CN114823166A - VO (PO3)2 with wide voltage window, preparation method and super capacitor - Google Patents
VO (PO3)2 with wide voltage window, preparation method and super capacitor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 28
- 239000003990 capacitor Substances 0.000 title abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920003081 Povidone K 30 Polymers 0.000 claims abstract description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 20
- 230000002687 intercalation Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000032798 delamination Effects 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229910021392 nanocarbon Inorganic materials 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 4
- 239000011157 advanced composite material Substances 0.000 description 3
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- 239000002184 metal Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GPQUEUOSGZMUQE-UHFFFAOYSA-N [O-2].[Hg+].[Hg+] Chemical compound [O-2].[Hg+].[Hg+] GPQUEUOSGZMUQE-UHFFFAOYSA-N 0.000 description 1
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(I) oxide Inorganic materials O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention belongs to the field of super capacitors, and relates to a self-supporting VO (PO) with a wide voltage window 3 ) 2 The method is used for effectively improving HER/OER overpotential to obtain the super capacitor with ultrahigh energy density. The method comprises adding ammonium metavanadate and citric acid into deionized water at 40 deg.C, dissolving, adding ammonium dihydrogen phosphate, F127 and PVP K30, 80 o C, preserving the heat for 10 minutes, performing hydrothermal reaction to form gel, freeze-drying the gel, putting the gel into a tube furnace, and adding N 2 Post CO 2 Calcining under the atmosphere of (1) to obtain the final product. The invention firstly converts VO (PO) 3 ) 2 Is applied to the field of super capacitors and is charged and discharged by Na + The reversible phase transition reaction of intercalation/delamination reaches the maximum voltage value of 2.8V of the water system super capacitor and obtains 123.1 Wh kg ‑1 Ultra high energy density of (2). The method is simple to operate and environment-friendly, and the material is endowed with high performance.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a self-supporting wide-voltage-window VO (PO3)2, a preparation method, an electrode and a super capacitor.
Background
The energy crisis is a great challenge for human beings, and the development of electrochemical energy storage devices is concerned. Supercapacitors are considered as the next generation of promising energy storage devices due to their high power density, ultra-high speed performance and long-term stability. Currently, the great technical challenges of supercapacitors are focused on increasing the energy density without reducing its power density and cycle life. For this purpose, based on E =1/2CV 2 It has proven effective to modify the high specific capacitance or to extend the wider operating voltage。
Thermodynamically, aqueous electrolytes can only provide an electrochemical stability window of 1.23V, limited primarily by the theoretical water splitting potential. It is reported at present that optimization is mainly carried out from electrolyte and electrode materials to solve the problem that the electrochemical stability window is too small. Ultra-high concentrations of "water in salt" (WIS) electrolyte (>20 molar concentration) allow detection of water molecules at low concentrations, providing ultra-high potential windows of > 2.0V in aqueous solution supercapacitors, but potential safety issues may prevent their widespread use in the future. Another approach is to modify the electrode by structural engineering, metal cation intercalation or building advanced composite materials. Due to poor circulation stability of structural engineering and high complexity of constructing advanced composite materials, the metal cation intercalation method provides great expansion for the utilization of electrode materials in the aspect of expanding working voltage. The mechanism by which metal ion intercalation improves the electrochemical window is that intercalation energy consumption competes with water electrolysis, resulting in an increase in threshold voltage. Despite the potential increase, there is still a need for further improvement of the operating voltage, with a focus on alternative electrode materials for cation intercalation. In summary, the development of new intercalation materials is a straightforward and effective strategy to widen the voltage window. Meanwhile, the method can be further improved.
Through the above analysis, the problems and defects of the prior art are as follows: the electrochemical stability window of the existing water system super capacitor is small, and higher energy density is difficult to obtain without sacrificing the power density and the cycle performance of the existing water system super capacitor.
The difficulty in solving the above problems and defects is: in a water-based supercapacitor, the existence of HER/OER overpotential can limit the electrochemical stability window of the supercapacitor, and the existing strategies all have certain technical difficulties. In addition, how to increase the cycle life of the intercalation electrode is another difficulty.
The significance of solving the problems and the defects is as follows: the ultra-high electrochemical stability window obtained by the higher intercalation energy can achieve ultra-high energy density without reducing power density and cycle life.
