CN113793760A - Preparation method of one-step electro-deposition nickel-iron sulfide nano composite electrode - Google Patents
Preparation method of one-step electro-deposition nickel-iron sulfide nano composite electrode Download PDFInfo
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 54
- FRWHRIRADSHXLL-UHFFFAOYSA-N iron(3+);nickel(2+);tetrasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[Fe+3].[Ni+2].[Ni+2].[Ni+2].[Ni+2] FRWHRIRADSHXLL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004744 fabric Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000012360 testing method Methods 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 12
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 11
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 11
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010276 construction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 238000000840 electrochemical analysis Methods 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 28
- 229910052976 metal sulfide Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000006479 redox reaction Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition metal sulfide Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
Abstract
The invention discloses a preparation method of a one-step electro-deposition nickel-iron sulfide nano composite electrode, which comprises the following steps: pretreating carbon fiber cloth: cutting the carbon fiber cloth into patterns with uniform sizes; performing ultrasonic treatment in a mixed solution of acetone and ethanol for a period of time; cleaning, and immersing in potassium permanganate solution for oil bath; finally, cleaning and drying; preparing an electrodeposition solution: electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction; the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations; electrochemical deposition: the carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting a cyclic voltammetry method, and multiple cyclic voltammetry tests are carried out at a certain scanning rate under the condition of a certain voltage range; the carbon cloth after electrodeposition was rinsed with a large amount of deionized water and then dried, and the mass load of Ni-Fe-S on the carbon cloth was determined by the mass difference before and after electrodeposition using an electronic balance.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method of a one-step electro-deposition nickel-iron sulfide nano composite electrode.
Background
With the further prosperity and development of the human society, fossil resources are being consumed at an accelerated rate, which has become a global problem. Therefore, efficient energy conversion and storage and the development of renewable energy sources have become a focus of global attention. Lithium ion batteries, as classical rechargeable energy storage devices, have proven to play a crucial role in the energy field of modern society due to their advantages in terms of high energy density and operating voltage, good rechargeability and complex commercialization.
However, besides the scarcity and unbalanced geographical distribution of lithium resources, the low power density of lithium ion batteries is a constant disadvantage, and becomes an inevitable obstacle in the development process of lithium ion batteries. Compared with a lithium ion battery, the super capacitor has the obvious advantages of high charging and discharging speed, long cycle life, high power density and the like. Because of such a wide attention, research on electrode materials of the super capacitor is popular among researchers. In recent years, common positive electrode materials have been mainly metal oxides/sulfides. Due to the similar electrochemical energy storage mechanism and abundant natural resources, Ni-Fe-S has more abundant electroactive centers and more excellent conductivity than single Ni or Fe sulfide, so that the Ni-Fe-S has higher theoretical specific capacitance. However, during charging and discharging, the rate retention ability is poor due to the poor conductivity of the binary metal sulfide.
In order to improve the rate capability and the cycle performance of the metal sulfide, researchers make many attempts. For example, m.f. Iqbal et al consider that graphene has very high conductivity, and therefore strontium sulfide nanorods are mixed with graphite oxide to obtain a high-performance composite material. Liu et al use NiCo2S4And the material is combined with a porous carbon sheet with high specific surface area to improve the conductivity of the material. The pseudocapacitor relies on a rapid faradaic redox reaction or highly reversible chemisorption and desorption for energy storage, and essentially relies on electrochemical charge transfer of active materials to generate capacitance. Because energy storage relies on redox reactions, pseudocapacitance occurs at the electrode surface. After a certain potential difference is applied, the electroactive material undergoes redox reaction or chemisorption and desorption.
For the pseudo capacitor, the transition metal sulfide is an ideal electrode material. This is mainly due to the unique properties of transition metal sulfides: the variable valence state can provide an ideal pseudocapacitance; allowing ions and electrons to intercalate into the crystal lattice of the metal sulfide; inherently good stability.
In recent years, transition metal sulfides have been developed by converting sulfides of one element into mixed metal sulfides of multiple elements, and the single crystal structure of the mixed metal sulfides has coexistence of two different metal elements and can participate in multiple redox reactions, so that the electrochemical capacity is improved to a certain extent. Furthermore, the synergistic effect between different metal elements in a mixed metal sulphide may lead to more electrically active sites than a single component metal sulphide, thereby inducing a significant capacitance increase. Based on the research, the Ni-Fe-S is expected to grow on the carbon fiber cloth, so that the conductivity of the material is improved, and a certain supporting effect on metal sulfides is achieved.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the defects in the prior art and provides a preparation method of a one-step electrodeposited nickel iron sulfide nano composite electrode.
