CN110540245B - Metal ion doped oxide prepared by quenching process and method and application thereof - Google Patents
Metal ion doped oxide prepared by quenching process and method and application thereof Download PDFInfo
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 29
- 238000010791 quenching Methods 0.000 title claims abstract description 20
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- 239000002184 metal Substances 0.000 claims abstract description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
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- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- -1 iron ions Chemical class 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 150000003608 titanium Chemical class 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 15
- 239000010406 cathode material Substances 0.000 abstract description 14
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- 239000010405 anode material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910020900 Sn-Fe Inorganic materials 0.000 description 3
- 229910019314 Sn—Fe Inorganic materials 0.000 description 3
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- 229910011212 Ti—Fe Inorganic materials 0.000 description 2
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a method for preparing metal ion doped oxide by using a quenching process and application thereof, wherein the preparation method comprises the following steps: dissolving trivalent ferric salt and sodium salt serving as reaction raw materials in water, adding carbon cloth to perform a precipitation hydrothermal reaction, washing, and drying to obtain a precursor; roasting the precursor, quickly putting the precursor into a low-temperature metal salt solution after heat preservation at the roasting temperature, standing, washing and drying to obtain Fe doped with metal ions2O3And (3) a negative electrode material. The resulting metal ion-doped Fe2O3The cathode material has uniform appearance and good repeatability, and the prepared super capacitor has obvious capacity and conductivity improvement.
Description
Technical Field
The invention belongs to the field of nanotechnology and the field of electrochemical application, and particularly relates to a metal ion doped oxide prepared by a quenching process, and a method and application thereof.
Background
With the continuous development of economy in China, the environmental problem is increasingly serious, and the exhaustion of fossil fuels is concerned by more and more people. Supercapacitors (SC), also called electrochemical capacitors, are the most advanced energy storage devices today, which can be charged and discharged quickly, have the advantages of high speed and high power density, have a long life, and can make up for the gap between batteries and conventional capacitors. This makes SC very likely to be the next generation of energy storage device for widespread use. However, to meet the ever-increasing energy demand, the energy density of the SC must be further increasedGood electrode materials are then required to achieve this. Fe2O3The capacitor has larger theoretical specific capacitance, the working window is negative potential, the cost is low, and the capacitor is nontoxic, but the use of the capacitor is limited due to poor conductivity of the capacitor. To overcome this drawback, many researchers have focused on structuring nanostructures to increase Fe2O3The specific surface area of the material is increased, or electron transmission channels among materials are increased, and transmission paths are shortened; or to study Fe2O3The composite material with the high-conductivity carbon nano material is used for improving the conductivity, but the method has high requirements on operation conditions and is complex to operate; or doping metal ions, such as cation exchange method, grinding and high-temperature calcination, etc., but the doping effect is not ideal. Therefore, if a simple and economical method for doping metal ions while increasing the specific surface area of the material could be developed for Fe2O3The preparation of the super capacitor obviously improves the capacity, the charge-discharge rate and other properties of the super capacitor, and is possible to meet the continuous requirements of production and life on energy sources.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a method for preparing a doped metal ion oxide by using a quenching process and application of the doped metal ion oxide as a super capacitor, and the cathode material has the advantages of large capacity, good stability and small resistivity.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a method for preparing a doped metal ion oxide by using a quenching process, which comprises the following steps:
(1) dissolving trivalent ferric salt and sodium salt serving as reaction raw materials in water, adding carbon cloth to perform a precipitation hydrothermal reaction, washing, and drying to obtain a precursor;
(2) roasting the precursor, keeping the temperature at the roasting temperature, putting the precursor into a metal salt solution, standing, washing and drying to obtain a metal ion-doped oxide, namely a metal ion-doped Fe2O3And (3) a negative electrode material.
Preferably, the ferric iron salt in the step (1) is ferric trichloride, and the sodium salt is sodium sulfate; dissolving the reaction raw materials by using deionized water; the hydrothermal reaction temperature is 90-160 ℃, and the hydrothermal reaction time is 6-12 h.
Preferably, the molar ratio of the ferric iron salt to the sodium salt in the step (1) is 1: 1-7; the area ratio of the amount of the ferric ion in the ferric salt to the carbon cloth is 5: 1-10: 1mol/m2The volume ratio of the amount of the ferric ions in the ferric salt to the water is 1: 15-1: 20 mol/L.
Preferably, the washing in the step (1) and the step (2) is washing with deionized water and absolute ethyl alcohol respectively for more than three times; the drying is blast drying or vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Preferably, the temperature of the metal salt solution in the step (2) is 4-25 ℃; the roasting temperature is 400-550 ℃, and the heat preservation time at the roasting temperature is 1-2 h.
