CN110277250B - Fe3O4-GO composite electrode and preparation method and application thereof - Google Patents
Fe3O4-GO composite electrode and preparation method and application thereof Download PDFInfo
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- CN110277250B CN110277250B CN201910645709.XA CN201910645709A CN110277250B CN 110277250 B CN110277250 B CN 110277250B CN 201910645709 A CN201910645709 A CN 201910645709A CN 110277250 B CN110277250 B CN 110277250B
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000004070 electrodeposition Methods 0.000 claims abstract description 64
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000002484 cyclic voltammetry Methods 0.000 claims description 11
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 10
- 229910001447 ferric ion Inorganic materials 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000003990 capacitor Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 25
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- 230000008569 process Effects 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000840 electrochemical analysis Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001448 ferrous ion Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910002836 PtFe Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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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
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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Abstract
The invention relates to Fe3O4A Graphene Oxide (GO) composite electrode, a preparation method and an application thereof; belongs to the technical field of electrochemistry. The composite electrode is prepared by directly depositing on a current collector by using a uniform and stable mixed solution formed by a ferric salt solution, a specific complexing agent and a GO dispersion liquid as an electrodeposition liquid through an electrodeposition technology to obtain the composite electrode. The invention has the advantages of simple preparation process, mild condition, stable system, high preparation speed, excellent performance and the like, and is suitable for industrial production.
Description
Technical Field
The invention relates to a super capacitor cathode and a preparation method and application thereof, belonging to the technical field of electrochemistry.
Background
In order to improve the performance of the super capacitor, namely, the advantages of high specific power and the like are kept while the specific energy is improved, and the super capacitor has better cycle stability, the research effect aiming at the transition metal oxide anode material for the super capacitor is obvious at present, and the specific capacitance of some anode materials can even reach more than 2000F/g. However, from the aspect of preparing high specific energy devices, the cathode materials capable of being used with these high specific capacitance cathode materials are still relatively lacking. The capacity of the carbon material widely used as the cathode can only reach about 200F/g generally at present, if the carbon material cathode and the transition metal oxide anode are used for preparing an asymmetric capacitor, in order to match and balance the capacities of the anode and the cathode in a device, the gram specific capacitance of the cathode material is obviously lower, the mass of an active substance in the cathode of the device is more than several times of that of the active substance of the anode, particularly the carbon material, the volume is obviously increased, and the specific energy of the final device is limited.
Because iron-based materials, particularly iron-based oxides, have the outstanding advantages of rich iron element resources, low price, environmental friendliness and the like, the iron-based materials are more and more concerned in research of the iron-based oxides as negative electrode materials in water-based supercapacitors. However, the iron oxide has the defects of poor conductivity and poor cycle stability, and the capacity is far lower than the theoretical capacity. Therefore, around these problems, researchers have adopted many methods to improve the electrochemical properties of iron oxides, with complexing with carbon materials being one of the most common methods. Graphene is commonly used to complex with iron oxides due to its high specific surface area, high conductivity and stability. However, the commonly used composite methods are chemical vapor deposition, hydrothermal method, high-temperature synthesis and the like, and have the disadvantages of long process, high energy consumption, expensive equipment and high material preparation cost. Therefore, it is difficult to realize industrialization. There have been attempts by scholars to prepare Fe by electrodeposition3O4(ii) a For example, Shuichi paper of Xiamen university for preparing PtFe and Fe by electrodeposition3O4Nano-catalyst and performance research thereof in the text, Fe with superior performance is prepared by electrodeposition3O4And (3) a nano catalyst. However, the addition of graphene and the Fe is not mentioned in this paper3O4Can be used as a report of electrodes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Fe3O4-GO composite electrodes and methods of making the same.
The invention finds that the Fe is treated in the research process3O4The preparation conditions of-GO composite electrodes are relatively harsh.
The invention relates to electro-deposition Fe3O4-GO composite electrode, said Fe3O4Co-depositing with GO on a current collector under the action of an electric field. Fe designed by the invention3O4-GO composite electrode, which does not require additional binder and conductive agent.
