroethylene glue are mixed according to the mass ratio of 75%, 20% and 5% and then coated on a 10 x 10mm foam Ni square piece, 2MPa pressure is applied to further combine the materials tightly so as to prepare the electrode material of the super capacitor, after the electrode material is soaked in 1mol/L sodium sulfate electrolyte for 12 hours, the cyclic voltammetry characteristic is tested and is shown in figure 4, and the specific capacitance is 120F/g.
At present, the research on the material of the super capacitor is mostly concentrated on MnO2In modification, the basic idea is to add metal powder with high conductivity, graphene and the like to improve the electron compensation speed during ion insertion. This does increase the MnO2However, the resistance of the active material is greatly reduced, and the voltage applied to the electrolyte is increased during actual operation, while the voltage applied to the active material is reduced, which is greatly disadvantageous for increasing the operating voltage of the supercapacitor. Solution of the inventionIs through MnO2The method has the advantages that firstly, the voltage drop is increased in the active medium, so that the ion insertion speed in the active medium is increased, and the efficiency is improved. And secondly, the voltage drop applied to the electrolyte is reduced, so that the window voltage of the whole system is increased, and the working voltage and the energy storage density are increased.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art can change or modify the technical content disclosed above into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (3)
1. A composite material with a pn junction structure for a super capacitor is characterized in that the pn junction structure is a pn junction formed by a p-type semiconductive metal oxide and an n-type semiconductive metal oxide;
the p-type semiconductive metal oxide is MnO2、RuO2、Mn3O4、MnO、CaMnO3、SrMnO3、LaMnO3、La1- xSrxMnO3、NiO、CoO、FeO、Cu2O、YBa2Cu3O7－δAnd Bi2Sr2Ca2Cu3O10－δAt least one of;
the n-type semiconductive metal oxide is Fe3O4、ZnFe2O4、CuFe2O4、CoFe2O4、NiFe2O4、MnFe2O4NiCuZn ferrite, MgFe2O4、TiO2、CaTiO3、BaTiO3、SrTiO3、BST、BZT、SnO2、CaSnO3、BaSnO3、SrSnO3And BiFeO3At least one of;
the molar ratio of metal atoms in the p-type semiconductive metal oxide to the n-type semiconductive metal oxide is 1-9: 9-1; the composite material is used as an electrode material of a super capacitor.
2. A preparation method of a supercapacitor electrode material is characterized by comprising the following steps:
s1, treating the metal oxide powder capable of realizing n-type semi-conduction in a reducing atmosphere or making the metal oxide powder semi-conductive by a donor doping method;
s2, growing or combining the n-type semiconductor metal oxide powder or the n-type semiconductor metal oxide powder obtained in the step S1 on the surface or the interface of the n-type semiconductor metal oxide powder or the n-type semiconductor metal oxide powder by a physical or chemical method to form a pn-junction powder;
s3, gluing and pressing the powder with the pn junction obtained in the S2 to form the electrode material of the super capacitor;
in step S1, the n-type semiconducting metal oxide includes Fe3O4、ZnFe2O4、CuFe2O4、CoFe2O4、NiFe2O4、MnFe2O4NiCuZn ferrite, MgFe2O4、ZnO、TiO2、CaTiO3、BaTiO3、SrTiO3、BST、BZT、SnO2、CaSnO3、BaSnO3、SrSnO3、BiFeO3At least one of;
the p-type semiconducting metal oxide comprises MnO2、RuO2、Mn3O4、MnO、CaMnO3、SrMnO3、LaMnO3、La1- xSrxMnO3、NiO、CoO、FeO、CuO、Cu2O、YBa2Cu3O7－δ、Bi2Sr2Ca2Cu3O10－δAt least one of;
in step S2, the n-type semiconductive metal oxide and the p-type semiconductive metal oxide are used in an amount such that the molar ratio of metal atoms in the n-type semiconductive metal oxide to the p-type semiconductive metal oxide is 1 to 9: 9-1;
in step S2, the physical or chemical method includes:
evaporation, hydrothermal method, chemical liquid phase precipitation or sol-gel method;
the pressing condition is 1 MPa-100 MPa.
