CN109119252B - Vulcanized Ni-Co-Al LDH electrode composite material and preparation method thereof - Google Patents
Vulcanized Ni-Co-Al LDH electrode composite material and preparation method thereof Download PDFInfo
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- CN109119252B CN109119252B CN201810841975.5A CN201810841975A CN109119252B CN 109119252 B CN109119252 B CN 109119252B CN 201810841975 A CN201810841975 A CN 201810841975A CN 109119252 B CN109119252 B CN 109119252B
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 229910018058 Ni-Co-Al Inorganic materials 0.000 title claims abstract description 31
- 229910018144 Ni—Co—Al Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 168
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000006260 foam Substances 0.000 claims abstract description 40
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 229940075397 calomel Drugs 0.000 claims description 11
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 11
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
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- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 150000002815 nickel Chemical class 0.000 abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001868 cobalt Chemical class 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
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- 238000009210 therapy by ultrasound Methods 0.000 description 8
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- 238000001035 drying Methods 0.000 description 6
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- 229910052723 transition metal Inorganic materials 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
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- 150000002823 nitrates Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 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 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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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)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of electrochemistry, and particularly discloses a preparation method of a vulcanized Ni-Co-Al LDH electrode composite material, which comprises the following steps: (1) placing foamed nickel in water in which divalent nickel salt, trivalent aluminum salt, nitrate and divalent cobalt salt are dissolved, and performing constant potential deposition on the foamed nickel by using a three-electrode system of an electrochemical workstation; (2) adding the deposited nickel foam into an aqueous solution containing thioacetamide for heating reaction. The electrode composite material has the advantages of high specific capacitance value, high energy density and good cyclic discharge stability, and can be used as an electrode material of a super capacitor.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a vulcanized Ni-Co-Al LDH electrode composite material and a preparation method thereof.
Background
With the progress of science and technology and the improvement of social civilization degree, the energy problem becomes the core of the strategy of sustainable development of human society, is a key factor influencing energy decision and science and technology guidance of all countries in the world at present, and is a great driving force for promoting the development of energy science and technology. From the viewpoint of the form of energy utilization, electric energy has become an indispensable "source power" for human material production and social development as a final form of energy utilization. In recent years, the development of small discrete and portable power sources has increased the form of use and range of applications of electrical energy. In addition, with the development of science and technology and the arrival of information society, the popularization of various electronic devices, medical devices, household appliances and mobile communication devices has become increasingly popular, and the demand for high-performance storage standby power is more urgent. In addition to certain requirements for energy density, the requirements for power density of these energy storage devices are increasing, and therefore, there is a strong need for high-power energy storage devices to meet the requirements of current special application fields.
Driven by the above-mentioned special needs, electrochemical capacitors have become a hot research topic in recent years. As a new energy storage element, electrochemical capacitors are increasingly receiving national attention.
Electrochemical capacitors, also known as supercapacitors, are a new class of energy storage devices between physical capacitors and secondary batteries. The capacitor has the characteristic that a physical capacitor can be charged and discharged quickly, and also has the energy storage mechanism of a chemical battery. Compared with a physical capacitor, the super capacitor has the characteristics of high power density, long cycle life, wide working temperature range, large using amount and the like.
As an energy storage device, a super capacitor is mainly used for discriminating the energy storage performance thereof according to specific capacity. According to the difference of energy storage mechanism, the super capacitor can be divided into two types of electrochemical double electric layer and Faraday pseudo-capacitance capacitor:
(1) electrochemical double layer capacitors rely on the accumulation of charge at the ionic contact interface of an active material and an electrolyte at the surface of an electrode, and the storage of energy by electrostatic adsorption.