Preferably, the metal salt in step (2) is a tin salt or a cerium salt; the molar ratio of iron ions in the ferric iron salt to metal ions in the metal salt is 1: 5-1: 10; the concentration of the tin salt solution and the cerium salt solution is 0.5-1 mol/L.
Preferably, the metal salt in step (2) is a titanium salt; the molar ratio of iron ions in the ferric iron salt to titanium ions in the titanium salt is 5-12: 1; the titanium salt solution is formed by dissolving titanium tetrachloride in ethanol, and the volume fraction of the titanium tetrachloride is 0.1-0.2%.
Preferably, the metal salt in the step (2) is more than one of tin chloride, cerium nitrate or titanium tetrachloride; the standing time is 15-60 min.
The invention provides a doped metal ion oxide prepared by the preparation method.
The invention provides application of the doped metal ion oxide in preparation of a super capacitor.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the invention provides Fe doped with metal ions2O3The preparation method of the cathode material is simpleThe cost is low, the obtained product has uniform appearance and good repeatability, and the method is used for improving the capacity and the conductivity of the super capacitor obviously;
(2) the surface doping of the metal ions can provide more potential centers, increase the carrier concentration and obviously improve the Fe2O3The capacitance and the conductivity of the cathode material enable the super capacitor to have higher capacity;
(3) the surface defects produced by the quenching process can better improve Fe2O3The conductivity of the cathode material enables the device to have lower resistance; fe2O3Initial capacity of 58.88mF/cm2After being quenched by deionized water, the capacity reaches 103.56 mF/cm2After quenching by the metal salt solution, the capacity is further improved to 138 mF/cm2And the capacities of other salt solutions are improved to different degrees after quenching, so that the capacity and the conductivity of the electrode material can be obviously improved by the preparation method.
Drawings
FIG. 1 is an XRD pattern of a negative electrode material prepared in comparative example and examples 1 to 4;
FIG. 2 shows Fe obtained in comparative example2O3SEM picture of @ CC;
FIG. 3 shows Sn-Fe prepared in example 12O3SEM image of @ CC cathode material;
FIG. 4 shows Ce-Fe prepared in example 22O3SEM image of @ CC cathode material;
FIG. 5 shows Ti-Fe prepared in example 32O3SEM image of @ CC cathode material;
FIG. 6 shows DIW-Fe prepared in example 42O3SEM image of @ CC cathode material;
FIG. 7 is a cyclic voltammetry curve of the negative electrode material of the supercapacitor described in the comparative example and examples 1-4;
FIG. 8 is a Mott Schottky curve of the negative electrode material of the supercapacitor described in the comparative example and examples 1 to 4.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Comparative example
This comparative example provides a Fe2O3The preparation method of the anode material comprises the following steps:
(1) 0.946 g ferric chloride hexahydrate (M = 270.3) and 0.497 g anhydrous sodium sulfate (M = 142.04) are respectively weighed, mixed and dissolved in 70 ml deionized water, stirred for 30 min at room temperature until the solution is clear, transferred to 100 ml polytetrafluoroethylene lining, and added with 2X 3 cm2Performing a hydrothermal reaction on carbon cloth by a precipitation method, wherein the temperature of the hydrothermal reaction is 160 ℃, the time of the hydrothermal reaction is 6h, cleaning the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and performing blast drying to obtain a precursor, wherein the drying temperature is 70 ℃, and the drying time is 12 h;
(2) roasting the precursor, and roasting the precursor in a muffle furnace for 1 h at 400 ℃ to obtain Fe2O3@CC。
Example 1
This example provides a metal ion doped Fe2O3The preparation method of the anode material comprises the following steps:
(1) 0.946 g ferric chloride hexahydrate (M = 270.3) and 0.497 g anhydrous sodium sulfate (M = 142.04) are respectively weighed, mixed and dissolved in 70 ml deionized water, stirred for 30 min at room temperature until the solution is clear, transferred to 100 ml polytetrafluoroethylene lining, and added with 2X 3 cm2Performing a hydrothermal reaction on carbon cloth by a precipitation method, wherein the temperature of the hydrothermal reaction is 160 ℃, the time of the hydrothermal reaction is 6h, cleaning the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and performing blast drying to obtain a precursor, wherein the drying temperature is 60 ℃, and the drying time is 12 h;