Disclosure of Invention
To the problems existing in the prior artThe invention provides a self-supporting, wide voltage window VO (PO) 3 ) 2 Preparation method, electrode and water system super capacitor
The invention is a VO (PO) with a self-supporting and wide voltage window 3 ) 2 The self-supporting, wide voltage VO (PO) 3 ) 2 The preparation method comprises the following steps:
preparation of gel: dissolving ammonium metavanadate and citric acid in deionized water, and continuing to add ammonium dihydrogen phosphate, F127 and PVP K30 for dissolution. Reacting to obtain a blue-green solution;
taking the solution, and carrying out hydrothermal reaction on the obtained uniform solution to obtain blue gel;
freeze-drying the prepared gel to keep the gel shape;
and transferring the dried gel precursor into a tubular furnace, and heating and preserving heat under the atmosphere of nitrogen firstly and then carbon dioxide to obtain a final product.
The carbon source provided by the citric acid in the formation of the gel plays a certain role in reduction in the final phosphorization stage and plays a role in protecting internal active sites in a later cycle performance test; and the nanowire structure is well preserved after high-temperature calcination, and is gradually converted into a three-dimensional interconnected hierarchical layered structure consisting of a plurality of nano carbons along with continuous phosphating reaction, and the structure is evolved and automatically stripped as a spacing layer, so that higher intercalation energy is generated. Provides a precondition for the subsequent intercalation of the electrolyte cation. The structure evolves an ultra-high electrochemically stable window and provides ultra-large energy density.
Further, preparation of a gel precursor: 40 o Dissolving 0.234 g of ammonium metavanadate and 0.576 g of citric acid in 30 ml of deionized water, adding 0.345 g of ammonium dihydrogen phosphate after dissolving, 100 mgF127 and 50 mg of PVP K30 for dissolving, and heating to 80 DEG C o And C, preserving the temperature for 10 min to obtain a blue-green solution.
Further, the blue-green solution was transferred to a 100 ml hydrothermal kettle at 170% o And reacting for 9 hours at the temperature of C to obtain stable blue gel.
And further, pre-freezing the obtained gel for 3-4 h, and freeze-drying for 2-3 days after pre-freezing to obtain a gel precursor.
Further, under nitrogen atmosphere, 2 o C/min is increased to 800 o C, keeping the temperature constant for 1 h, and changing nitrogen into carbon dioxide to keep the temperature constant for 2 h to obtain a final product.
Another object of the present invention is to provide a VO (PO) with a self-supporting and wide voltage window 3 ) 2 。
It is another object of the present invention to provide an electrode that is self-supporting from the wide voltage VO (PO) 3 ) 2 VO (PO) prepared by the preparation method of 3 ) 2 Thermally carbonizing at pyrolysis temperature to obtain VO (PO) by mechanical pressing to desired shape and density 3 ) 2 A self-supporting electrode. The mass loading of the active substance is about 1.5. + -. 0.2 mg cm -2 。
Another object of the present invention is to provide a supercapacitor using the electrode.
Another object of the present invention is to provide an automobile mounted with the battery.
By combining all the technical schemes, the invention has the advantages and positive effects that: according to the invention, an advanced composite material vanadium-based material is selected according to the fact that the electrochemical stability window of the aqueous electrolyte is too low caused by the inherent HER/OER overpotential, and the intercalation generated by the intercalation of electrolyte cations can improve the HER/OER overpotential to obtain a higher electrochemical stability window, so that VO (PO) is prepared 3 ) 2 The ultra-high electrochemical stability window and energy density are shown, and the performance of the super capacitor reaches the maximum value in a water system super capacitor.
The invention firstly proposes that VO (PO) is prepared by hydrothermal growth and phase transformation method 3 ) 2 The self-supporting electrode is used for an aqueous super capacitor; the electrode has a unique layered structure, and the outer layer of the electrode is provided with a protective layer of nano carbon, so that a large number of active sites are provided for electrolyte cation intercalation, and a premise is provided for obtaining higher intercalation energy; VO (PO) prepared 3 ) 2 The electrode material used for the water system super capacitor can reach the maximum value of the performance in the water system super capacitor; the preparation method has the characteristic of simple and convenient operation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a self-supporting, wide voltage window VO (PO) provided by an embodiment of the present invention 3 ) 2 The preparation method of (1) is a flow chart.
FIG. 2 is a self-supporting, wide voltage window VO (PO) provided by an embodiment of the present invention 3 ) 2 The structure evolution flow chart of the preparation method of (1).