(2) The Faraday pseudo-capacitance capacitor is a capacitor which stores energy by means of faradaic reaction of active substances and electrolyte ions on the surface of an electrode through charges. Good electrical conductivity is generally required for the faraday pseudocapacitance electrode material to facilitate collection and distribution of charge in the electrode. In addition, it should have other advantages such as strong rapid charge and discharge capability, high specific capacity, etc. The electrode materials of the current Faraday pseudo capacitor mainly comprise metal oxide and conductive polymer. When the conductive polymer material is used as an electrode material of a super capacitor, volume expansion occurs in the charge and discharge process, so that the cycle stability of the super capacitor is poor. At present, the metal compound electrode materials mainly comprise transition metal (hydrogen) oxygen or sulfide and hydrate thereof. The electrode reaction can be deeply and deeply conducted into a shallow electrode, so that energy is stored in a super-two-dimensional space, and the energy density is greatly improved.
LDH (layered double hydroxide) based materials have attracted considerable attention as electrochemical biosensors due to their unique physicochemical properties, such as good adsorption, biocompatibility, thermal stability, low toxicity and low price, which are suitable as modification materials. LDH contains abundant lamella, and as the electrode material of ultracapacitor system, it can utilize two kinds of energy storage mechanisms of electric double layer capacitance and Faraday's quasicapacitance simultaneously, on the one hand can improve its electric double layer capacitance by providing large specific surface area, on the other hand can provide Faraday's quasicapacitance that is much higher than electric double layer capacitance by using the redox reaction of transition metal element on the plywood. However, most of the LDH-based materials synthesized by the coprecipitation method and the hydrothermal method need to be directly drop-coated on the modified electrode to be fixed by using a cross-linking agent, and the stability of the modified electrode is not good.
LDS is formed after the LDH is vulcanized, the material is composed of two parts, wherein the material contains the unsulfurized LDH and the metal sulfide formed after vulcanization, the sulfur source is introduced to improve the conductivity of the material, and the formed reticular structure is more beneficial to the stability of the material, so that the electrochemical performance of the material is improved. The electrode prepared by the in-situ vulcanization method has better conductivity and electrochemical performance than the electrode prepared by being dripped on the foamed nickel.
Disclosure of Invention
The invention aims to provide a vulcanized Ni-Co-Al LDH electrode composite material and a preparation method thereof, the invention directly decorates a Ni-Co-Al LDH base material on a foam nickel electrode by utilizing an electrochemical synthesis method, the decoration time is short, meanwhile, in the decoration process, no binder is needed to be added, the Ni-Co-Al LDH base material is combined with a foam nickel substrate more firmly, the invention also takes Ni-Co-Al LDH as a seed, and introduces a sulfur-containing precursor thioacetamide to carry out vulcanization reaction to obtain the dynamically favorable transition metal sulfide (TMC) phase vulcanized Ni-Co-Al LDH electrode composite material, the vulcanized Ni-Co-Al LDH electrode composite material inherits the inherent structure and stability of a parent metal nano particle network, and the specific capacitance value is higher, the electrode composite material has high energy density and good cyclic discharge stability. Moreover, the preparation method has the advantages of simple process, less time consumption, no need of adding a binder, easy process control and higher popularization and application values.
In order to achieve the above object, the present invention provides a preparation method of a vulcanized Ni-Co-Al LDH electrode composite material, the preparation method comprising the steps of:
(1) placing foamed nickel in water in which divalent nickel salt, trivalent aluminum salt, nitrate and divalent cobalt salt are dissolved, and performing constant potential deposition on the foamed nickel by using a three-electrode system of an electrochemical workstation; wherein the molar ratio of the divalent nickel salt, the trivalent aluminum salt, the nitrate and the divalent cobalt salt is 1:1-3:1-3: 1-3;
(2) adding the deposited nickel foam into an aqueous solution containing thioacetamide for heating reaction.
The invention also provides a vulcanized Ni-Co-Al LDH electrode composite material prepared by the preparation method.