(2) weighing 6.135 g of stannic chloride pentahydrate (M =350.6) and dissolving in 35 ml of deionized water, stirring for 30 min at room temperature until the solution is clear, and transferring the solution to a refrigerator at 4 ℃ for refrigeration for 6h to obtain a tin salt solution;
(3) transferring the precursor obtained in the step (1) into a muffle furnace for 400 ℃ roasting for 1 h, then quickly transferring into the tin salt solution prepared in the step (2) for quenching, standing for 15min, then respectively cleaning with deionized water and absolute ethyl alcohol for three times, and after cleaning, transferring into a blast drying box for 70 ℃ drying for 10 h to obtain Sn-Fe2O3@CC。
Example 2
This example provides a metal ion doped Fe2O3The preparation method of the anode material comprises the following steps:
(1) 0.946 g ferric chloride hexahydrate (M = 270.3) and 1.74 g anhydrous sodium sulfate (M = 142.04) are respectively weighed, mixed and dissolved in 63 ml deionized water, stirred at room temperature for 30 min until the solution is clear, transferred to 100 ml polytetrafluoroethylene lining, and added with 2X 2 cm2Performing a hydrothermal reaction on carbon cloth by a precipitation method, wherein the temperature of the hydrothermal reaction is 120 ℃, the time of the hydrothermal reaction is 9 h, cleaning the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and performing blast drying to obtain a precursor, wherein the drying temperature is 70 ℃, and the drying time is 10 h;
(2) weighing 7.5989 g of cerous nitrate hexahydrate (M =434.22) and dissolving in 35 ml of deionized water, stirring for 30 min at room temperature to obtain a clear solution, and transferring to a refrigerator at 10 ℃ for refrigeration for 6h to obtain a cerium salt solution;
(3) transferring the precursor obtained in the step (1) into a muffle furnace for roasting for 1.5 h at 500 ℃, quickly transferring into a cerium salt solution prepared in the step (2) for quenching, standing for 40 min, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and transferring into a blast drying box for drying for 12h at 60 ℃ to obtain Ce-Fe2O3@CC。
Example 3
This example provides a metal ion doped Fe2O3The preparation method of the anode material comprises the following steps:
(1) 0.946 g ferric chloride hexahydrate (M = 270.3) and 3.48 g anhydrous sodium sulfate (M = 142.04) are respectively weighed, mixed and dissolved in 52.5 ml deionized water, stirred at room temperature for 30 min to obtain a clear solution, transferred to a 100 ml polytetrafluoroethylene liner, and added with 2X 1.75 cm2Performing a hydrothermal reaction on carbon cloth by a precipitation method, wherein the temperature of the hydrothermal reaction is 90 ℃, the time of the hydrothermal reaction is 12h, cleaning the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and performing blast drying to obtain a precursor, wherein the drying temperature is 80 ℃, and the drying time is 8 h;
(2) wherein 70. mu.L of titanium tetrachloride (M =189.68, 1.726 g/cm) was measured3) Dissolving in 35 ml ethanol, stirring at room temperature for 30 min to obtain clear solution, and refrigerating in 25 deg.C refrigerator for 6 hr to obtain titanium salt solution;
(3) transferring the precursor obtained in the step (1) into a muffle furnace for roasting at 550 ℃ for 2h, then quickly transferring into the titanium salt solution prepared in the step (2) for quenching, standing for 60min, then respectively cleaning with deionized water and absolute ethyl alcohol for three times, and after cleaning, transferring into a blast drying box 80 ℃ for drying for 8 h to obtain Ti-Fe2O3@CC。
Example 4
The other processes are the same as those in example 1 except for the difference (2) from example 1, and will not be described again. Wherein 35 ml of deionized water is directly refrigerated without adding metal salt, and the cathode material of the super capacitor prepared in the embodiment is marked as DIW-Fe2O3@CC。
The XRD patterns of the cathode materials prepared in the comparative example and the examples 1-4 are shown in figure 1, and it can be seen from the XRD patterns of the cathode materials quenched in different metal salt solutions, the XRD patterns are not obviously changed, and the method is proved to be capable of doping a small amount of metal ions on the basis of no phase change.
In SEM images of the cathode materials prepared in the comparative example and the examples 1-4, as shown in FIGS. 2-6, the structure of the material is not changed by the quenching process, and a small amount of metal ions can be doped on the basis of keeping the original shape of the material.