The technical scheme is as follows: the preparation method of the one-step electrodeposition nickel iron sulfide nanometer composite electrode comprises the following steps:
(1) pretreating carbon fiber cloth:
cutting the carbon fiber cloth into patterns with uniform sizes;
performing ultrasonic treatment in a mixed solution of acetone and ethanol for a period of time;
cleaning, and immersing in potassium permanganate solution for oil bath;
finally, cleaning and drying;
(2) preparing an electrodeposition solution:
electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction;
the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations, namely Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4 and Ni-Fe-S-5;
(3) electrochemical deposition:
the carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting a cyclic voltammetry method, and multiple cyclic voltammetry tests are carried out at a certain scanning rate under the condition of a certain voltage range;
the carbon cloth after electrodeposition was rinsed with a large amount of deionized water and then dried in an oven at 85 ℃ for 12 hours, and the mass load of Ni-Fe-S on the carbon cloth was determined by the mass difference before and after electrodeposition using an electronic balance.
Further, the carbon fiber cloth is subjected to ultrasonic treatment in a mixed solution of acetone and ethanol for 1-2 hours to remove dust and oil stains.
Further, the concentration of the potassium permanganate solution is 5%.
Furthermore, the temperature of the oil bath is 80-90 ℃, and the soaking time is 40-50 minutes.
Further, the electrodeposition solution contained 200 mL of 5 mM ferric chloride hexahydrate containing nickel dichloride hexahydrate and 0.75M thiourea in different concentrations of 2.5, 5, 7.5, 10, 12.5 mM.
Further, the concentration is 5 mV · s-1Is performed for 10-20 CV cycles at the scan rate of (a).
Furthermore, the voltage interval of the scanning is-1.2-0.2V.
Further, the method also comprises the testing of the electrode.
Further, the testing of the electrodes comprises: and performing electrochemical test by adopting a CHI 660D electrochemical workstation, and measuring the electrochemical performance of a single electrode in a voltage range of 0-0.8V by adopting a three-electrode system, using electrodeposited carbon cloth as a working electrode, Pt as a counter electrode and Hg/HgCl as a reference electrode in the three-electrode system under 1 moL/L sulfuric acid.
Has the advantages that: the method adopts a one-step electrodeposition process to combine with the carbon fiber cloth to prepare the nickel-iron vulcanized nano composite material and apply the nickel-iron vulcanized nano composite material to the asymmetric supercapacitor; after the Ni-Fe-S-3 material with the nano structure is combined with the carbon fiber cloth, the circulating stability and the rate capability of the composite material are further improved; nickel iron sulfide formed uniformly deposited nanoarrays on conductive carbon substrates exhibiting high specific capacitance (770F g)-1) And at 40A g-1The retention rate can reach 87.3%; the method proves that the binary metal sulfide is prepared on the carbon cloth by electrodeposition, so that the conductivity of the carbon cloth is effectively improved; after 10000 cycles, the specific capacity retention rate can reach 92.3 percent, and a simple one-step sulfide electrodeposition process is found, and has great application potential in various energy storage technologies.
Drawings
FIG. 1 is a schematic illustration of an analytical map of an electrode material according to the present invention;
FIG. 2 is a scan test chart of the electrode material of the present invention;
FIG. 3 is a high power transmission diagram of an electrode oxide nanoplate of the present invention;
FIG. 4 is a graph of electrochemical performance of an electrode according to the present invention;
FIG. 5 is a composite cycle test graph of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
Example 1
The preparation method of the one-step electro-deposition nickel iron sulfide nanometer composite electrode comprises the following steps:
(1) pretreating carbon fiber cloth:
cutting the carbon fiber cloth into a pattern with uniform size, for example, cutting the carbon fiber cloth into strips with the size of 3cm multiplied by 20 cm;
removing dust in a mixed solution of acetone and ethanol by ultrasonic treatment for 1 hour;
after cleaning, immersing the mixture into a 5% potassium permanganate solution for oil bath, wherein the temperature of the oil bath is 80 ℃, and the immersion time is 40 minutes;
then ultra-pure water is used for ultrasonic cleaning until the cleaning solution is clear and transparent, and finally drying is carried out in a 60 ℃ drying oven;
(2) preparing an electrodeposition solution:
electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction;
the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations, namely Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4 and Ni-Fe-S-5, taking 200 mL of the electrodeposition solution as an example, wherein the electrodeposition solution contains 5 mM of ferric trichloride hexahydrate with different concentrations of 2.5, 5, 7.5, 10, 12.5 mM of nickel dichloride hexahydrate and 0.75M of thiourea;
(3) electrochemical deposition:
carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting cyclic voltammetry, and under the condition that the voltage range is-1.2-0.2V, the electrokinetic deposition is carried out at 5 mV s-110 cyclic voltammetry tests were performed at the scan rate of (a);
the electrodeposited carbon cloth was rinsed with a large amount of deionized water and then dried in an oven at 85 c for 12 hours. The mass load of Ni-Fe-S on the carbon cloth was determined by using the mass difference of an electronic balance (resolution of 1. mu.g) before and after electrodeposition.