By adopting the technical scheme, the invention directly modifies the Ni-Co-Al LDH substrate on the foam nickel electrode by using the electrochemical synthesis method, the modification time is short, meanwhile, in the modification process, no binder is needed to be added, the Ni-Co-Al LDH substrate is combined with the foam nickel substrate more firmly, the Ni-Co-Al LDH is used as a seed, thioacetamide serving as a sulfur-containing precursor is introduced to carry out a vulcanization reaction, the dynamically favorable transition metal sulfide (TMC) phase vulcanized Ni-Co-Al LDH electrode composite material is obtained, the vulcanized electrode composite material is abbreviated as LDS, the material inherits the inherent structure and stability of a parent metal nanoparticle network, obtains an electrode composite material with higher specific capacitance value, higher energy density and good cyclic discharge stability, and can be used as an electrode material of a super capacitor. Moreover, the preparation method has the advantages of simple process, less time consumption, no need of adding a binder, easy process control and higher popularization and application values.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) image of an LDS composite material prepared in example 2.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the LDS composite material prepared in example 2.
FIG. 3 is a graph of energy dispersive X-ray detection (EDX) of the LDS composite prepared in example 2.
FIG. 4 is an X-ray diffraction (HRTEM) image of the LDS composite material prepared in example 2: 0.25nm (101) is the crystal plane of CoS, 0.28nm (110) is the crystal plane of NiS, and 0.32(220) is the crystal plane of porous sulfide.
FIG. 5 is a plot of Cyclic Voltammetry (CV) for LDS composites prepared in example 2.
FIG. 6 is a constant current charge and discharge (CP) plot of the LDS composite material prepared in example 2.
FIG. 7 is a graph of 4000 constant current charge and discharge cycles (portions) at a current density of 10A/g for the LDS composite material prepared in example 2.
FIG. 8 is a graph of impedance before and after cycling for the LDS composite prepared in example 2.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a vulcanized Ni-Co-Al LDH electrode composite material, which comprises the following steps:
(1) placing foamed nickel in water in which divalent nickel salt, trivalent aluminum salt, nitrate and divalent cobalt salt are dissolved, and performing constant potential deposition on the foamed nickel by using a three-electrode system of an electrochemical workstation; wherein the molar ratio of the divalent nickel salt, the trivalent aluminum salt, the nitrate and the divalent cobalt salt is 1:1-3:1-3: 1-3;
(2) adding the deposited nickel foam into an aqueous solution containing thioacetamide for heating reaction.
Through the technical scheme, the Ni-Co-Al LDH substrate is directly modified on the foam nickel electrode by an electrochemical synthesis method, the modification time is short, meanwhile, in the modification process, no binder is needed to be added, the Ni-Co-Al LDH substrate is firmly combined with the foam nickel substrate, the Ni-Co-Al LDH is used as a seed, a sulfur-containing precursor thioacetamide is introduced to carry out a vulcanization reaction, and a transition metal sulfide (TMC) phase vulcanized Ni-Co-Al LDH electrode composite material favorable in dynamics is obtained, and the vulcanized Ni-Co-Al LDH electrode composite material inherits the inherent structure and stability of a parent metal nanoparticle network, so that the electrode composite material with high specific capacitance value, high energy density and good cyclic discharge stability is obtained. Moreover, the preparation method has the advantages of simple process, less time consumption, no need of adding a binder, easy process control and higher popularization and application values.
In a preferred embodiment of the present invention, in order to obtain an electrode composite material having a high specific capacitance, a high energy density, and good cycle discharge stability, the amount of the divalent nickel salt is preferably 0.001 to 0.003mol per 0.08g of nickel foam; the dosage of thioacetamide is 0.001-0.003 mol.
According to the raw material proportion of the technical scheme, the electrode composite material of the invention can be obtained, and the concentration of each component can be adjusted in a wide range, in a preferred embodiment of the invention, in order to obtain the electrode composite material with higher specific capacitance, larger energy density and good cyclic discharge stability, the dosage of water in the step (1) is preferably 30-60mL, and the dosage of water in the step (2) is preferably 10-40 mL.
The potential for potentiostatic deposition can be adjusted within a wide range, and in a preferred embodiment of the invention, in order to obtain an electrode composite material with a high specific capacitance, a high energy density and good cyclic discharge stability, the deposition potential is preferably in the range of-1.0 to-0.6V.
The time for potentiostatic deposition can be adjusted within a wide range, and in a preferred embodiment of the invention, the deposition time is preferably in the range of 60 to 200s in order to obtain an electrode composite with a high specific capacitance, a high energy density and good cyclic discharge stability.
