CN114694979A - Fluorinated and reconstructed electrode material and preparation method and application thereof - Google Patents
Fluorinated and reconstructed electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 19
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 17
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- 239000004202 carbamide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 14
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- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
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- SUOTZEJYYPISIE-UHFFFAOYSA-N iron(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SUOTZEJYYPISIE-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
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- 239000002105 nanoparticle Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
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- 239000000126 substance Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 6
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- 239000002135 nanosheet Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 238000004729 solvothermal method Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- -1 F)-And the like) Chemical class 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Images
Classifications
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a fluorinated and reconstructed electrode material and a preparation method and application thereof. The preparation method of the fluorinated reconstituted electrode material comprises the following steps: and (3) immersing the double-transition metal electrode material into molten ammonium fluoride for surface reconstruction. The preparation method of the fluorinated and reconstructed electrode material is simple to operate, easy to implement, short in reaction time and obvious in reaction effect, and the prepared fluorinated and reconstructed electrode material improves the capacity of the electrode material; meanwhile, the polarity and the chemical environment of the electrode surface are obviously improved, and the electrode has higher intrinsic activity and larger charge storage capacity. The fluorinated and reconstructed electrode material and the preparation method thereof are applied to the field of super capacitors for the first time, and the fluorinated and reconstructed electrode material shows excellent electrochemical performance.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a fluorinated and reconstructed electrode material and a preparation method and application thereof.
Background
In recent years, the increasing consumption of fossil energy and the increasing problem of environmental pollution have become two major problems that plague human society. It is predicted by the international energy prospect in 2018 (IEO2018) codified by the U.S. energy information agency that 41% of the dramatic rise in world energy consumption will occur from 2010 to 2040. At the same time, the prospect also suggests that by 2040 years the electricity production from renewable energy sources will rapidly develop at an average growth rate of 2.6% per year. It is seen that the vigorous development of renewable energy sources represented by new generation wind, tidal and solar energy and the establishment of sustainable clean energy storage and conversion systems are effective ways to solve the above two problems. However, due to the uncertainty of the storage time of natural energy and the low conversion efficiency, it is difficult to replace the traditional fossil energy rapidly in a short period of time, and thus the natural energy becomes a main sustainable energy. Therefore, how to establish a fixed and efficient energy storage system to meet the requirements of daily life becomes a main problem to be solved urgently in the field of sustainable energy development.
A super capacitor, also called an electrochemical capacitor, is a novel energy storage device between a battery and a conventional capacitor, and has attracted extensive attention in the field of energy storage due to its advantages of high power density, long cycle stability, rapid charging and discharging, environmental protection, safety, and the like. The super capacitor can be used alone or combined with a battery, and is applied to the fields of standby power supplies, industrial equipment, hybrid power/electric vehicles and the like. For example, supercapacitors are currently available in heavy vehicles, trucks and buses hybrid platforms, for intermittent renewable energy load balancing systems, and regenerative braking energy systems for storage of electric vehicles and light rails, among others. However, the lower energy density of supercapacitors compared to lithium ion batteries limits their further applications. Therefore, on the premise of ensuring the advantages of the supercapacitor, the improvement of the energy density is the research focus in the field of the supercapacitor at present.
For the energy density of the super capacitor, the energy density can be improved by preparing electrode materials with high specific capacity and assembling the electrode materials into an asymmetric capacitor. Cobalt, nickel based electrode materials in comparison to noble metal oxides (e.g., RuO)2、IrO2Etc.) has the obvious advantages of rich resources, low cost, etc., and simultaneously, the cobalt-nickel base electrode material is also activated by the excellent conductivity and the rich and active electrochemical oxidation-reduction reaction couple (such as Co)0/2+/3+/4+) While possessing high theoretical specific capacity (e.g. Co)3O4Is 3560F g-1) And reversibility, which is considered to be a very promising electrode material. However, the practical capacitance of cobalt and nickel-based electrode materials is limited by the effective exposure area and the low surface reactivity, and it is difficult to develop the theoretical value.
