CN111403181A - Method for preparing capacitor cathode material with ultrahigh capacity and stability - Google Patents
Method for preparing capacitor cathode material with ultrahigh capacity and stability Download PDFInfo
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- CN111403181A CN111403181A CN201910365539.XA CN201910365539A CN111403181A CN 111403181 A CN111403181 A CN 111403181A CN 201910365539 A CN201910365539 A CN 201910365539A CN 111403181 A CN111403181 A CN 111403181A
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- vanadium oxide
- phosphate
- sodium
- phosphoric acid
- electrode material
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title abstract description 4
- 239000003990 capacitor Substances 0.000 title description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007772 electrode material Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 239000007773 negative electrode material Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- -1 phosphoric acid functional group modified vanadium oxide Chemical class 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- ZQKXOSJYJMDROL-UHFFFAOYSA-H aluminum;trisodium;diphosphate Chemical compound [Na+].[Na+].[Na+].[Al+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZQKXOSJYJMDROL-UHFFFAOYSA-H 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical group [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 2
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 2
- 239000011706 ferric diphosphate Substances 0.000 claims description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims description 2
- 229940099402 potassium metaphosphate Drugs 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 229960003339 sodium phosphate Drugs 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims 1
- 239000000463 material Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- GSLNTGVHPTZSME-UHFFFAOYSA-N [O-2].[V+5].[C+4] Chemical compound [O-2].[V+5].[C+4] GSLNTGVHPTZSME-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005298 paramagnetic effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910000147 aluminium phosphate Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910007613 Zn—MnO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a method for preparing a vanadium oxide electrode material with ultrahigh capacity and stability. The method adopts a preparation method of surface modified metal oxide to obtain the vanadium oxide electrode material modified by phosphoric acid functional group. The prepared vanadium oxide not only modifies the surface with phosphoric acid functional groups, but also obviously improves the performance of the supercapacitor in a negative potential window, effectively breaks through the bottleneck of poor stability of the vanadium oxide, provides a good cathode material for the conventional supercapacitor, and has great application prospect.
Description
Technical Field
The invention belongs to the technical field of energy storage material modification, and particularly relates to a preparation method of a vanadium oxide electrode material modified by phosphoric acid functional groups.
Background
The growing demand for energy and the worsening of the environment, and industryThe development of a great demand for energy storage devices has led to an increasing interest in the development and exploration of new types of energy storage devices. The rapid development of flexible wearable electronics has led to a great interest in exploring new storage devices with high chemical properties and good flexibility. Among these flexible devices, including lithium ion batteries, supercapacitors and Zn-MnO2Batteries, all of which have made significant progress. The flexible Asymmetric Super Capacitors (ASCs) have been widely used by researchers due to their superior performance such as fast charge/discharge capability, excellent and stable high power density, and wide working voltage window. The main bottleneck of the flexible asymmetric super capacitor at the present stage is that the energy density of the flexible asymmetric super capacitor is lower than that of a battery, and the key for developing the density of the performance hybrid super capacitor is to improve the specific capacity of an electrode material. Generally, one electrode in the asymmetric supercapacitor is an energy type electrode, pseudo capacitance provided by faradaic redox reaction is mainly used for storing and releasing energy, and pseudo capacitance electrode materials such as metal oxides, conductive polymers and the like are generally adopted; the other electrode is a power type electrode, stores and releases energy mainly through an electric double layer capacitance mechanism, and generally adopts carbon materials, so that the asymmetric super capacitor not only has electric double layer capacitance but also has Faraday capacitance characteristics. Most of the current negative electrode materials are carbon materials, and the carbon materials have the advantages of excellent electronic conductivity, ultra-high specific surface area, abundant and cheap raw material sources and the like, and are widely applied to the fields of electrochemical sensors, batteries, capacitors and the like. However, the capacitance capacity is often unsatisfactory only by rapid electron absorption and desorption of the electric double layer. Therefore, in order to improve the energy density of the hybrid supercapacitor, active exploration of a novel asymmetric supercapacitor anode material with high capacitance and stability is one of the key research directions of scientific research at present.