The conditions for the heating reaction can be adjusted within a wide range, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material with high specific capacitance, high energy density and good cyclic discharge stability, the conditions for the heating reaction in step (2) preferably include: the temperature is 100 ℃ and 140 ℃, and the time is 3-5 h.
While there are many options available to those skilled in the art for the preparation of the feedstock, in a preferred embodiment of the present invention, in order to use clean nickel foam, it is preferred to further include the following pretreatment step before potentiostatic deposition of the nickel foam: ultrasonically cleaning the foamed nickel by using 2-4mol/L HCl for 8-15min, and then alternately cleaning by using deionized water and absolute ethyl alcohol for 10-20min for 3 times.
There are, of course, many options for the treatment of the intermediate Ni-Co-Al LDH prior to sulphidation, and in a preferred embodiment of the invention, it is preferred to include a step of washing the deposited nickel foam with water and drying it in vacuo at 50-70 ℃ before carrying out step (2).
For the three-electrode system, those skilled in the art can adjust it widely, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material with high specific capacitance, high energy density and good stability of cyclic discharge, it is preferable that the three-electrode system has nickel foam as a working electrode, calomel electrode as a reference electrode and Pt electrode as a counter electrode.
In the above technical solution, the divalent nickel salt may be selected from a wide range as long as it can ionize divalent nickel ions in water, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material with high specific capacitance, high energy density, and good cycle discharge stability, the divalent nickel salt is preferably nickel chloride hexahydrate and/or nickel nitrate hexahydrate.
In the above technical solution, the trivalent aluminum salt can be selected from a wide range as long as it can ionize trivalent aluminum ions in water, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material with high specific capacitance, high energy density and good cycle discharge stability, the trivalent aluminum salt is preferably anhydrous aluminum chloride and/or aluminum nitrate nonahydrate.
In the above-described embodiments, the nitrate salt can be selected from a wide range, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material having a high specific capacitance value, a high energy density, and good cycle discharge stability, the nitrate salt is preferably potassium nitrate and/or sodium nitrate.
In the above technical solution, the divalent cobalt salt can be selected from a wide range as long as it can ionize divalent cobalt ions in water, and in a preferred embodiment of the present invention, in order to obtain an electrode composite material with high specific capacitance, high energy density, and good cycle discharge stability, the divalent cobalt salt is preferably cobalt chloride hexahydrate and/or cobalt acetate tetrahydrate.
In the above technical solution, the water may be selected from water for routine experiments, such as deionized water, primary distilled water, double distilled water, ultrapure water, and the like, and the present invention may be implemented, which is not always enumerated herein.
The invention also provides a vulcanized Ni-Co-Al LDH electrode composite material prepared by the preparation method.
Through the technical scheme, the Ni-Co-Al LDH substrate is directly modified on the foam nickel electrode by an electrochemical synthesis method, the modification time is short, meanwhile, in the modification process, no binder is needed to be added, the Ni-Co-Al LDH substrate is firmly combined with the foam nickel substrate, the Ni-Co-Al LDH is used as a seed, a sulfur-containing precursor thioacetamide is introduced to carry out a vulcanization reaction, and a transition metal sulfide (TMC) phase vulcanized Ni-Co-Al LDH electrode composite material favorable in dynamics is obtained, and the vulcanized Ni-Co-Al LDH electrode composite material inherits the inherent structure and stability of a parent metal nanoparticle network, so that the electrode composite material with high specific capacitance value, high energy density and good cyclic discharge stability is obtained. Moreover, the preparation method has the advantages of simple process, less time consumption, no need of adding a binder, easy process control and higher popularization and application values.
The present invention will be described in detail below by way of examples.