The invention relates to electro-deposition Fe3O4-a GO composite electrode, said composite electrode material being an oxide of Fe attached to GO, co-deposited on a current collector,and form Fe3O4-a GO composite electrode.
The invention relates to a method for preparing Fe3O4-a method of GO composite electrode comprising the steps of:
step one
Stirring soluble ferric salt in water, then dropwise adding a complexing agent to form a mixed solution, and then dropwise adding alkali to form a transparent dark green solution; the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water;
in the mixed solution, the molar ratio of the complexing agent to the iron element is more than or equal to 1, preferably more than or equal to 1.3;
the molar ratio of hydroxide radical to iron element brought by alkali is more than or equal to 10;
step two
Transparent dark green solution by volume: adding 0.1-2 mg/mL of GO dispersion into the transparent dark green solution obtained in the step one according to the proportion of 0.8-1:0.8-1.2, and performing ultrasonic dispersion to obtain an electrodeposition solution;
step three
Taking a current collector material as a cathode, placing the cathode in the electrodeposition liquid obtained in the step two, performing electrodeposition under the stirring condition, and co-depositing on the current collector to obtain Fe3O4-a GO composite electrode.
The invention relates to electro-deposition Fe3O4A preparation method of the GO composite electrode, wherein in the step one, the soluble ferric salt is selected from at least one of ferric sulfate, ferric nitrate and ferric chloride.
The invention relates to electro-deposition Fe3O4In the first step, the complexing agent is one or more of ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, Triethanolamine (TEA) and sodium gluconate.
The invention relates to electro-deposition Fe3O4In the preparation method of the-GO composite electrode, in the step one, the added NaOH is in an amount that the molar concentration ratio of NaOH to ferric ions is more than 10: 1.
The invention relates to electro-deposition Fe3O4And in the second step, in the formed uniform and stable electrodeposition liquid, the concentration of ferric ions is not more than 0.01mol/L, the concentration of GO dispersion liquid is not more than 1mg/mL, and preferably the concentration of GO in the electrodeposition liquid is 0.2-1 mg/mL. In the experimental process, the phenomenon of coagulation due to the fact that a large amount of ferric ions and GO are easily adsorbed by static electricity once the ferric ions and GO exceed the range defined by the invention is found, so that the performance of the obtained product is extremely poor, and even the target product cannot be obtained.
The invention relates to electro-deposition Fe3O4And in the second step, continuous ultrasonic dispersion is required during the mixing preparation of the electrodeposition liquid.
The invention relates to electro-deposition Fe3O4And in the second step, the frequency of ultrasonic waves used for ultrasonic dispersion is 40kHz-100 kHz.
The invention relates to electro-deposition Fe3O4And in the third step, the current collector can be a stainless steel sheet, a titanium sheet, carbon paper, ITO and other conductive substrates.
The invention relates to electro-deposition Fe3O4And a preparation method of the-GO composite electrode, wherein in the third step, the stirring speed of the magnetic stirrer is 60-300 r/min, and the electrodeposition temperature is controlled at 30-70 ℃.
The invention relates to electro-deposition Fe3O4A preparation method of the GO composite electrode, wherein in the third step, the deposition mode adopted during the electrodeposition is one selected from cyclic voltammetry electrodeposition, constant potential electrodeposition and constant current deposition;
in the cyclic voltammetry electrodeposition, the cyclic window is-1.6-0.5V (relative to a saturated calomel electrode SCE), and preferably-1.5-0V; the scanning rate is 20-500 mV/s, preferably 50-200 mV/s; the number of cycles is 10-50.
In the constant potential electrodeposition, the control potential is between-1.5 and-0.9V (relative to SCE), preferably between-1.4 and-1V; the deposition time is 300-1800 s.
During the constant current electrodeposition, the current density is controlled to be 4-50 mA/cm2The deposition time is 100-1800 s.
The invention relates to electro-deposition Fe3O4And a preparation method of the-GO composite electrode, wherein in the third step, the obtained composite electrode is subjected to codeposition and then dried for more than 3 hours, preferably 70-100 ℃ at the temperature of 50-150 ℃.