Example 2
The preparation method of the one-step electro-deposition nickel iron sulfide nanometer composite electrode comprises the following steps:
(1) pretreating carbon fiber cloth:
cutting the carbon fiber cloth into a pattern with uniform size, for example, cutting the carbon fiber cloth into strips with the size of 3cm multiplied by 20 cm;
removing dust by ultrasonic treatment in a mixed solution of acetone and ethanol for 2 hours;
after cleaning, immersing the mixture into a 5% potassium permanganate solution for oil bath, wherein the temperature of the oil bath is 90 ℃, and the immersion time is 50 minutes;
then ultra-pure water is used for ultrasonic cleaning until the cleaning solution is clear and transparent, and finally drying is carried out in an oven at 80 ℃;
(2) preparing an electrodeposition solution:
electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction;
the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations, namely Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4 and Ni-Fe-S-5, taking 200 mL of the electrodeposition solution as an example, wherein the electrodeposition solution contains 5 mM of ferric trichloride hexahydrate with different concentrations of 2.5, 5, 7.5, 10, 12.5 mM of nickel dichloride hexahydrate and 0.75M of thiourea;
(3) electrochemical deposition:
carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting cyclic voltammetry, and under the condition that the voltage range is-1.2-0.2V, the electrokinetic deposition is carried out at 5 mV s-120 cyclic voltammetry tests at a scanning rate of (a);
the electrodeposited carbon cloth was rinsed with a large amount of deionized water and then dried in an oven at 85 c for 12 hours. The mass load of Ni-Fe-S on the carbon cloth was determined by using the mass difference of an electronic balance (resolution of 1. mu.g) before and after electrodeposition.
Example 3
The preparation method of the one-step electro-deposition nickel iron sulfide nanometer composite electrode comprises the following steps:
(1) pretreating carbon fiber cloth:
cutting the carbon fiber cloth into a pattern with uniform size, for example, cutting the carbon fiber cloth into strips with the size of 3cm multiplied by 20 cm;
removing dust by ultrasonic treatment for 1.5 hours in a mixed solution of acetone and ethanol;
after cleaning, immersing the mixture into a 5% potassium permanganate solution for oil bath, wherein the temperature of the oil bath is 85 ℃, and the immersion time is 45 minutes;
then ultra-pure water is used for ultrasonic cleaning until the cleaning solution is clear and transparent, and finally drying is carried out in a 70 ℃ oven;
(2) preparing an electrodeposition solution:
electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction;
the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations, namely Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4 and Ni-Fe-S-5, taking 200 mL of the electrodeposition solution as an example, wherein the electrodeposition solution contains 5 mM of ferric trichloride hexahydrate with different concentrations of 2.5, 5, 7.5, 10, 12.5 mM of nickel dichloride hexahydrate and 0.75M of thiourea;
(3) electrochemical deposition:
carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting cyclic voltammetry, and under the condition that the voltage range is-1.2-0.2V, the electrokinetic deposition is carried out at 5 mV s-115 cyclic voltammetry tests were performed at the scan rate of (a);
the electrodeposited carbon cloth was rinsed with a large amount of deionized water and then dried in an oven at 85 c for 12 hours. The mass load of Ni-Fe-S on the carbon cloth was determined by using the mass difference of an electronic balance (resolution of 1. mu.g) before and after electrodeposition.
At the end of the steps of the above example, the electrodes also need to be tested:
electrochemical testing was performed using the CHI 660D electrochemical workstation. In a three-electrode system under 1 moL/L sulfuric acid, the three-electrode system is adopted, electrodeposited carbon cloth is taken as a working electrode, Pt is taken as a counter electrode, and Hg/HgCl is taken as a reference electrode. The electrochemical performance of the single electrode was measured within a voltage range of 0-0.8V.
The specific electrode material morphology and elemental analysis results are as follows:
different numbered materials (Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4, and Ni-Fe-S-5) prepared from different components of the electrodeposition bath were measured at 20 mV S-1Cyclic voltammetry was performed at a sweep rate of (1). As shown in FIG. 1(a), among all the samples, Ni-Fe-S-3, a sample having a nickel salt concentration of 0.75 mM in the electrodeposition bath, hadMaximum integrated area, and for a material concentration of 10 mM, a very pronounced polarization peak appears[8]. The Ni-Fe-S-3 material has the most excellent electrochemical performance in various materials with different proportions.