Example 1
Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min and 3 times respectively;
vacuum drying the pretreated foamed nickel at 60 ℃, and weighing 0.0801g of the foamed nickel;
weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760, KNO30.7583g of the pure nickel is respectively dissolved in 50mL of deionized water at room temperature, electrodeposition is carried out by using a three-electrode system of an electrochemical workstation CHI660C (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode), constant potential deposition is carried out by selecting-0.9V, and the deposition time is 100 s;
after deposition, the foam nickel is washed by deionized water and dried in vacuum at 60 ℃;
weighing Thioacetamide (TAA) 0.06g, ultrasonically dispersing in 30mL deionized water, transferring to a high-pressure reaction kettle after dispersion, adding foamed nickel with an active material into the high-pressure reaction kettle, setting the temperature at 120 ℃, and keeping the time at 4 h.
And when the temperature of the reaction kettle is reduced to room temperature, washing the foamed nickel by using ethanol, removing oxides on the surface by ultrasonic waves, and drying in vacuum at 60 ℃.
Example 2
(1) Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min3 times respectively;
(2) vacuum drying the pretreated foamed nickel at 60 ℃, wherein the weighed mass is 0.0745 g;
(3) weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760g, KNO30.7583g in the chamberDissolving in 50mL deionized water at room temperature, performing electrodeposition (foamed nickel as a working electrode, calomel as a reference electrode, and a Pt electrode as a counter electrode) with a three-electrode system CHI660C electrochemical workstation, and performing constant potential deposition at-0.9V for 100 s;
(4) after deposition, the foam nickel is washed by deionized water and dried in vacuum at 60 ℃;
(5) weighing Thioacetamide (TAA) 0.09g, ultrasonically dispersing in 30mL deionized water, transferring to a high-pressure reaction kettle after dispersion, adding foamed nickel with an active material into the high-pressure reaction kettle, setting the temperature at 120 ℃, and keeping the time at 4 h.
(6) And when the temperature of the reaction kettle is reduced to room temperature, washing the foamed nickel by using ethanol, removing oxides on the surface by ultrasonic waves, and drying in vacuum at 60 ℃.
Example 3
(1) Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min3 times respectively;
(2) vacuum drying the pretreated foamed nickel at 60 ℃, wherein the weighed mass is 0.0811 g;
(3) weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760, KNO30.7583g of the pure nickel is respectively dissolved in 50mL of deionized water at room temperature, electrodeposition is carried out by using a three-electrode system of an electrochemical workstation CHI660C (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode), constant potential deposition is carried out by selecting-0.9V, and the deposition time is 100 s;
(4) after deposition, the foam nickel is washed by deionized water and dried in vacuum at 60 ℃;
(5) weighing 0.12g of Thioacetamide (TAA), ultrasonically dispersing in 30mL of deionized water, transferring into a high-pressure reaction kettle after dispersion, adding foamed nickel with an active material into the high-pressure reaction kettle, setting the temperature at 120 ℃, and keeping the time at 4 h.
(6) And when the temperature of the reaction kettle is reduced to room temperature, washing the foamed nickel by using ethanol, removing oxides on the surface by ultrasonic waves, and drying in vacuum at 60 ℃.
Example 4
Foam nickel pretreatment: performing ultrasonic treatment with 2M HCl for 15min, and washing with deionized water and anhydrous ethanol for 20min 3 times respectively;
vacuum drying the pretreated foam nickel at 60 ℃, and weighing the foam nickel with the mass of 0.08 g;
0.001mol of NiCl is taken2·6H2O，0.001mol AlCl3·6H2O，0.001mol CoCl2·6H2O，0.001mol KNO3Dissolving the materials in 30mL of deionized water at room temperature, performing electrodeposition (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode) by using a three-electrode system of an electrochemical workstation CHI660C, and selecting-1.0V for constant potential deposition, wherein the deposition time is 200 s;
after deposition, the foam nickel is washed by deionized water and dried in vacuum at 50 ℃;
taking 0.001mol of Thioacetamide (TAA), ultrasonically dispersing in 10mL of deionized water, transferring to a high-pressure reaction kettle after dispersing, adding foamed nickel with an active material into the high-pressure reaction kettle, setting the temperature to be 100 ℃, and keeping the time to be 5 hours;
and when the temperature of the reaction kettle is reduced to room temperature, washing the foamed nickel by using ethanol, removing oxides on the surface by ultrasonic waves, and drying in vacuum at 60 ℃.