In recent years, anionic surface modifications have been found, particularly strongly electronegative anions (e.g., F)-And the like), the polarity and the chemical environment of the electrode surface can be obviously improved, meanwhile, weak metal-fluorine bonds generated on the surface are easy to break under the electrochemical oxidation condition, and a multilevel structure with a high-activity surface rich in M-OH and even more exposed active sites is formed, so that the electrode has higher intrinsic activity and larger charge storage capacity. At present, the common preparation methods of the fluorine ion surface modified supercapacitor electrode material are a chemical vapor deposition method, an electrodeposition method and a solvothermal method. The chemical vapor deposition method and the electrodeposition method tend to deposit new components on the electrode material, which inevitably reduces the gram volume density of the electrode material, and few reports indicate that the chemical deposition can successfully introduce fluorine into the electrode material, which may be related to strong electronegativity and ionicity of the electrode material; the cobalt and nickel-based electrode materials are modified by fluorinions by a solvothermal method, the raw materials of the cobalt and nickel-based electrode materials need high-risk hydrogen fluoride, the fluorine doping effect can only be achieved, and the atomic configuration and the micro-morphology of the surface of a product cannot be optimized.
Therefore, the method for fluoridizing and reconstructing is developed to achieve the effects of modifying the anionic surface and constructing a surface multilevel structure, and the preparation method of the electrode material with good stability and high energy density has very high application value.
Disclosure of Invention
The invention aims to solve the technical problems of low effective exposure area and surface reactivity and low electrochemical performance of the existing nano electrode material, and provides a fluorinated and reconstructed electrode material and a preparation method and application thereof.
The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a fluorinated and reconstructed electrode material, which comprises the following steps:
and (3) immersing the double-transition metal electrode material into molten ammonium fluoride for surface reconstruction.
In the invention, the molten ammonium fluoride firstly plays an etching role on the transition metal particles on the surface of the double-transition metal electrode; along with the prolonging of the reaction time, a large amount of transition metal ions are enriched at the interface of the molten ammonium fluoride and the metal, and combined reconstruction of the transition metal ions generates a large amount of metastable nanosheets. In the present invention, the ammonium fluoride may be ammonium fluoride which is conventional in the art and has a CAS number of 12125-01-8.
In the present invention, the ammonium fluoride in a molten state can be ammonium fluoride in a molten state which is conventional in the art, and those skilled in the art know that ammonium fluoride in a molten state is obtained according to the melting point of ammonium fluoride, and the melting temperature of the ammonium fluoride in a molten state is generally not lower than 98 ℃; preferably, the temperature is 240 to 280 ℃, for example, 250 ℃.
Wherein, preferably, the melting time of the ammonium fluoride in a molten state is at least 8 minutes; more preferably 10 to 15 minutes.
Wherein, the melting heating device of the ammonium fluoride in the molten state can be conventional in the field, and is preferably a hot table.
The melting operation of the ammonium fluoride in the molten state can be conventional in the art, and the ammonium fluoride is preferably melted by laying the ammonium fluoride on the bottom of the container.
In the present invention, the skilled person is aware of the list according to the double transition metal electrode materialThe mass of ammonium fluoride is suitably selected for the area, preferably at least 0.17g/cm2(ii) a Preferably 0.17 to 0.5g/cm2。
Preferably, the immersion time is not less than 15 seconds; more preferably 15 to 90 seconds; further preferably 45 to 90 seconds; still more preferably 60 to 90 seconds.
In the present invention, the steps generally further include a post-treatment step, which may be conventional in the art and generally refers to washing and drying.
Wherein the washing operation may be conventional in the art, preferably with water.
Preferably, the double-transition metal electrode material is a cobalt-nickel electrode material or a nickel-iron electrode material.
Wherein, the cobalt-nickel electrode material refers to an electrode substrate material loaded with cobalt-nickel nano particles; the nickel-iron electrode material refers to an electrode substrate material loaded with nickel-iron nano particles.
Wherein, the electrode substrate material can be conventional electrode substrate material in the field, such as carbon cloth, carbon paper, foamed cobalt, foamed copper or foamed nickel; preferably nickel foam.
The preparation method of the cobalt-nickel electrode material preferably comprises the following steps:
carrying out hydrothermal reaction on an electrode substrate material in a mixed aqueous solution of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and ammonium fluoride, and carrying out first-step calcination and second-step calcination to obtain the electrode substrate material;
wherein, preferably, the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate, the urea and the ammonium fluoride is 1: 1: 2.5-7.5: 1-3; more preferably 1: 1: 5: 2.
wherein, the temperature of the hydrothermal reaction is preferably 100-150 ℃; more preferably 120 deg.c.