Among the many negative electrode materials, vanadium oxide is less expensive (about $ 12 per kilogram) than other non-noble metal oxides, and vanadium is abundant in soil. Vanadium has been used as an anode material to assemble a super capacitor because of its many valence states, wide potential window and high theoretical capacity. They have been used as negative electrode groupsThere have been few reports of supercapacitors because their supercapacitor performance in the negative potential interval (vs. sce) has been less than ideal, and until recently their potential as an asymmetric supercapacitor negative electrode material has not begun to be explored6O13The potential window of the material extends to a negative potential interval (-1V-0V vs. SCE), and the electrode material is found to have a potential of 0.72F/cm under this potential window2(1mA/cm2) Significant capacitive behavior. However, like most other reported vanadium oxide positive electrode materials, this sulfur-doped V is prone to form soluble vanadate ions in aqueous electrolytes and their structure changes during cycling6O13The negative electrode material capacitance decayed rapidly after 200 cycles, losing 52.3% of the capacitance. Although the carbon coating or the coating of the conductive polymer can improve the stability of the vanadium oxide electrode to some extent; in 2017, in another research on vanadium oxide as a negative electrode material, the prepared vanadium oxide electrode material can keep good cycle stability (10 ten thousand cycle numbers) in a negative potential interval, but the electrode material is 2mA/cm2The capacitance capacity under the current density is only 0.28F/cm2(106F/g). In summary, designing a vanadium oxide electrode material with a desired high capacitance and stability in the negative potential window is still a serious challenge.
Disclosure of Invention
In order to overcome the defects of poor capacitance performance and poor stability of vanadium oxide in a negative potential interval in the prior art, the invention provides a preparation method of a phosphoric acid functional group modified vanadium oxide electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a phosphoric acid functional group modified vanadium oxide electrode material is characterized by comprising the following steps: the vanadium oxide electrode material modified by phosphoric acid functional group is obtained by adopting the method and the preparation method of the surface modified metal oxide. In specific implementation, the method can comprise the following steps:
(1) placing phosphate in front of the original vanadium oxide sample;
(2) taking inert gas as carrier gas, reacting for 0.5-32 hours at the temperature of 100-450 ℃ (5 ℃/min) to obtain the vanadium oxide electrode material modified by phosphoric acid functional group.
Preferably, the inert gas is argon or nitrogen.
Preferably, the phosphate is sodium acid pyrophosphate, calcium hypophosphite, diammonium phosphate, calcium phosphate, monoammonium phosphate, calcium hydrogen phosphate, monopotassium phosphate, dipotassium phosphate, monosodium phosphate, magnesium phosphate, disodium phosphate, ferric pyrophosphate, sodium phosphate, sodium pyrophosphate, potassium polymetaphosphate, sodium hypophosphite, sodium aluminum phosphate, sodium metaphosphate, sodium polyphosphate, magnesium hydrogen phosphate, potassium pyrophosphate, sodium ferric pyrophosphate, trimetaphosphate, or sodium tripolyphosphate.
Preferably, the vanadium oxide is V2O3、V6O13、VO、V3O7、VO2Or V2O5。
The vanadium oxide electrode material modified by phosphate radical obtained by the method can be used as an asymmetric supercapacitor negative electrode material.
The method adopts phosphoric acid functional group surface modification to prepare the capacitor cathode material with ultrahigh capacity and stability. The prepared vanadium oxide not only modifies phosphoric acid functional groups on the surface, but also obviously improves the performance of the supercapacitor in a negative potential window, effectively breaks through the bottleneck of poor stability of the vanadium oxide, and obtains the vanadium oxide energy storage electrode material with high electrochemical performance by setting proper oxidation temperature and time.
The invention has the beneficial effects that: the method has the characteristics of simple operation, low energy consumption, wide raw material source, low cost, no toxicity, safety, environmental friendliness and the like. In addition, the surface of the prepared vanadium oxide negative electrode material is modified with phosphoric acid functional groups, so that the performance of the prepared vanadium oxide negative electrode material in a super capacitor with a negative potential window is obviously improved, the bottleneck of poor stability of the vanadium oxide is effectively broken through, and the prepared vanadium oxide negative electrode material has a great application prospect in the aspect of energy storage.
Drawings
FIG. 1 is a Raman diagram of a virgin vanadium oxide and a phosphoric acid functional group-modified vanadium oxide; the lower curve in the figure is for the original sample and the upper curve in the figure is for the vanadium oxide modified with phosphoric acid functional groups.
FIG. 2 is a Fourier infrared spectrum of a virgin vanadium oxide and a phosphoric acid functional group-modified vanadium oxide.
FIG. 3 is a graph of paramagnetic resonance of the original vanadium oxide and the vanadium oxide modified with phosphoric acid functional groups.
FIG. 4 is a graph of electrochemical performance tests of vanadium oxide and modified vanadium oxide; FIG. 4a shows cyclic voltammetry (10mV/s) in comparison, and FIG. 4b shows iR voltage drop in comparison.
FIG. 5 is a graph of electrochemical lifetime measurements and triplicate parallel test samples of vanadium oxide and modified vanadium oxide with a sweep rate of 100 mV/s.