The invention relates to electro-deposition Fe3O4The application of the GO composite electrode is that the composite electrode is used as a negative electrode of a water system super capacitor under a neutral or alkaline condition, and the mass specific capacity of an active substance of the composite electrode is 200-450F/g. Preferably 400-450F/g.
The invention relates to electro-deposition Fe3O4-a GO composite electrode, said electrode being detected under the conditions:
using 0.5-6 mol/L KOH or 0.5-1M Li2SO4The water solution is electrolyte solution, the composite electrode prepared by the invention is used as a working electrode, and the area is 2 multiplied by 2cm2The platinum electrode is used as a counter electrode to assemble a three-electrode system to carry out cyclic voltammetry test, the test potential range under alkaline conditions is-1.1 to 0V (Hg/HgO), and the test potential range in neutral electrolyte is-1.3 to-0.4V (Hg/Hg)2SO4)。
Principles and advantages
The principle is as follows:
the invention prevents Fe by selecting a proper amount of soluble ferric salt to be complexed with a complexing agent3+With OH in solution-Forming a precipitate to obtain a stable alkaline electrodeposition solution; then, ferric ions are utilized to obtain electrons on the cathode to form a complex product of the ferrous ions and the complexing agent, and the complex product reacts with the ferric ions to form Fe3O4(ii) a On the other hand, the surface of GO has negative charge functional groups, part of iron ions can be adsorbed to GO due to electrostatic acting force, then under the action of an electric field, the iron ions migrate to the surface of the cathode in the direction of the cathode to generate charge transfer, and the iron ions and part of GO are reduced at the same time to form Fe3O4Co-depositing with partially reduced GO on the cathode surface to obtain a self-bonded composite electrode.
The advantages are that:
(1) production of Fe in the usual case3O4Need to make sure thatMaintaining the presence of ferrous ions in the feedstock, it is desirable to avoid the problem of oxidation of ferrous ions, and the present feedstock does not require the presence of ferrous ions, resulting in Fe3O4The ferrous ion in the composite electrode material is obtained by reducing ferric ion in the raw material in situ on the surface of the electrode, so that the used electrodeposition solution is stable and can be repeatedly used for preparing the composite electrode material.
(2) The complexing of a proper amount of complexing agent and ferric ions with proper concentration is not only used for preparing Fe by electrodeposition3O4And meanwhile, ferric ions and GO are prevented from being subjected to coagulation due to large-scale electrostatic adsorption (at the moment, the quantity and concentration of GO must be strictly controlled), so that the two components can stably exist and are uniformly dispersed in the electrodeposition solution.
(3) The active substance of the composite electrode is directly attached to the surface of the electrode, so that the conductivity between the active substance and the current collector is ensured, and additional binder and conductive agent are not needed, so that the electrochemical performance of the electrode can be integrally improved.
(4)Fe3O4Co-depositing directly with GO to make Fe3O4Good in bonding property with GO, and partially reduces GO in an electrochemical reduction mode, so that the conductivity of the composite electrode is improved, and Fe is used3O4Attached to GO, thereby improving its cycling stability.
(5) The composite electrode is synthesized in one step through electrochemistry, the process is simple, the operation is easy, the requirements on equipment and environment are low, and the time and the cost are saved.
Drawings
FIG. 1 shows Fe prepared in example one3O4-cyclic voltammogram of GO composite electrode.
FIG. 2 shows Fe prepared under the conditions of the examples3O4SEM image of-GO composite electrode
FIG. 3 is Fe prepared in example one3O4-XRD pattern of GO composite electrode.
The specific capacitance of the corresponding electrode material can be calculated from the curve in fig. 1.
The Fe produced can be seen from FIG. 23O4-micro-topography of GO composite electrode.
As can be seen from fig. 3: fe3O4Diffraction peak of (2) with standard Fe3O4The characteristic peaks of the PDF card are matched, which indicates that the prepared electrode active substance is Fe3O4。
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The specific embodiment of the invention is as follows:
example one
Mixing Fe2(SO4)3Preparation of Fe with TEA+3And TEA is respectively 0.01 and 0.012mol/L mixed solution system Fe-TEA; then 0.4mol/L NaOH solution is prepared. The NaOH solution was then added dropwise to the Fe-TEA while stirring continuously until a clear solution was formed.