Figure 3 is an X-ray diffraction pattern of a material prepared as provided by an embodiment of the present invention.
FIG. 4 is an optical image and a scanning electron micrograph of a prepared material provided in an embodiment of the present invention
FIG. 5 is a transmission electron micrograph of a prepared material provided by an embodiment of the present invention.
Fig. 6 is a schematic mechanism diagram of a structure provided by an embodiment of the present invention.
FIG. 7 is a graph of energy density and power density regions for performance characterization provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a VO (PO) with a self-supporting and wide voltage window 3 ) 2 The invention relates to a preparation method, an electrode and a super capacitor, and the invention is described in detail below with reference to the accompanying drawings.
As shown in FIG. 1, the VO (PO) with self-supporting and wide voltage window provided by the invention 3 ) 2 The preparation method comprises the following steps:
S101:40 o dissolving 0.234 g of ammonium metavanadate and 0.576 g of citric acid in 30 ml of deionized water, adding 0.345 g of ammonium dihydrogen phosphate after dissolving, 100 mgF127 and 50 mg of PVP K30 for dissolving, and heating to 80 DEG C o C, preserving the heat for 10 min to obtain a blue-green solution;
s102: the blue-green solution was transferred to a 100 ml hydrothermal kettle at 170% o Reacting for 9 hours under C to obtain stable blue gel;
s103: pre-freezing the obtained gel for 3-4 h, and freeze-drying for 2-3 days after pre-freezing to obtain a gel precursor;
s104: the precursor was placed in a tube furnace under nitrogen atmosphere at 2 o C/min is increased to 800 o C, keeping the temperature constant for 1 h, and changing nitrogen into carbon dioxide to keep the temperature constant for 2 h to obtain a final product.
The VO (PO) with self-supporting and wide voltage window provided by the invention 3 ) 2 The preparation method of (1) VO (PO) with a self-supporting and wide voltage window provided by the invention can also be implemented by other steps by persons of ordinary skill in the art 3 ) 2 The preparation method of (2) is merely one specific example.
The prepared material is pressed into the required shape and density by a machine, and thermally carbonized at the pyrolysis temperature to obtain VO (PO) 3 ) 2 A self-supporting electrode; using electrode material as working electrode, Na 2 SO 4 KOH as an electrolyte, saturated calomel (Na) 2 SO 4 ) And a mercury mercurous oxide electrode (KOH) is used as a reference electrode, a platinum sheet is used as a counter electrode to assemble a three-electrode system, and the electrochemical performance of the electrode material is tested.
The invention provides a method for preparing VO (PO) with self-supporting and wide voltage window by a phosphorization strategy 3 ) 2 (ii) a VO (PO) prepared by the method 3 ) 2 The nano-wire has a unique layered structure of nano-wire accumulation, and has very high intercalation energy, so that the electrochemical stability window of the device can be enlarged; VO (PO) prepared 3 ) 2 The largest electrochemical stability window of the current water system super capacitor is achieved, and simultaneously, the energy density and the cycle performance are higher; simple operation and easy batch preparation.
The prepared gel material has V shown by XRD 6 O 12 ·5H 2 The crystal lattice structure corresponding to O shows different crystal lattice structures under different atmospheres; it is used for VO (PO) 3 ) 2 //VO(PO 3 ) 2 The symmetrical super capacitor shows ultrahigh electrochemical stability window opening of 2.0V (6M KOH) and 2.8V (1M Na) in different water system electrolytes 2 SO 4 ) (ii) a Characterization of scanning electron microscope shows VO (PO) 3 ) 2 Better retains the precursor V 6 O 12 ·5H 2 And (4) the shape of the nanowire of O. Smooth surface on CO 2 After the intermediate phosphorization, the three-dimensional interconnected layered structure formed by a plurality of nano carbons is converted to be used as a spacing layer, and the structure evolution is automatically stripped. Transmission electron microscopy further confirmed the presence of nanocarbon, which clearly shows the crystallographic features of long range ordered lattice fringes. The thickness of the single layer of the nano-sheets is 5-10 nm, the transverse dimension is 6-8 μm, and the nano-sheets have obvious stripes. The method is applicable to the preparation of various VPO materials.
The invention is further described below with reference to experimental data and results.
FIG. 1 is a self-supporting, wide voltage window VO (PO) provided by an embodiment of the present invention 3 ) 2 The preparation method of (1) is a flow chart.