Wherein, the time of the hydrothermal reaction is preferably 10 to 15 hours; more preferably 12 hours.
Wherein, preferably, the environment of the first step calcination is argon environment.
Wherein, the temperature of the first step calcination is preferably 250 to 350 ℃; more preferably 300 deg.c.
Wherein, the time of the first step of calcination is preferably 1 to 3 hours; more preferably 2 hours.
Wherein, preferably, the environment of the second step calcination is a mixed gas environment of 10% hydrogen and 90% argon, and the percentage of the hydrogen and the argon is the volume ratio of the hydrogen to the argon in the mixed gas.
Wherein, the temperature of the second step of calcination is preferably 400 to 600 ℃; more preferably 500 deg.c.
Wherein, the time of the second step of calcination is preferably 1 to 3 hours; more preferably 2 hours.
The preparation method of the nickel-iron electrode material preferably comprises the following steps:
the electrode substrate material is prepared by hydrothermal reaction, first-step calcination and second-step calcination in a mixed aqueous solution of cobalt nitrate hexahydrate, ferrous nitrate hexahydrate, urea and ammonium fluoride;
wherein, preferably, the molar ratio of the nickel nitrate hexahydrate, the ferrous nitrate hexahydrate, the urea and the ammonium fluoride is 1: 1: 2.5-7.5: 1-3; more preferably 1: 1: 5: 2.
wherein, the temperature of the hydrothermal reaction is preferably 100-150 ℃; preferably 120 deg.c.
Wherein, the time of the hydrothermal reaction is preferably 10 to 15 hours; preferably 12 hours.
Wherein, preferably, the environment of the first step calcination is argon environment, and the temperature of the first step calcination is 250-350 ℃; more preferably 300 deg.c.
Wherein, the time of the first step of calcination is preferably 1 to 3 hours; more preferably 2 hours.
Wherein, preferably, the environment of the second step calcination is a mixed gas environment of 10% hydrogen and 90% argon, and the percentage of the hydrogen and the argon is the volume ratio of the hydrogen to the argon in the mixed gas.
Wherein, the temperature of the second step of calcination is preferably 400 to 600 ℃; more preferably 500 deg.c.
Wherein, the time of the second step of calcination is preferably 1 to 3 hours; more preferably 2 hours.
The electrode substrate material is pretreated as known by those skilled in the art, and the pretreatment method is conventional in the art, and generally refers to that the electrode substrate material is sequentially ultrasonically cleaned in acetone, absolute ethyl alcohol, dilute hydrochloric acid (2mol/L) and deionized water for 10min, and then is vacuum-dried at room temperature for 24h to remove surface impurities and oxide layers.
Wherein, the electrode substrate material after the hydrothermal reaction is washed and dried, and then is subjected to a first step calcination and a second step calcination, as known by those skilled in the art.
Wherein, the container for the hydrothermal reaction can be conventional in the field, and is preferably a hydrothermal kettle.
Wherein the hydrothermal reaction environment may be conventional in the art, preferably heating in an oven.
Wherein the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate, the ferrous nitrate hexahydrate, the urea, and the ammonium fluoride may be conventional in the art. The CAS number of the cobalt nitrate hexahydrate is 10026-22-9; the CAS number of the nickel nitrate hexahydrate is 13478-00-7; the CAS number of the ferrous nitrate hexahydrate is 14013-86-6; the CAS number of the urea is 57-13-6; the CAS number for the ammonium fluoride is 12125-01-8.
Wherein the water may be deionized water as is conventional in the art.
In a preferred embodiment of the present invention, the amount of cobalt nitrate hexahydrate is 0.58g, the amount of nickel nitrate hexahydrate is 0.58g, the amount of urea is 0.6g, the amount of ammonium fluoride is 0.148g, the amount of water is 40mL, the electrode substrate material is nickel foam, the size of the electrode substrate material is 2 × 3cm, and the specification of the hydrothermal kettle is 50 mL.
In another preferred embodiment of the present invention, the dosage of the cobalt nitrate hexahydrate is 0.58g, the dosage of the ferrous nitrate hexahydrate is 0.58g, the dosage of the urea is 0.6g, the dosage of the ammonium fluoride is 0.148g, the dosage of the water is 40mL, the electrode substrate material is foamed nickel, the size of the electrode substrate material is 2 × 3cm, and the specification of the hydrothermal kettle is 50 mL.