Therefore, we further analyzed the morphology and element content of Ni-Fe-S-3. We performed energy spectrum tests on the material (fig. 1(c)), and it can be seen from the spectrum that the elements Ni and Fe are present in large amounts in the compound, indicating the successful performance of electrodeposition. As can be seen more clearly from the results of the quantitative analysis of the elements in FIG. 1(b), the total content of Fe and Ni elements is more than 20%, and the content of S element is also nearly 10%. The method also provides more active substances for the electrochemical reaction process, and is beneficial to further improving the material performance.
Next, we performed a scan test on the Ni-Fe-S-3 material. As shown in FIG. 2, the microscopic morphology of the material is composed of many nanoparticles with a diameter of about 200 nm, and has a rough surface, which also provides sufficient active sites for electrochemical reaction[10]. The nano particles have small size and are favorable for the rapid permeation of electrolyte[11]. Meanwhile, the deposition of the iron-nickel sulfide on the carbon cloth is relatively complete and regular, and the iron-nickel sulfide can be uniformly deposited, so that the Ni-Fe-S on the carbon fiber has strong adhesion. Due to the advantages of uniform material coating and electrodeposition techniques, the resulting electrode maintains good macroporous properties without blocking its macropores even after severe material deposition. This morphology facilitates efficient flow of electrolyte ions throughout the electrode structure, resulting in extensive contact of the electrode material of the electrode structure with the electrolyte ions enhancing the charge storage reaction.
TEM test is carried out on the composite material, and the obtained Ni-Fe-S is further proved to be a cubic crystal with a crystalline structure. Fig. 3 is a high-power transmission picture of an oxide nanosheet, in which a row of clear crystal planes on the surface of the composite material can be seen, and the crystal plane spacing can be measured to be about 0.295 nm by a ruler, and the crystal plane spacing of 0.295 nm corresponds to the (100) crystal plane of FeNiS. The inset is a Fourier diffraction ring diagram, and it can be seen that the diffracted spots are clear and form a ring, reflecting that the crystal form of the sulfide is a single crystal structure.
And testing the electrochemical performance of the prepared composite material. Fig. 4(a) is a CV curve of a material at different current densities. All curves have good symmetry, indicating good electrochemical reversibility and very excellent stability with increasing sweep rate. At sweep rates of 2-20 mV/s, we found that the redox peak of nickel iron sulfide is very clear and well symmetrical, indicating good reversibility of its redox reaction, with the oxidation peak being located near 0.3V and the reduction peak being located near 0.18V. As the sweep rate increased, the oxidation peak shifted to the right and the reduction peak shifted to the left, and at a sweep rate of 50 mV/s, the curve polarization was very severe. The redox peak in the CV test was attributed to Ni2+And Ni3+Oxidation-reduction reaction of[12]And Fe2+And Fe3+Oxidation-reduction reaction of[13]. In the constant current charge and discharge curve of fig. 4(b), the potential of the charge and discharge plateau corresponds well to the potential of the redox peak in the graph (a). It can be observed in the impedance plot of fig. 4(c) that the material has a smaller cross-sectional intercept in the high frequency region, indicating that the material has a smaller internal resistance. The high frequency region half circle has a smaller diameter, indicating that the material also has a smaller charge transfer resistance. In the low frequency region, the impedance spectrum is a straight line close to the Y-axis. Fig. 4(d), from the constant current charge and discharge curve, we calculated the specific capacity of the material. At a current density of 1A g-1The specific capacity of the material can reach 770F g-1. It is worth noting that with increasing current density, there is only a slight decay in the specific capacity of the material. When the current density is increased to 40A g-1When the specific capacity is still kept at 672F g-1. The retention rate of the specific capacity can reach 87.3%. Jinxiaoqing et al with CoMoO4As a precursor, the CoMoS is synthesized by an ion exchange reaction4The electrode material is characterized and tested on the appearance, microstructure and electrochemical performance. The test shows that the prepared CoMoS4Compared with the single metal sulfide, the electrochemical performance of the active substance is greatly improved, and when the current density is 1A/g, the CoMoS4Specific electric potential of electrode materialThe capacity value was 456F/g. Wu et al report a specific surface area of 37.8 m2 g-1Mesoporous NiCo of (2)2S4Nanosheet, mesoporous NiCo2S4The specific capacitance of the nano-sheet reaches 744F g-1(Current Density l A g-1Time). Preparing NiCo by electrochemical deposition of Liupeng and the like on foamed nickel in a mixed solution of nickel nitrate, cobalt nitrate and thiourea with a certain concentration by cyclic voltammetry2S4And (3) nano materials. At a discharge current of 1A g-1When the specific capacitance is 586F g-1. Compared with the performance of the transition metal sulfide material reported in the prior art, the Ni-Fe-S prepared by the method has excellent electrochemical performance, and the rate capability is obviously improved compared with that of a simple binary metal sulfide material.