The Chinese and English symbols in the attached drawings explain: VO is original vanadium oxide; PVO is vanadium oxide modified with phosphoric acid functional group.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Firstly, vanadium oxide is obtained by a hydrothermal method, i.e. the following steps are performed:
(a) will be (NH)4)VO3Dissolving in a mixed solution prepared by deionized water and ethanol, and stirring until the solution is dissolved;
(b) adjusting pH to 1.5-3.5 with concentrated acid (concentrated hydrochloric acid or concentrated nitric acid);
(c) transferring the solution to a reaction kettle;
(d) immersing the carbon cloth into the solution, sealing, placing the carbon cloth in an oven, setting the temperature at 140 ℃ and 180 ℃, reacting for 12 hours, and naturally cooling;
(e) and taking out the vanadium oxide carbon cloth material obtained after the reaction, washing the vanadium oxide carbon cloth material with ethanol and deionized water for three times respectively, and air-drying.
Then, modifying the obtained vanadium oxide carbon cloth material by adopting a vapor deposition method, namely executing the following steps:
(f) placing potassium phosphate in front of the vanadium oxide sample (near the air inlet);
(g) placing the VO carbon cloth material in a tank zone (downstream of the airflow) behind the phosphate;
(h) argon or nitrogen is taken as carrier gas, the temperature is set to be 100-450 ℃ (the heating speed is 5 ℃/min), and after reaction for one hour, the temperature is naturally reduced;
(i) and (4) sealing and storing the vanadium oxide material modified by the phosphoric acid functional group obtained in the last step.
In order to verify the basic phase change and the performance difference of the vanadium oxide modified by the phosphoric acid functional group, performance tests are respectively carried out on the vanadium oxide before and after the phosphoric acid functional group is modified.
The raman spectrum characterization was performed on the vanadium oxide before and after the phosphoric acid functional group modification, and the results are shown in fig. 1, and the scanning electron microscopy electron micrograph shows that the basic raman characteristic peak position of the hydrothermal original vanadium oxide is not obviously changed after the vanadium oxide is modified with phosphoric acid groups.
FIG. 2 shows Fourier infrared spectrum characterization of vanadium oxide modified with phosphoric acid functional group to increase infrared characteristic peak of phosphoric acid functional group in the spectrum.
Paramagnetic resonance analysis is respectively applied to the vanadium oxide before and after the modification of the phosphoric acid functional group, and the paramagnetic resonance in fig. 3 shows that the peak position of the vanadium oxide after the modification of the phosphoric acid functional group is not moved, and the peak intensity is much larger than that of the original sample.
The capacitance performance of the vanadium oxide before and after the phosphoric acid functional group modification is analyzed and researched by adopting a cyclic voltammetry method and a constant current charging and discharging method in an electrochemical method, and the result is shown in fig. 4. The calculation shows that the electrochemical performance of the vanadium oxide modified by the phosphoric acid functional group in the negative potential interval is obviously enhanced, and the internal resistance is reduced.
The life performance of the electrochemical device was tested and studied by cyclic voltammetry, and the results are shown in fig. 5. The calculation shows that the capacitance retention rate of the modified vanadium oxide is still 100% after 20000 cycles of charge and discharge at the sweep rate of 100mV/s, and three parallel test sample graphs are obtained.
Therefore, in a tubular furnace using nitrogen or argon as carrier gas, the capacitance performance and the circulation stability of the vanadium oxide modified by the phosphoric acid functional group in a negative potential interval can be improved, and the vanadium oxide modified by the phosphoric acid functional group has a great application prospect in the aspect of energy storage. For example, the modified material of the phosphoric acid functional group can be used as a novel flexible asymmetric supercapacitor negative electrode material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of a vanadium oxide electrode material modified by phosphoric acid functional groups is characterized by comprising the following steps: the method adopts a preparation method of surface modified metal oxide to obtain the vanadium oxide electrode material modified by phosphoric acid functional group.
2. The method of claim 1, comprising the steps of:
(1) placing phosphate in front of the original vanadium oxide sample;
(2) taking inert gas as carrier gas, reacting for 0.5-32 hours at the temperature of 100-450 ℃ (5 ℃/min) to obtain the vanadium oxide electrode material modified by phosphoric acid functional group.
3. The method of claim 2, wherein the inert gas is argon or nitrogen.
4. The method of claim 2, wherein the phosphate is sodium acid pyrophosphate, calcium hypophosphite, diammonium phosphate, calcium phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, magnesium phosphate, disodium hydrogen phosphate, ferric pyrophosphate, sodium phosphate, sodium pyrophosphate, potassium polymetaphosphate, sodium hypophosphite, sodium aluminum phosphate, sodium metaphosphate, sodium polyphosphate, magnesium hydrogen phosphate, potassium pyrophosphate, sodium iron pyrophosphate, trimetaphosphoric acid, or sodium tripolyphosphate.