And adding the transparent solution into the 1mg/mLGO dispersion liquid in the same volume, and performing ultrasonic dispersion to obtain uniform and stable electrodeposition liquid.
Cutting area of 4 × 1cm2The carbon paper of (2) serves as a current collector. Firstly using 4mol/L H2SO4Soaking the carbon paper for 1h, then washing the carbon paper to be neutral by using deionized water, then soaking the carbon paper for 1h by using a mixed solution with the same volume of acetone-alcohol, washing the carbon paper by using the deionized water, and drying the carbon paper for later use. Using 4X 4cm2The titanium mesh electrode coated with ruthenium oxide on the surface was used as an anode, and the carbon paper subjected to surface treatment was used as a cathode (working area 2X 1 cm)2) And using SCE as a reference electrode, and placing the SCE and the reference electrode in an electrodeposition solution at 50 ℃ for electrodeposition. The deposition is carried out by cyclic voltammetry, the scanning rate is 50mV/s, and the number of cycles is 20. The deposition was followed by drying in an oven at 70 ℃ for more than 6 hours.
Using 1mol/L lithium sulfate aqueous solution as electrolyte and Fe3O4the-GO composite electrode is used as a working electrode and has an area of 2 x 2cm2The platinum electrode is a counter electrode, the mercury-mercurous sulfate electrode is a reference electrode to assemble a three-electrode system, cyclic voltammetry is carried out, the test potential range is-1.3 to-0.4V, the scanning rate is 5 to 200mV/s, the obtained cyclic voltammetry curve is shown in figure 1, and the specific capacitance of the electrode active substance is 321F/g according to the cyclic voltammetry curve (50mV/s scanning rate).
Example two:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
and carrying out electrochemical test on the composite electrode obtained by electrodeposition in a 4mol/L KOH aqueous solution, wherein the reference electrode is an Hg/HgO electrode, the test potential window is-1.1-0V, and the measured specific mass capacity is 255F/g.
Example three:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
the stainless steel sheet is used as a current collector of a working electrode, and is firstly polished by 800-mesh abrasive paper, then is ultrasonically cleaned by acetone and deionized water, and then is dried after being cleaned by alcohol. Fe2(SO4)3Preparation of Fe with TEA+3And TEA is respectively 0.005 and 0.006mol/L mixed liquid system Fe-TEA; and preparing 0.2mol/L NaOH solution, carrying out electrochemical test on the obtained composite electrode in 4mol/L KOH aqueous solution at the electrodeposition temperature of 30 ℃ for 10 circles of circulating cycles, wherein the reference electrode is an Hg/HgO electrode, the test potential window is-1.1-0V, and the measured specific mass capacity is 415F/g.
Example four:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
using FeCl3·6H2O instead of Fe2(SO4)3Complexation with TEA, TEA: fe3+The molar ratio was 1.5: 1. The composite electrode obtained by using carbon paper as a current collector is arranged at 1MLi2SO4Electrochemical test is carried out in the aqueous solution, the test potential window is-1.4 to-0.4V, and the measured specific capacity of the electrode active material is 440F/g.
Example five:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
with Fe (NO)3)3·6H2O instead of Fe2(SO4)3Complexation with TEA, TEA: fe3+The molar ratio was 1.5: 1. The carbon paper is used as a current collector, and the obtained composite electrode is arranged in 1MLi2SO4And carrying out electrochemical test in the aqueous solution, wherein the specific capacity of the electrode active material is 420F/g, which is measured by a test potential window of-1.3 to-0.4V.
Example six:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
with Fe (NO)3)3·6H2O instead of Fe2(SO4)3Complexation with TEA, TEA: fe3+The molar ratio was 1.5: 1. The stainless steel sheet is used as a current collector, firstly, the stainless steel sheet is polished by 800-mesh abrasive paper, then acetone and deionized water are used for ultrasonic cleaning, and then alcohol is used for washing and drying. And carrying out electrochemical test on the composite electrode obtained by electrodeposition in a 4M KOH aqueous solution, wherein the test potential window is-1.1-0V, and the measured specific capacity of the electrode active material is 234F/g.