The material Ni-Fe-S-3 was also tested for cycle stability. As shown in FIG. 5, after the Ni-Fe-S-3 is continuously subjected to 10000 charge-discharge cycles in the acid electrolyte, the average capacitance retention rate is still as high as 92.3%, and excellent cycle stability is shown, which also achieves the expected result. The reasonable design of the Ni-Fe-S-3 nano structure electrodeposited on the carbon cloth obviously improves the structural stability.
The invention combines a simple one-step electrodeposition process with carbon fiber cloth to prepare the nickel-iron vulcanized nano composite material for application to the asymmetric super capacitor. After the Ni-Fe-S-3 material with the nano structure is combined with the carbon fiber cloth, the circulating stability and the rate capability of the composite material are further improved. Nickel iron sulfide formed uniformly deposited nanoarrays on conductive carbon substrates exhibiting high specific capacitance (770F g)-1) And at 40A g-1The retention rate can reach 87.3%. This well proves that the electrical deposition on the carbon cloth to prepare the binary metal sulfide effectively improves the electrical conductivity. After 10000 cycles, the specific capacity retention rate can reach as high as 92.3 percent. A simple one-step sulfide electrodeposition process is found, and the process has great application potential in various energy storage technologies.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the one-step electro-deposition nickel-iron sulfide nanometer composite electrode is characterized by comprising the following steps of: the method comprises the following steps:
(1) pretreating carbon fiber cloth:
cutting the carbon fiber cloth into patterns with uniform sizes;
performing ultrasonic treatment in a mixed solution of acetone and ethanol for a period of time;
cleaning, and immersing in potassium permanganate solution for oil bath;
finally, cleaning and drying;
(2) preparing an electrodeposition solution:
electrochemically co-depositing Ni-Fe-S on a flexible carbon cloth having a woven carbon fiber construction;
the electrodeposition solution contains ferric trichloride hexahydrate and nickel dichloride hexahydrate and thiourea with different concentrations to obtain five compounds with different concentrations, namely Ni-Fe-S-1, Ni-Fe-S-2, Ni-Fe-S-3, Ni-Fe-S-4 and Ni-Fe-S-5;
(3) electrochemical deposition:
the carbon cloth is used as a working electrode, Pt is used as a counter electrode, Hg/HgCl is used as a reference electrode, electrokinetic deposition is carried out on a three-electrode system by adopting a cyclic voltammetry method, and multiple cyclic voltammetry tests are carried out at a certain scanning rate under the condition of a certain voltage range;
the carbon cloth after electrodeposition was rinsed with a large amount of deionized water and then dried in an oven at 85 ℃ for 12 hours, and the mass load of Ni-Fe-S on the carbon cloth was determined by the mass difference before and after electrodeposition using an electronic balance.
2. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: the carbon fiber cloth is subjected to ultrasonic treatment in a mixed solution of acetone and ethanol for 1-2 hours to remove dust and oil stains.
3. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: the concentration of the potassium permanganate solution is 5%.
4. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: the temperature of the oil bath is 80-90 ℃, and the soaking time is 40-50 minutes.
5. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: 200 mL of the electrodeposition solution contains 5 mM of ferric chloride hexahydrate and different concentrations of 2.5, 5, 7.5, 10, 12.5 mM of nickel dichloride hexahydrate and 0.75M of thiourea.
6. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: said at 5 mV · s-1Is performed for 10-20 CV cycles at the scan rate of (a).
7. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 6, characterized in that: the voltage interval of the scanning is-1.2-0.2V.
8. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 1, wherein: testing of the electrodes is also included.
9. The method for preparing the one-step electrodeposited nickel iron sulfide nanocomposite electrode according to claim 8, wherein: the testing of the electrodes includes: and performing electrochemical test by adopting a CHI 660D electrochemical workstation, and measuring the electrochemical performance of a single electrode in a voltage range of 0-0.8V by adopting a three-electrode system, using electrodeposited carbon cloth as a working electrode, Pt as a counter electrode and Hg/HgCl as a reference electrode in the three-electrode system under 1 moL/L sulfuric acid.
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