Example 5
Foam nickel pretreatment: performing ultrasonic treatment with 4M HCl for 8min, washing with deionized water and anhydrous ethanol for 10min, respectively, 3 times;
vacuum drying the pretreated foam nickel at 60 ℃, and weighing the foam nickel with the mass of 0.08 g;
taking 0.003mol NiCl2·6H2O，0.009mol AlCl3·6H2O，0.009mol CoCl2·6H2O，0.009mol KNO3Dissolving the materials in 60mL of deionized water at room temperature, performing electrodeposition (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode) by using a three-electrode system of an electrochemical workstation CHI660C, and selecting-0.6V for constant potential deposition, wherein the deposition time is 60 s;
after deposition, the foam nickel is washed by deionized water and dried in vacuum at 70 ℃;
taking 0.003mol of Thioacetamide (TAA), ultrasonically dispersing in 40mL of deionized water, transferring to a high-pressure reaction kettle after dispersing, adding foamed nickel with an active material into the high-pressure reaction kettle, setting the temperature to be 140 ℃, and keeping the time to be 3 hours;
and when the temperature of the reaction kettle is reduced to room temperature, washing the foamed nickel by using ethanol, removing oxides on the surface by ultrasonic waves, and drying in vacuum at 60 ℃.
Comparative example 1
Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min3 times respectively;
vacuum drying the pretreated foamed nickel at 60 ℃, and weighing 0.0803g of the foamed nickel;
weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760, KNO30.7583g of the precipitate was dissolved in 50mL of deionized water at room temperature, electrodeposition was performed using a three-electrode system of electrochemical workstation CHI660C (foamed nickel as a working electrode, calomel as a reference electrode, and a Pt electrode as a counter electrode), and constant potential deposition was performed at-0.9V for 60 s;
after deposition, the nickel foam was rinsed with deionized water and dried under vacuum at 60 ℃.
Comparative example 2
Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min3 times respectively;
vacuum drying the pretreated foamed nickel at 60 ℃, and weighing the foamed nickel with the mass of 0.0738 g;
weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760, KNO30.7583g of the pure nickel is respectively dissolved in 50mL of deionized water at room temperature, electrodeposition is carried out by using a three-electrode system of an electrochemical workstation CHI660C (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode), constant potential deposition is carried out by selecting-0.9V, and the deposition time is 100 s;
after deposition, the nickel foam was rinsed with deionized water and dried under vacuum at 60 ℃.
Comparative example 3
Foam nickel pretreatment: performing ultrasonic treatment with 3M HCl for 10min, washing with deionized water and anhydrous ethanol for 15min3 times respectively;
vacuum drying the pretreated foamed nickel at 60 ℃, and weighing 0.0804g of the foamed nickel;
weighing NiCl2·6H2O is 0.2377g, AlCl3·6H2O is 0.2145g, CoCl2·6H2O is 0.4760, KNO30.7583g of the pure nickel is respectively dissolved in 50mL of deionized water at room temperature, electrodeposition is carried out by using a three-electrode system of an electrochemical workstation CHI660C (foamed nickel is used as a working electrode, calomel is used as a reference electrode, and a Pt electrode is used as a counter electrode), constant potential deposition is carried out by selecting-0.9V, and the deposition time is 200 s;
after deposition, the nickel foam was rinsed with deionized water and dried under vacuum at 60 ℃.
Example of detection
FIG. 1 is a Scanning Electron Microscope (SEM) image of an LDS composite material prepared in example 2. As shown in fig. 1, the product was flower-like nanoplatelets. Fig. 2 is a Transmission Electron Microscope (TEM) image of the LDS composite material prepared in example 2.
The network structure formed in the figure can rapidly transfer charges, and the introduced sulfur source can improve the conductivity of the material, so that the electrochemical performance of the material is improved.
FIG. 3 is a graph of energy dispersive X-ray detection (EDX) of the LDS composite prepared in example 2. As shown in fig. 3, the EDX plot can detect all elements contained in the synthetic substance.