Example seven:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
and (3) taking the treated stainless steel sheet as a current collector, carrying out electro-deposition at the temperature of 70 ℃, carrying out 5-turn deposition, carrying out electrochemical test on the obtained composite electrode in a 4M KOH aqueous solution, wherein the test potential window is-1.1-0V, and the measured specific capacity of the electrode active material is 303F/g.
Example eight:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
using the treated stainless steel sheet as a current collector, performing electrodeposition at 50 deg.C with constant current deposition at a deposition current density of 5mA cm-2And depositing for 180s, and performing electrochemical test on the obtained composite electrode in a 4M KOH aqueous solution, wherein the test potential window is-1.1-0V, and the measured specific capacity of the electrode active material is 349F/g.
Comparative example one:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
mixing Fe2(SO4)3Preparation of Fe with TEA3+And TEA were 0.01 and 0.13mol/L, respectively, of Fe-TEA, and then only 0.4mol/L of NaOH was added to form a transparent solution as an electrodeposition solution; using a stainless steel sheet as a working electrode current collector, and electrodepositing to obtain pure Fe3O4And carrying out electrochemical test on the electrode in a KOH aqueous solution of 4mol/L, wherein the reference electrode is an Hg/HgO electrode, the test potential window is-1.05-0V, and the measured specific mass capacity is 142F/g.
Comparative example two:
the operation process and other conditions are consistent with the embodiment, and different condition parameters are as follows:
mixing Fe2(SO4)3Preparation of Fe with TEA3+And TEA were 0.01 and 0.13mol/L, respectively, of Fe-TEA, and then only 0.4mol/L of NaOH was added to form a transparent solution as an electrodeposition solution; using a stainless steel sheet as a working electrode current collector, and electrodepositing to obtain pure Fe3O4Electrode at 1mol/L Li2SO4Electrochemical tests were carried out in aqueous solution, the reference electrode being Hg/Hg2SO4The electrode has a test potential window of-1.3 to-0.4V, and the measured specific mass capacity is 176F/g. Comparative example No. three
The operation process and the conditions thereof are consistent with the examples, and different condition parameters are as follows:
mixing Fe2(SO4)3Preparation of Fe with TEA+3And TEA is respectively 0.1 and 0.2mol/L of mixed liquid system Fe-TEA; then preparing 2mol/L NaOH solution with the same volumeAnd (4) liquid. The NaOH solution was then added dropwise to the Fe-TEA while stirring continuously until a clear solution was formed.
When the above-mentioned clear solution was added in an equal volume to 1mg/mLGO dispersion and ultrasonically dispersed, the final deposition solution formed a precipitate and failed to form a stable plating solution.
Comparative example No. four
Adding 0.006mol/L Fe2(SO4)3And 0.012mol/L of FeSO4Preparing a mixed solution according to the molar concentration ratio of 2:1, quickly adding an equal volume of 0.5mg/mLGO dispersion liquid after forming a transparent solution, and performing ultrasonic dispersion to finally form a stable electrodeposition liquid; the electrodeposition process needs to be protected continuously with inert gas to prevent Fe2+Even under the protection of inert atmosphere, the electrodeposition liquid can be partially oxidized in the process of taking out and putting in the gap of the working electrode, and the condition is controlled rigorously. The method comprises the steps of adopting a treated stainless steel sheet as a working electrode, a graphite sheet as an anode and a saturated calomel electrode as a reference electrode, circulating for 10 circles in a potential window of-1.4-0V by a cyclic voltammetry method of 50mV/s, and obtaining a composite electrode containing a large amount of Fe elementary substance phase through electrodeposition. And carrying out electrochemical test in 4mol/L KOH after drying, wherein the tested potential window is-1.1-0V, and the specific mass capacity is only 40F/g.