In the invention, the particle diameter of the prepared double-transition metal electrode material is 100-500 nm.
Wherein the particle diameter of the prepared cobalt-nickel electrode material is 200 nm.
Wherein the particle diameter of the prepared nickel-iron electrode material is 400 nm.
The invention provides a fluorinated reconstituted electrode material prepared by the preparation method.
The invention provides an application of the fluorinated restructured electrode material in the field of electrochemistry.
Preferably, the fluorinated and reconstructed electrode material is applied to a positive electrode material of a super capacitor or an electrocatalytic oxygen evolution electrode material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the preparation method of the fluorinated and reconstructed electrode material is realized by a molten salt method, is simple to operate, uses few equipment, is common equipment and is easy to realize.
2. The preparation method of the fluorinated and reconstructed electrode material has short reaction time and obvious reaction effect, and a large number of metastable nanosheet structures are formed on the surface of the prepared fluorinated and reconstructed electrode material, so that the effective exposure area is increased, and the capacity of the electrode material is improved; meanwhile, abundant weak M-F bonds are introduced on the surface of the electrode material reconstructed by fluorination, so that the polarity and the chemical environment of the electrode surface can be obviously improved, and a high-activity surface rich in M-OH is formed under the electrochemical oxidation condition, so that the electrode material has higher intrinsic activity and larger charge storage capacity.
3. The fluorinated and reconstructed electrode material and the preparation method thereof are applied to the field of super capacitors for the first time, and the fluorinated and reconstructed electrode material shows excellent electrochemical performance; the fluorinated reconstructed cobalt-nickel electrode material is 1A g-1The specific capacity reaches 2476F g at the current density of-1(ii) a Even at 10A g-1Still has 1390F g at high current-1At 10A g-1The capacity is kept 85.6% after the next 10000 cycles of circulation; the fluorinated and reconstructed ferronickel electrode material only needs 218mV overpotential to obtain 10mA cm-2The response current of (2), and meanwhile, the electrode can also stably generate oxygen for more than 50 hours.
Drawings
FIG. 1 is an X-ray diffraction pattern of a fluorinated reconstituted electrode material prepared in example 1 of the invention.
FIG. 2 is a scanning electron micrograph of cobalt nickel electrode material and the resulting fluorinated reconstituted electrode material used in examples 1-3 of the present invention.
FIG. 3 is a transmission electron micrograph of cobalt nickel electrode material and the resulting fluorinated reconstituted electrode material used in examples 1-3 of the present invention.
Fig. 4 shows the results of specific surface area measurements of fluorinated reconstituted electrode material made in example 1 of the invention.
FIG. 5 shows the results of electrochemical performance tests on fluorinated and reconstituted electrode materials prepared in examples 1-3 of the present invention as positive electrode materials for supercapacitors, wherein 4a is sweep rate of 5mV s-1CV curve of (4 b) is 1Ag-14c is a comparison of the mass to capacity at different current densities.
Fig. 6 shows the results of cycle performance testing of fluorinated reconstituted electrode material made in example 1 of the invention.
Fig. 7 is a scanning electron micrograph of a nickel-iron electrode material used in example 4 of the present invention and a fluorinated reconstituted electrode material prepared.
FIG. 8 shows the results of electrochemical performance tests of fluorinated reconstituted electrode material prepared in example 4 of the present invention as an electrocatalytic oxygen evolution electrode.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, cobalt nitrate hexahydrate having a CAS number of 10026-22-9, nickel nitrate hexahydrate having a CAS number of 13478-00-7, ferrous nitrate hexahydrate having a CAS number of 14013-86-6, urea having a CAS number of 57-13-6, and ammonium fluoride having a CAS number of 12125-01-8 were used.
In embodiments 1 to 3 of the present invention, a method for performing a supercapacitor performance test on a prepared fluorinated restructured electrode material includes:
and (3) testing conditions are as follows: the electrochemical measurement system is a standard three-electrode system, namely, the fluorinated reconstructed electrode material prepared by the invention is a working electrode, a platinum sheet is a counter electrode, and a saturated calomel electrode is a reference electrode, and the electrochemical test is carried out on an Autolab PGSTAT302N electrochemical workstation by taking a 1M potassium hydroxide solution as an electrolyte solution.