FIG. 2 is a self-supporting, wide voltage window VO (PO) provided by an embodiment of the present invention 3 ) 2 The structure evolution flow chart of the preparation method of (1).
Figure 3 is an X-ray diffraction pattern of a material prepared as provided by an embodiment of the present invention.
FIG. 4 is an optical image and a scanning electron micrograph of a prepared material provided in an embodiment of the present invention
FIG. 5 is a transmission electron micrograph of a prepared material provided by an embodiment of the present invention.
Fig. 6 is a schematic mechanism diagram of a structure provided by an embodiment of the present invention.
FIG. 7 is a graph of energy density and power density regions for performance characterization provided by an embodiment of the present invention.
Experiments show that:
the water-based electrolyte cannot obtain a higher electrochemical stability window due to the limitation of HER/OER overpotential, and the layered structure which is protected by the outer layer of nano-carbon and formed by the nano-wire stack can be structurally evolved by the hydrothermal growth and phase transformation method, so that a wider voltage window is structurally evolved.
The invention selects the pluggable layer material as an electrode according to the difference of charge storage mechanisms of the aqueous electrolyte, utilizes the intercalation energy generated by electrolyte ions during intercalation to increase HER/OER overpotential and prepare VO (PO) 3 ) 2 The material has excellent overall performance, and the performance of the material reaches the maximum electrochemical stability window in the current water system super capacitor
The invention firstly provides a hydrothermal growth and phase transformation method for preparing vanadium-phosphorus-oxygen materials; VO (PO) prepared by the method 3 ) 2 The composite membrane has a unique layered structure, and the outer layer of the composite membrane is provided with a protective layer of nano carbon, so that a large number of active sites are provided for electrolyte cation intercalation, and a premise is provided for obtaining higher intercalation energy. Experiments prove that VO (PO) prepared by the invention 3 ) 2 The electrode material used for the water system super capacitor can reach the largest electrochemical stability window of the current water system super capacitor; the preparation method has the characteristics of simple and convenient operation and wide applicability.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. VO (PO) with self-supporting and wide voltage window 3 ) 2 Characterized in that the self-supporting, wide voltage window VO (PO) 3 ) 2 The preparation method comprises the following steps:
preparation of a gel precursor: dissolving ammonium metavanadate and citric acid in deionized water, continuously adding ammonium dihydrogen phosphate, dissolving F127 and PVP K30, slowly dropwise adding deionized water, and reacting to obtain a blue-green solution;
taking the solution, and carrying out hydrothermal reaction on the obtained uniform solution to obtain blue gel;
freeze-drying the prepared gel to keep the gel shape;
and transferring the dried gel precursor into a tubular furnace, and heating and preserving heat under the atmosphere of nitrogen firstly and then carbon dioxide to obtain a final product.
2. Self-supporting, wide voltage window VO (PO) as claimed in claim 1 3 ) 2 The preparation method is characterized in that the preparation of the gel precursor comprises the following steps: 40 o Dissolving 0.234 g of ammonium metavanadate and 0.576 g of citric acid in 30 ml of deionized water, adding 0.345 g of ammonium dihydrogen phosphate, 100 mgF127 and 50 mg of PVP K30 after dissolving, and heating to 80 DEG C o And C, preserving the temperature for 10 min to obtain a blue-green solution.
3. Self-supporting, wide voltage window VO (PO) as claimed in claim 1 3 ) 2 The preparation method is characterized in that the blue-green solution is transferred to a 100 ml hydrothermal kettle and is treated at 170 DEG o And reacting for 9 hours at the temperature of C to obtain stable blue gel.
4. Self-supporting, wide voltage window VO (PO) as claimed in claim 1 3 ) 2 The preparation method is characterized in that the obtained gel is pre-frozen for 3-4 h, and is frozen and dried for 2-3 days after the pre-freezing is finished, so as to obtain a gel precursor.
5. Self-supporting, wide voltage window VO (PO) as claimed in claim 1 3 ) 2 The method is characterized in that the precursor is put into a tube furnace and is heated to 2 degrees under nitrogen atmosphere o C/min is increased to 800 o C, keeping the temperature for 1 hour,and changing nitrogen into carbon dioxide, and keeping the temperature constant for 2 hours to obtain a final product.