Impedance and cyclic voltammetry tests are carried out by using the cathode materials of the super capacitor prepared in the comparative example and the examples 1 to 4, and the test conditions are as follows: the implementation frequency is 1khz, the voltage range is-0.8-0V, and the material mass is 0.1 g; the sweep rate is 100 mV/s, the voltage range is 0-1.6V, and the area of the carbon cloth is 1 multiplied by 1 cm2The reference electrode is a saturated calomel electrode, and the counter electrode is a platinum net. The results are shown in FIGS. 7 and 8. As can be seen from the view in figure 7,M-Fe prepared in examples 1 to 42O3The flat band potential and the donor density of the @ CC electrode material are reduced, wherein in examples 1-3, the carrier concentration of the material can be improved due to surface doping of metal ions, the conductivity is further enhanced, the surface reduction reaction rate is enhanced, and the DIW-Fe prepared in example 42O3@ CC, because of the quenching process, the material surface generates defects, the specific surface area of the material is increased, and further the conductivity is enhanced. As can be seen from FIG. 8, M-Fe prepared in examples 1 to 42O3The capacity of the @ CC electrode material is improved to different degrees compared with that of a reference sample; and Sn-Fe2O3@ CC has the largest capacity, is Fe2O3More than twice of @ CC, which shows that the metal ion surface doping can provide more potential centers, obviously improves the capacitance of the material, DIW-Fe2O3The @ CC capacity is also significantly improved, indicating that the supercapacitor has higher capacity due to more active sites exposed by surface defects.
Example 5
The weighed mass of tin chloride pentahydrate was 12.271g, which is different from example 1, and the other processes are the same as example 1 and will not be described again. The negative electrode material Sn-Fe prepared in this example2O3@ CC, Properties of Sn-Fe prepared in example 12O3@ CC has the same properties and an area capacity (measured under the same conditions as example 1) of 128.96 mF/cm2。
Example 6
Except for weighing 12.158 g of cerous nitrate hexahydrate in the same manner as in example 2, the other processes are the same as in example 1 and will not be repeated herein. The anode material Ce-Fe prepared in the example2O3The @ CC has the same performance as the anode material prepared in example 2, and the area capacity (tested under the same test conditions as example 1) is 116.93mF/cm2。
Example 7
The only difference from example 3 is that 32. mu.L of titanium tetrachloride was measured, and the other processes were the same as in example 3 and will not be described herein again. The negative electrode material Ti-Fe prepared in this example2O3Preparation of @ CC with example 3The performance of the negative electrode material is the same, and the area capacity (tested under the same test conditions as example 1) is 129.35mF/cm2。
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. A method for preparing doped metal ion oxide by quenching process is characterized by comprising the following steps:
(1) dissolving trivalent ferric salt and sodium salt serving as reaction raw materials in water, adding carbon cloth to perform a precipitation hydrothermal reaction, washing, and drying to obtain a precursor;
(2) roasting the precursor, keeping the temperature at the roasting temperature, putting the precursor into a metal salt solution, standing, washing and drying to obtain a metal ion-doped oxide, namely a metal ion-doped Fe2O3A negative electrode material;
in the step (2), the metal salt is more than one of stannic chloride, cerous nitrate or titanium tetrachloride;
when the metal salt in the step (2) is tin chloride or cerium nitrate; the molar ratio of iron ions in the ferric iron salt to metal ions in the metal salt is 1: 5-1: 10; the concentration of the tin salt solution and the cerium salt solution is 0.5-1 mol/L;
when the metal salt is titanium tetrachloride; the molar ratio of iron ions in the ferric iron salt to titanium ions in the titanium salt is 5-12: 1; the titanium salt solution is formed by dissolving titanium tetrachloride in ethanol, and the volume fraction of the titanium tetrachloride is 0.1-0.2%;
the temperature of the metal salt solution in the step (2) is 4-25 ℃.
2. The method for preparing a doped metal ion oxide by using a quenching process as claimed in claim 1, wherein the ferric salt in the step (1) is ferric trichloride, and the sodium salt is sodium sulfate; dissolving the reaction raw materials by using deionized water; the hydrothermal reaction temperature is 90-160 ℃, and the hydrothermal reaction time is 6-12 h.
3. The method for preparing the doped metal ion oxide by using the quenching process as claimed in claim 1, wherein the molar ratio of the ferric iron salt to the sodium salt in the step (1) is 1: 1-7; the ratio of the amount of ferric ions in the ferric salt to the area of the carbon cloth is 5: 1-10: 1mol/m2The volume ratio of the amount of the ferric ions in the ferric salt to the water is 1: 15-1: 20 mol/L.
4. The method for preparing a doped metal ion oxide by quenching process according to claim 1, wherein the washing in step (1) and step (2) is three times or more washing with deionized water and absolute ethanol, respectively; the drying is blast drying or vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
5. The method for preparing the metal ion doped oxide by using the quenching process as claimed in claim 1, wherein the roasting temperature in the step (2) is 400-550 ℃, and the heat preservation time at the roasting temperature is 1-2 h.
6. The method for preparing doped metal ion oxide by quenching process according to claim 1, wherein the standing time in step (2) is 15-60 min.
7. A doped metal ion oxide prepared by the production method according to any one of claims 1 to 6.
8. Use of the doped metal ion oxide of claim 7 in the manufacture of a supercapacitor.
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