The testing process comprises the following steps: under the condition of constant temperature of 25 ℃, the fluorinated and reconstructed electrode material prepared by the method is placed in electrolyte, and the electrode activation process is completed by performing a cyclic 20-circle test at a scanning speed of 50mV/s within a potential interval of 0-0.6V (relative to saturated calomel). Then, performing cyclic voltammetry test at a scanning rate of 5mV/s in a potential range of-0.1-0.5V (relative to saturated calomel), so as to obtain a CV curve; obtaining a GCD curve through a charge and discharge test; during the cycle test, the fluorinated reconstructed electrode material prepared by the invention is placed in electrolyte under the constant current density (10 Ag)-1) And (5) testing charging and discharging, and recording the change condition of the specific capacity to obtain a stability curve.
In example 4 of the present invention, a method for testing the oxygen evolution performance of an electrode on a fluorinated and reconstituted electrode material is as follows:
and (3) testing conditions are as follows: the electrochemical measurement system is a standard three-electrode system, namely, the fluorinated reconstructed electrode material prepared by the method is a working electrode, the graphite rod is a counter electrode, the saturated Ag/AgCl electrode is a reference electrode, and the electrochemical test is carried out on a CHI 760 electrochemical workstation by taking a 1M potassium hydroxide solution as an electrolyte solution.
The testing process comprises the following steps: and introducing oxygen into the electrolyte for about 30min at a constant temperature of 25 ℃ to saturate the oxygen in the solution, placing the fluorinated and reconstructed electrode material prepared by the invention into the electrolyte, and performing a cyclic 20-turn test at a scanning speed of 50mV/s within a potential interval of 0-0.7V (relative to saturated Ag/AgCl) to complete the activation process of the electrode. Then, performing cyclic voltammetry test at a scanning rate of 5mV/s in a potential range of 0-0.8V (relative to saturated Ag/AgCl) to obtain an oxygen evolution polarization curve; the fluorinated and reconstructed electrode material prepared by the method is placed in electrolyte, and the potential change condition is tested under constant oxygen evolution current, so that a stability curve can be obtained.
Example 1
And (3) performing hydrothermal reaction on the pretreated foamed nickel (2 multiplied by 3cm) in a mixed aqueous solution of 0.58g of cobalt nitrate hexahydrate, 0.58g of nickel nitrate hexahydrate, 0.6g of urea and 0.148g of ammonium fluoride, cleaning, drying, calcining in the first step and calcining in the second step to obtain the cobalt-nickel electrode material.
The pretreatment method comprises the steps of sequentially ultrasonically cleaning foamed nickel in acetone, absolute ethyl alcohol, dilute hydrochloric acid (2mol/L) and deionized water for 10min, and then carrying out vacuum drying for 24h at room temperature to remove surface impurities and an oxidation layer. The amount of water used was 40 mL. The temperature of the hydrothermal reaction is 120 ℃; the hydrothermal reaction time is 12 hours; the container of the hydrothermal reaction is a 50mL hydrothermal kettle; the hydrothermal reaction is carried out in an oven. The environment of the first step of calcination is argon environment; the temperature of the first step of calcination is 300 ℃; the time for the first calcination step was 2 hours. The second step of calcination is performed in a mixed gas environment of 10% of hydrogen and 90% of argon, and the percentage of the hydrogen and the argon is the volume ratio of the hydrogen to the argon in the mixed gas; the temperature of the second step of calcination is 500 ℃; the time for the second calcination step was 2 hours.
And (3) immersing the cobalt-nickel electrode material into molten ammonium fluoride for surface reconstruction, washing with water and drying to obtain the fluorinated reconstructed electrode material F-CoNi-60 s.
Wherein the amount of ammonium fluoride is 1 g. The melting temperature of the ammonium fluoride in the molten state was 250 ℃. The melting time of the ammonium fluoride in the molten state was 10 minutes. The melting and heating device of the ammonium fluoride in a molten state is a hot table. The immersion time was 60 seconds.