6. A self-supporting, wide voltage window VO (PO) as defined in any one of claims 1 to 5 3 ) 2 VO (PO) with self-supporting and wide voltage window prepared by the preparation method 3 ) 2 。
7. An electrode comprising the self-supporting, wide voltage window VO (PO) of any one of claims 1 to 5 3 ) 2 The preparation method comprises the steps of obtaining VO (PO) by mechanical pressing into a required shape and density and thermal carbonization at a pyrolysis temperature 3 ) 2 Self-supporting electrode, mass loading of active material is about 1.5 + -0.2 mg cm -2 。
8. An electrode material is characterized by having the property of self-supporting as an electrode sheet, and the voltage window can be as high as 2.8V.
9. An ultracapacitor, wherein the ultracapacitor uses the electrode of claim 7.
10. A new energy automobile mounted with the supercapacitor of claim 8.
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CN115312331A (en) * | 2022-07-19 | 2022-11-08 | 曲阜师范大学 | Transverse and longitudinal heterostructures (V) 2 O 3 @VPO 4 -NC), preparation method and all-solid-state micro capacitor |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103219164A (en) * | 2013-04-19 | 2013-07-24 | 中国科学院物理研究所 | Ultra-thin, self-supporting, flexible and all-solid-state super capacitor and manufacturing method thereof |
US20130316250A1 (en) * | 2012-04-30 | 2013-11-28 | Brookhaven Science Associates, Llc | Cubic Ionic Conductor Ceramics for Alkali Ion Batteries |
CN112978700A (en) * | 2021-03-26 | 2021-06-18 | 华南理工大学 | Lithium ion battery negative electrode material vanadium oxygen metaphosphate and preparation method and application thereof |
US20210319958A1 (en) * | 2020-04-08 | 2021-10-14 | The Board Of Trustees Of The University Of Illinois | Carbon-metal oxide composite electrode for a supercapacitor and method of making a carbon-metal oxide composite electrode |
-
2021
- 2021-12-03 CN CN202111469435.7A patent/CN114823166B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130316250A1 (en) * | 2012-04-30 | 2013-11-28 | Brookhaven Science Associates, Llc | Cubic Ionic Conductor Ceramics for Alkali Ion Batteries |
CN103219164A (en) * | 2013-04-19 | 2013-07-24 | 中国科学院物理研究所 | Ultra-thin, self-supporting, flexible and all-solid-state super capacitor and manufacturing method thereof |
US20210319958A1 (en) * | 2020-04-08 | 2021-10-14 | The Board Of Trustees Of The University Of Illinois | Carbon-metal oxide composite electrode for a supercapacitor and method of making a carbon-metal oxide composite electrode |
CN112978700A (en) * | 2021-03-26 | 2021-06-18 | 华南理工大学 | Lithium ion battery negative electrode material vanadium oxygen metaphosphate and preparation method and application thereof |
Non-Patent Citations (5)
Title |
---|
CHOU WU, YANMING ZHAO: "Facile synthesis and electrochemical properties of amorphous/crystalline VO (PO3)2@C as the anodes for Lithium-ion battery", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 895, no. 115541 * |
GRAHAM J. HUTCHINGS: "Effect of promoters and reactant concentration on the selective oxidation of n-butane to maleic anhydride using vanadium phosphorus oxide catalysts", ELSEVIER SCIENCE PUBLISHERS B.V., vol. 71, no. 1, pages 2 - 8 * |
HANNOUR, FK: "Ammoxidation of toluene on vanadyl polyphosphates -: VO(PO3)2, 1.: Synthesis and characterization of the parent samples", REACTION KINETICS AND CATALYSIS LETTERS, vol. 63, no. 2, 1 March 1998 (1998-03-01), pages 225 - 233 * |
NORMAN HERRON, * DAVID L. THORN, RICHARD L. HARLOW, AND GEORGE W. COULSTON: "Molecular Precursors to Vanadyl Pyrophosphate and Vanadyl Phosphite", AMERICAN CHEMICAL SOCIETY, vol. 119, no. 30, pages 7149 - 7150 * |
PROKOFIEV, AV: "Flux and chemical vapor transport growth and characterization of α- and β-VO(PO3)2 single crystals", JOURNAL OF CRYSTAL GROWTH, vol. 271, no. 1, 15 October 2004 (2004-10-15), pages 113 - 119, XP004591328, DOI: 10.1016/j.jcrysgro.2004.07.043 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115312331A (en) * | 2022-07-19 | 2022-11-08 | 曲阜师范大学 | Transverse and longitudinal heterostructures (V) 2 O 3 @VPO 4 -NC), preparation method and all-solid-state micro capacitor |
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