Claims (7)
1. Electro-deposition Fe3O4-a GO composite electrode characterized in that: the composite electrode material is formed by attaching Fe oxide on GO, co-depositing on a current collector and forming Fe3O4-a GO composite electrode;
the composite electrode is prepared by the following steps:
step one
Stirring soluble ferric salt in water, then dropwise adding a complexing agent to form a mixed solution, and then dropwise adding alkali to form a transparent dark green solution; the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water;
in the mixed solution, the molar ratio of the complexing agent to the iron element is more than or equal to 1;
the molar ratio of hydroxide radical to iron element brought by alkali is more than or equal to 10;
step two
Transparent dark green solution by volume: adding 0.1-2 mg/mL GO dispersion into the transparent dark green solution obtained in the step one according to the ratio of GO dispersion =0.8-1:0.8-1.2, and performing ultrasonic dispersion to obtain an electrodeposition solution; in the electrodeposition liquid, the concentration of ferric ions is not more than 0.01mol/L, and the concentration of GO in the electrodeposition liquid is 0.2-1 mg/mL;
step three
Taking a current collector material as a cathode, placing the cathode in the electrodeposition liquid obtained in the step two, performing electrodeposition under the stirring condition, and co-depositing on the current collector to obtain Fe3O4-a GO composite electrode.
2. Electrodeposited Fe as claimed in claim 13O4-a GO composite electrode characterized in that: in the first step, the soluble ferric salt is at least one selected from ferric sulfate, ferric nitrate and ferric chloride.
3. Electrodeposited Fe as claimed in claim 13O4-a GO composite electrode characterized in that: in the first step, the complexing agent is one or more of ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, triethanolamine and sodium gluconate.
4. Electrodeposited Fe as claimed in claim 13O4-a GO composite electrode characterized in that: in the second step, continuous ultrasonic dispersion is needed when the electrodeposition liquid is prepared by mixing; the frequency of the ultrasonic wave used for ultrasonic dispersion is 40kHz-100 kHz.
5. Electrodeposited Fe as claimed in claim 13O4-a GO composite electrode characterized in that:
in the third step, the current collector is selected from one of stainless steel sheet, titanium sheet, carbon paper and ITO;
in the third step, the stirring speed of the magnetic stirrer is 60-300 r/min, and the electrodeposition temperature is controlled at 30-70 ℃.
6. Electrodeposited Fe as claimed in claim 13O4-a GO composite electrode characterized in that:
in the third step, the deposition mode adopted in the electrodeposition is selected from one of cyclic voltammetry electrodeposition, constant potential electrodeposition and constant current deposition;
during cyclic voltammetry electrodeposition, the cyclic window is-1.6-0.5V, and the scanning rate is 20-500 mV/s; the number of cycles is 10-50;
during the constant potential electrodeposition, controlling the potential to be within-1.5 to-0.9V, and the deposition time to be 300 to 1800 s;
during the constant current electrodeposition, the current density is controlled to be 4-50 mA/cm2The deposition time is 100-1800 s;
and in the third step, drying the obtained composite electrode for more than 3 hours at the temperature of 50-150 ℃ after codeposition.
7. Electrodeposited Fe as claimed in any one of claims 1 to 23O4-use of a GO composite electrode, characterized in that: the composite electrode is used as a negative electrode of a water system super capacitor under a neutral or alkaline condition, and the specific mass capacity of an active substance of the composite electrode is 200-450F/g.
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| CN104018197A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Method for preparing ferroferric oxide magnetic layer on stainless steel fiber surface |
| CN106252091A (en) * | 2016-08-30 | 2016-12-21 | 郑州轻工业学院 | A kind of Fe3o4/ graphene composite material and preparation method thereof |
| CN107967997A (en) * | 2017-11-28 | 2018-04-27 | 中国科学院深圳先进技术研究院 | A kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104018197A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Method for preparing ferroferric oxide magnetic layer on stainless steel fiber surface |
| CN106252091A (en) * | 2016-08-30 | 2016-12-21 | 郑州轻工业学院 | A kind of Fe3o4/ graphene composite material and preparation method thereof |
| CN107967997A (en) * | 2017-11-28 | 2018-04-27 | 中国科学院深圳先进技术研究院 | A kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and application |
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