The X-ray diffraction pattern of the prepared fluorinated reconstructed electrode material is shown in figure 1, and the structure of the cobalt-nickel electrode material is not changed by the fluorinated reconstruction. Fig. 2 and 3 respectively compare the obtained fluorinated and reconstructed electrode material with the scanning and transmission electron micrographs of other examples, that is, it can be observed that the surface of the cobalt-nickel electrode material is fluorinated and reconstructed to generate a metastable nanosheet structure, and the nanosheets gradually increase with the extension of the reaction time. Figure 4 shows the increase in specific surface area of the resulting fluorinated reconstituted electrode material.
F-CoNi-60s-A in FIGS. 5 and 6 shows the electrochemical performance of the fluorinated reconstituted electrode material prepared in this example, at 1A g-1The specific capacity reaches 2476F g at the current density of-1Even at 10Ag-1Still has 1390F g at high current-1High capacity of (2); at 10A g-1The capacity remained 85.6% after the next 10000 cycles.
Example 2
The same procedure as in example 1, but with a 15 second immersion time, gave F-CoNi-15s, which was a fluorinated reconstituted electrode material.
The SEM image of the fluorinated reconstituted electrode material prepared in this example is shown in F-CoNi-15s in FIG. 2. The transmission electron micrograph of the fluorinated reconstituted electrode material prepared in this example is shown in FIG. 3 as F-CoNi-15 s. The electrochemical performance of the fluorinated reconstituted electrode material prepared in this example is shown in FIG. 5 as F-CoNi-15 s-A.
Example 3
The same procedure as in example 1, but with a dipping time of 45 seconds, gave F-CoNi-45s, which was a fluorinated reconstituted electrode material.
The SEM image of the fluorinated reconstituted electrode material prepared in this example is shown in F-CoNi-45s in FIG. 2. A transmission electron micrograph of the fluorinated reconstituted electrode material prepared in this example is shown in FIG. 3 as F-CoNi-45 s. The electrochemical performance of the fluorinated reconstituted electrode material prepared in this example is shown in FIG. 5 as F-CoNi-45 s-A.
Example 4
The same as example 1, but 0.58g of cobalt nitrate hexahydrate is replaced by 0.58g of ferrous nitrate hexahydrate, and the fluorinated and reconstructed electrode material F-NiFe-60s is obtained.
Fig. 7 is a scanning electron micrograph of the used ferronickel electrode material and the prepared fluorinated and reconstructed electrode material, and it can be observed that the surface of the ferronickel electrode material is fluorinated and reconstructed to generate a metastable nanosheet structure.
FIG. 8 shows the results of OER activity and stability tests on fluorinated reconstituted electrode material prepared in example 4, with a F-NiFe-60s sample requiring only 218mV overpotential to obtain 10mA cm-2The response current of the electrode is high, and meanwhile, the electrode can stably generate oxygen for more than 50 hours.
Claims (10)
1. A method of preparing a fluorinated reconstituted electrode material, comprising the steps of: and (3) immersing the double-transition metal electrode material into molten ammonium fluoride for surface reconstruction.
2. The method of preparing a fluorinated reconstituted electrode material of claim 1, wherein the ammonium fluoride in a molten state has a melting temperature of not less than 98 ℃; preferably, 240 to 280 ℃, for example, 250 ℃;
and/or the melting time of the ammonium fluoride in a molten state is at least 8 minutes; preferably 10 to 15 minutes;
and/or the melting heating device of the ammonium fluoride in the molten state is a hot table;
and/or the melting operation of the ammonium fluoride in the molten state is to melt the ammonium fluoride by flatly laying the ammonium fluoride on the bottom of the container.
3. The method of making a fluorinated reconstituted electrode material of claim 1, wherein the double transition metal electrode material is a cobalt nickel electrode material or a nickel iron electrode material;
and/or the immersion time is not less than 15 seconds; preferably 15 to 90 seconds; more preferably 45 to 90 seconds; further preferably 60 to 90 seconds;
and/or the steps of the preparation method of the fluorinated reconstituted electrode material further comprise a post-treatment step, wherein the post-treatment step is cleaning and drying.