FIG. 4 is an X-ray diffraction (HRTEM) image of the LDS composite material prepared in example 2. 0.25nm (101) is the crystal plane of CoS, 0.28nm (110) is the crystal plane of NiS, and 0.32(220) is the crystal plane of porous sulfide. Indicating successful synthesis of the LDS complex.
The composite materials of examples 1, 3-5 were examined to be similar in SEM, TEM, EDX, HRTEM to those of example 2.
Electrochemical performance test
1. And (3) taking the composite material nanosheet prepared by electrodeposition as a working electrode, taking a calomel electrode as a reference electrode and taking a Pt electrode as a counter electrode. The electrolyte is 6mol/L KOH solution.
2. And (3) electrochemical performance testing: the whole three-electrode system was completed with the electrochemical workstation CHI660C test system.
FIG. 5 is a plot of Cyclic Voltammetry (CV) for LDS composites prepared in example 2. The material can be seen to have obvious oxidation reduction peaks, which indicates that the material has good capacitance performance.
FIG. 6 is a constant current charge and discharge (CP) plot of the LDS composite material prepared in example 2. As shown in FIG. 6, the LDS composite material has good electrochemical performance, and the mass specific capacitance reaches 2693.3F/g when the current density is 1A/g; at 10A/g, the specific capacitance can still reach 2173.3F/g.
FIG. 7 is a graph of 4000 constant current charge and discharge cycles (portions) at a current density of 10A/g for the LDS composite material prepared in example 2. FIG. 8 is a graph of impedance before and after cycling for the LDS composite prepared in example 2.
The properties of examples 1-3 and comparative examples 1-3 were determined as shown in Table 1:
TABLE 1
Remarking: the corresponding electrochemical data listed in the above table were obtained at a current density of 1A/g.
As shown in table 1: comparative examples 1-3 are the discussion of different deposition times without sulfidation, the corresponding electrochemical performance is relatively poor, the specific capacitance value is relatively low, and the energy density is relatively low; it is clear from examples 1 to 3 that a significant improvement in electrochemical performance can be observed.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A preparation method of a vulcanized Ni-Co-Al LDH electrode composite material is characterized by comprising the following steps:
(1) 0.0745g of foamed nickel were placed in a bath of dissolved NiCl2·6H2O、AlCl3·6H2O、KNO3And CoCl2·6H2In water of O, performing constant potential deposition on the foamed nickel by using a three-electrode system of an electrochemical workstation; wherein NiCl2·6H2The dosage of O is 0.2377g and AlCl3·6H2The amount of O used was 0.2145g, CoCl2·6H2The dosage of O is 0.4760g, KNO3The dosage of the medicine is 0.7583 g;
(2) adding the deposited nickel foam into an aqueous solution containing 0.09g of thioacetamide for heating reaction;
wherein the dosage of the water in the step (1) is 50mL, and the dosage of the water in the step (2) is 30 mL.
2. The production method according to claim 1, wherein the conditions of potentiostatic deposition include: the deposition potential is-1.0 to-0.6V; and/or the deposition time is 60-200 s.
3. The production method according to claim 1, wherein the conditions for the heating reaction in the step (2) include: the temperature is 100 ℃ and 140 ℃, and the time is 3-5 h.
4. The production method according to any one of claims 1 to 3, further comprising a step of subjecting the nickel foam to the following pretreatment before the potentiostatic deposition of the nickel foam: ultrasonically cleaning the foamed nickel by using 2-4mol/L HCl for 8-15min, and then alternately cleaning by using deionized water and absolute ethyl alcohol for 10-20min for 3 times.
5. The production method according to any one of claims 1 to 3, further comprising a step of washing the deposited nickel foam with water and vacuum-drying at 50 to 70 ℃ before performing step (2).
6. The preparation method according to any one of claims 1 to 3, wherein the foamed nickel is used as a working electrode, the calomel electrode is used as a reference electrode, and the Pt electrode is used as a counter electrode in a three-electrode system.
7. The vulcanized Ni-Co-Al LDH electrode composite material prepared by the preparation method of any one of claims 1 to 6.
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