5. The method of claim 2, wherein the vanadium oxide is V2O3、V6O13、VO、V3O7、VO2Or V2O5。
6. A phosphoric acid functional group modified vanadium oxide electrode material obtainable by a process according to any one of claims 1 to 5.
7. Use of the phosphoric acid functional group modified vanadium oxide electrode material according to claim 6.
8. The use according to claim 7, wherein the phosphoric acid functional group modified vanadium oxide electrode material is used as a novel flexible asymmetric supercapacitor negative electrode material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112850789A (en) * | 2021-01-05 | 2021-05-28 | 西南大学 | Metal oxide/nitrogen-phosphorus co-doped carbon composite material, preparation method thereof and application thereof in negative electrode material of sodium-ion battery |
| CN113223865A (en) * | 2021-05-11 | 2021-08-06 | 辽宁大学 | Vanadium oxide electrode material with nanorod structure and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040262571A1 (en) * | 2003-06-03 | 2004-12-30 | Jeremy Barker | Battery active materials and methods for synthesis |
| JP2010027482A (en) * | 2008-07-23 | 2010-02-04 | Sony Corp | Method for manufacturing positive electrode active material and positive electrode active material |
| CN101814379A (en) * | 2010-04-28 | 2010-08-25 | 复旦大学 | Super capacitor |
| WO2011081507A2 (en) * | 2009-12-31 | 2011-07-07 | Universite Mohammed V-Agdal | Production of thin-film naxvopo4, nh2o cathodic materials |
| JP2014051425A (en) * | 2012-09-10 | 2014-03-20 | National Institute Of Advanced Industrial & Technology | Single crystal particle of titanium oxide, method for producing the same, electrode active material containing the single crystal particle of titanium oxide and electricity storage device using the electrode active material |
| US20140332733A1 (en) * | 2011-08-30 | 2014-11-13 | Cornell University | Pure metal and ceramic nanofibers |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN109841423A (en) * | 2019-04-18 | 2019-06-04 | 江西师范大学 | Valence state regulation and surface modification prepare novel barium oxide negative electrode material |
-
2019
- 2019-05-01 CN CN201910365539.XA patent/CN111403181A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040262571A1 (en) * | 2003-06-03 | 2004-12-30 | Jeremy Barker | Battery active materials and methods for synthesis |
| JP2010027482A (en) * | 2008-07-23 | 2010-02-04 | Sony Corp | Method for manufacturing positive electrode active material and positive electrode active material |
| WO2011081507A2 (en) * | 2009-12-31 | 2011-07-07 | Universite Mohammed V-Agdal | Production of thin-film naxvopo4, nh2o cathodic materials |
| CN101814379A (en) * | 2010-04-28 | 2010-08-25 | 复旦大学 | Super capacitor |
| US20140332733A1 (en) * | 2011-08-30 | 2014-11-13 | Cornell University | Pure metal and ceramic nanofibers |
| JP2014051425A (en) * | 2012-09-10 | 2014-03-20 | National Institute Of Advanced Industrial & Technology | Single crystal particle of titanium oxide, method for producing the same, electrode active material containing the single crystal particle of titanium oxide and electricity storage device using the electrode active material |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN109841423A (en) * | 2019-04-18 | 2019-06-04 | 江西师范大学 | Valence state regulation and surface modification prepare novel barium oxide negative electrode material |
Non-Patent Citations (2)
| Title |
|---|
| DAVIES, A; HOBSON, RJ; NEAT, RJ；ET AL.: "VANADIUM PHOSPHATE-GLASSES - EFFECT OF COMPOSITION ON THEIR STRUCTURE AND PERFORMANCE AS CATHODES IN HIGH-TEMPERATURE LITHIUM POLYMER-ELECTROLYTE CELLS", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 张蓉瑜: "锂离子电池正极材料磷酸钒锂的表面改性与应用研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112850789A (en) * | 2021-01-05 | 2021-05-28 | 西南大学 | Metal oxide/nitrogen-phosphorus co-doped carbon composite material, preparation method thereof and application thereof in negative electrode material of sodium-ion battery |
| CN112850789B (en) * | 2021-01-05 | 2022-04-26 | 西南大学 | Metal oxide/nitrogen-phosphorus co-doped carbon composite material, preparation method thereof and application thereof in negative electrode material of sodium-ion battery |
| CN113223865A (en) * | 2021-05-11 | 2021-08-06 | 辽宁大学 | Vanadium oxide electrode material with nanorod structure and preparation method and application thereof |
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