4. The method of making a fluorinated reconfigured electrode material of claim 3 wherein the cleaning operation is water rinsing;
and/or the mass of the ammonium fluoride is at least 0.17g/cm2(ii) a Preferably 0.17 to 0.5g/cm2；
And/or the cobalt-nickel electrode material is an electrode substrate material loaded with cobalt-nickel nanoparticles;
and/or the ferronickel electrode material is an electrode substrate material loaded with ferronickel nano particles;
and/or the particle diameter of the double transition metal electrode material is 100-500 nm;
and/or the particle diameter of the cobalt-nickel electrode material is 200 nm;
and/or the particle diameter of the nickel-iron electrode material is 400 nm.
5. The method of making a fluorinated reconfigured electrode material of claim 4 wherein the electrode substrate material is carbon cloth, carbon paper, cobalt foam, copper foam or nickel foam; preferably nickel foam;
and/or the preparation method of the cobalt-nickel electrode material comprises the following steps:
carrying out hydrothermal reaction on an electrode substrate material in a mixed aqueous solution of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and ammonium fluoride, and carrying out first-step calcination and second-step calcination to obtain the electrode substrate material;
and/or the preparation method of the nickel-iron electrode material comprises the following steps:
the electrode substrate material is prepared by hydrothermal reaction, first-step calcination and second-step calcination in a mixed aqueous solution of cobalt nitrate hexahydrate, ferrous nitrate hexahydrate, urea and ammonium fluoride;
and/or, pretreating the electrode substrate material: and ultrasonically cleaning the electrode substrate material in acetone, absolute ethyl alcohol, dilute hydrochloric acid and deionized water for 10min respectively, and then vacuum-drying for 24h at room temperature.
6. The method of preparing a fluorinated reconstituted electrode material according to claim 5, wherein in the method of preparing a cobalt-nickel electrode material, the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate, the urea and the ammonium fluoride is 1: 1: 2.5-7.5: 1-3; more preferably 1: 1: 5: 2;
and/or in the preparation method of the ferronickel electrode material, the molar ratio of the nickel nitrate hexahydrate, the ferrous nitrate hexahydrate, the urea and the ammonium fluoride is 1: 1: 2.5-7.5: 1-3; more preferably 1: 1: 5: 2;
and/or the container of the hydrothermal reaction is a hydrothermal kettle;
and/or the hydrothermal reaction environment is heating in an oven;
and/or the temperature of the hydrothermal reaction is 100-150 ℃; preferably 120 ℃;
and/or the time of the hydrothermal reaction is 10-15 hours; preferably 12 hours;
and/or the environment of the first step of calcination is an argon environment;
and/or the temperature of the first step of calcination is 250-350 ℃; preferably 300 ℃;
and/or the time of the first step of calcination is 1-3 hours; preferably 2 hours;
and/or the environment of the second-step calcination is a mixed gas environment of 10% of hydrogen and 90% of argon, and the percentages of the hydrogen and the argon are volume ratios of the hydrogen and the argon in the mixed gas;
and/or the temperature of the second step of calcination is 400-600 ℃; preferably 500 ℃;
and/or the time of the second step of calcination is 1-3 hours; preferably 2 hours.
7. The method of preparing a fluorinated reconstituted electrode material according to claim 6, wherein the hydrothermally reacted electrode base material is washed and dried, followed by a first calcination step and a second calcination step;
and/or the water is deionized water;
and/or the dosage of the cobalt nitrate hexahydrate is 0.58g, the dosage of the nickel nitrate hexahydrate is 0.58g, the dosage of the urea is 0.6g, the dosage of the ammonium fluoride is 0.148g, the dosage of the water is 40mL, the electrode substrate material is foamed nickel, the size of the electrode substrate material is 2 x 3cm, and the specification of the hydrothermal kettle is 50 mL;
and/or the dosage of the cobalt nitrate hexahydrate is 0.58g, the dosage of the ferrous nitrate hexahydrate is 0.58g, the dosage of the urea is 0.6g, the dosage of the ammonium fluoride is 0.148g, the dosage of the water is 40mL, the electrode substrate material is foamed nickel, the size of the electrode substrate material is 2 x 3cm, and the specification of the hydrothermal kettle is 50 mL.
8. A fluorinated reconstituted electrode material prepared by the method of preparing a fluorinated reconstituted electrode material according to any one of claims 1 to 7.
9. Use of a fluorinated reconstituted electrode material according to claim 8 in the electrochemical field.
10. Use of the fluorinated reconstituted electrode material according to claim 8 on a supercapacitor positive electrode material or an electrocatalytic oxygen evolution electrode material.
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