3. Supercapacitor electrode material, characterized in that it is obtained with the composite material according to claim 1, compounded with electrolyte and foam Ni by gluing, pressing.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810923104.8A CN108962626B (en) | 2018-08-14 | 2018-08-14 | A composite material with pn junction structure for supercapacitor |
| PCT/CN2018/101309 WO2020034234A1 (en) | 2018-08-14 | 2018-08-20 | Composite material having pn junction structure for supercapacitor, electrode material for supercapacitor and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810923104.8A CN108962626B (en) | 2018-08-14 | 2018-08-14 | A composite material with pn junction structure for supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108962626A CN108962626A (en) | 2018-12-07 |
| CN108962626B true CN108962626B (en) | 2021-03-26 |
Family
ID=64469790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810923104.8A Expired - Fee Related CN108962626B (en) | 2018-08-14 | 2018-08-14 | A composite material with pn junction structure for supercapacitor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108962626B (en) |
| WO (1) | WO2020034234A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109003821B (en) * | 2018-08-14 | 2021-03-26 | 东北大学 | Ultrahigh dielectric constant composite material, preparation method and application thereof |
| CN110233046A (en) * | 2019-05-22 | 2019-09-13 | 东北大学秦皇岛分校 | A kind of electric slurry and preparation method and application of large value capacitor medium |
| CN110931263B (en) * | 2019-11-21 | 2021-08-03 | 杭州电子科技大学 | A kind of supercapacitor electrode structure and enhancement method |
| CN111847526B (en) * | 2020-07-29 | 2021-04-23 | 十堰浩达新能源科技有限公司 | High-capacity super capacitor |
| CN111883372B (en) * | 2020-08-10 | 2021-10-29 | 嘉兴嘉卫检测科技有限公司 | Zn-doped MnFe2O4@ C composite material for super capacitor and preparation method thereof |
| CN115246983B (en) * | 2022-07-25 | 2024-04-02 | 华南理工大学 | A composite dielectric material, its preparation method and its application in capacitors |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263155C (en) * | 2003-08-27 | 2006-07-05 | 浙江大学 | Indium tin oxide pn node used on semiconductor device |
| CN101312079B (en) * | 2008-06-25 | 2012-04-25 | 武汉理工大学 | Heterostructure dielectric film possessing different arrangement mode and method for making same |
| EP3062323B1 (en) * | 2013-09-29 | 2018-11-21 | Shanghai Institute of Ceramics, Chinese Academy of Sciences | Titanium oxide-based supercapacitor electrode material and method of manufacturing same |
| CN103871750B (en) * | 2014-03-20 | 2017-01-11 | 华中科技大学 | Anatase TiO2 nano-dendritic array and its application in solar cell fabrication |
| CN105664941A (en) * | 2014-11-18 | 2016-06-15 | 天津城建大学 | Method for preparing nano-composite photocatalyst with P-N homojunction structure |
| CN105321721B (en) * | 2015-12-02 | 2018-02-09 | 常州大学 | A kind of preparation method of dye-sensitized solar cell anode material |
| CN105948735B (en) * | 2016-04-28 | 2018-08-07 | 山东大学 | A kind of SrTiO3Heterogeneous cladding BaTiO3The synthetic method of hyperfine nano-powder |
| CN107537501B (en) * | 2017-08-28 | 2020-08-04 | 武汉理工大学 | ZnO/CuO composite material with hierarchical structure and preparation method thereof |
-
2018
- 2018-08-14 CN CN201810923104.8A patent/CN108962626B/en not_active Expired - Fee Related
- 2018-08-20 WO PCT/CN2018/101309 patent/WO2020034234A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020034234A1 (en) | 2020-02-20 |
| CN108962626A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108962626B (en) | A composite material with pn junction structure for supercapacitor | |
| Shi et al. | CoNiSe2 nanorods directly grown on Ni foam as advanced cathodes for asymmetric supercapacitors | |
| Bhujun et al. | Study of mixed ternary transition metal ferrites as potential electrodes for supercapacitor applications | |
| Qin et al. | Oxygen vacancies boost δ-Bi2O3 as a high-performance electrode for rechargeable aqueous batteries | |
| Javed et al. | Tracking pseudocapacitive contribution to superior energy storage of MnS nanoparticles grown on carbon textile | |
| Bao et al. | Novel porous anatase TiO2 nanorods and their high lithium electroactivity | |
| CN105355886B (en) | A kind of sodium-ion battery positive pole Na2+2xFe2‑x(SO4)3@carbon composites and preparation method thereof | |
| Kumar et al. | Facile hydrothermal synthesis of ternary CeO2–SnO2/rGO nanocomposite for supercapacitor application | |
| CN107611382B (en) | Graphene composite carbon-limited-domain metal oxide nano-dot material and preparation method and application thereof | |
| CN109003821B (en) | Ultrahigh dielectric constant composite material, preparation method and application thereof | |
| Wu et al. | Characterization of spherical-shaped Li4Ti5O12 prepared by spray drying | |
| Yuan et al. | Cu-doped NiO for aqueous asymmetric electrochemical capacitors | |
| Chen et al. | Crystallization of Fe 3+ in an alkaline aqueous pseudocapacitor system | |
| Nagaraju et al. | Enhanced electrochemical performance of α-MoO 3/graphene nanocomposites prepared by an in situ microwave irradiation technique for energy storage applications | |
| Liu et al. | Magnetic-field-assisted preparation of one-dimensional (1-D) wire-like NiO/Co3O4 composite for improved specific capacitance and cycle ability | |
| Chen et al. | MOF-derived Fe 3 O 4/carbon octahedral nanostructures with enhanced performance as anode materials for lithium-ion batteries | |
| CN105870447A (en) | Preparation method of nitrogen-doped rutile TiO2/C negative electrode material for sodium ion battery | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| CN106504907A (en) | A kind of molybdenum sulfide/cobalt tetroxide composite material and its preparation method and application | |
| Cheng et al. | Accelerating water oxidation kinetics via synergistic in-layer modification and interlayer reconstruction over hetero-epitaxial Fe-Mn-O nanosheets | |
| Ren et al. | Facile synthesis of hierarchical porous ZnMn2O4 rugby-balls on Ni foam for lithium-ion batteries with enhanced electrochemical properties | |
| CN107819125A (en) | A kind of preparation method of straw bundle shape cobaltosic oxide and its application in lithium ion battery | |
| Zhu et al. | Self-sacrificial template formation of ultrathin single-crystalline ZnMn 2 O 4 nanoplates with enhanced Li-storage behaviors for Li-ion batteries | |
| Yetiman et al. | Unlocking the Potential of Bismuth‐Based Materials in Supercapacitor Technology: A Comprehensive Review | |
| CN108682562B (en) | A kind of γ-Fe of C doping2O3Nanocomposite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210326 Termination date: 20210814 |