CN113053674A - Binderless electrode material, and preparation method and application thereof - Google Patents
Binderless electrode material, and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000011530 conductive current collector Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 238000004729 solvothermal method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006258 conductive agent Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000006260 foam Substances 0.000 description 20
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
-
- 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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a preparation method of an adhesive-free electrode material, which comprises the following steps: s1) soaking the three-dimensional conductive current collector substrate in a solution containing a nickel source, a precipitating agent and a morphology regulator to carry out hydrothermal reaction or solvothermal reaction to obtain an intermediate; s2), in a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other, and heat treatment is carried out, so that the binderless electrode material is obtained. Compared with the prior art, the method directly grows Ni (OH) on the three-dimensional conductive current collector substrate through a simple two-step method2/Ni2The P composite material not only avoids the use of a binder and a conductive agent, but also Ni in the composite material2P has high conductivity, Ni (OH)2Has a high theoryThe capacity, good electrochemical activity and low cost, so that the obtained binderless electrode material has high performance and good application prospect in the field of supercapacitors.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to an adhesive-free electrode material, and a preparation method and application thereof.
Background
In order to reduce the dependence on fossil fuels, the development of renewable/sustainable energy sources and devices for energy storage/conversion is urgently required. In recent years, supercapacitors have been widely studied for their excellent properties, such as high power density, fast charge and discharge rate, safety, environmental protection, long cycle life, etc., and have been widely used in the fields of portable electronic products and electric vehicles.
The electrochemical performance of a supercapacitor is closely related to the electrode material. Among them, nickel hydroxide is often used as an electrode material of a supercapacitor due to its advantages of high theoretical capacity, high electrochemical activity, low price, etc., however, its actual electrochemical performance is not ideal due to its poor conductivity and slow reaction kinetics.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a binderless electrode material, a preparation method and an application thereof, wherein the binderless electrode material has high electrical conductivity, high theoretical capacity and good electrochemical activity.
The invention provides a preparation method of an adhesive-free electrode material, which comprises the following steps:
s1) soaking the three-dimensional conductive current collector substrate in a solution containing a nickel source, a precipitating agent and a morphology regulator to carry out hydrothermal reaction or solvothermal reaction to obtain an intermediate;
s2), in a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other, and heat treatment is carried out, so that the binderless electrode material is obtained.
Preferably, the three-dimensional conductive current collector substrate is selected from a metal foam or a metal mesh; the nickel source is selected from nickel nitrate; the precipitating agent is selected from urea; the morphology modifier is selected from ammonium fluoride; the phosphorus source is selected from sodium hypophosphite.
Preferably, the concentration of the nickel source in the solution is 0.02 g/ml-0.04 g/ml; the concentration of the precipitant in the solution is 0.005-0.02 mg/ml; the concentration of the morphology regulator in the solution is 0.001-0.005 g/ml; the solvent of the solution is water and/or ethanol.
Preferably, the temperature of the hydrothermal reaction or the solvothermal reaction is 150-170 ℃; the time of the hydrothermal reaction or the solvothermal reaction is 3.5-4.5 h.
Preferably, the three-dimensional conductive current collector substrate is subjected to ultrasonic cleaning and drying, then is soaked in a solution containing a nickel source, a precipitating agent and a morphology regulator, and then is subjected to hydrothermal reaction or solvothermal reaction;
and after the hydrothermal reaction or the solvothermal reaction, carrying out ultrasonic treatment on the three-dimensional conductive current collector substrate after the reaction in water, washing and drying to obtain an intermediate.
Preferably, the mass ratio of the mass difference between the intermediate and the three-dimensional conductive current collector substrate to the phosphorus source is 1: (10-20).
Preferably, the temperature of the heat treatment is 300-400 ℃; the heat treatment time is 1-3 h; the heating rate of the heat treatment is 1.5-2.5 ℃/min.
Preferably, the heat treatment is carried out in a tube furnace; the phosphorus source is located upstream of the tube furnace; the distance between the phosphorus source and the intermediate is 4-5 cm.
The invention also provides an adhesive-free electrode material, which comprises a three-dimensional conductive current collector substrate and Ni (OH) loaded on the three-dimensional conductive current collector substrate2/Ni2P composite material.
The invention also provides a super capacitor which comprises the binderless electrode material.
The invention provides a preparation method of an adhesive-free electrode material, which comprises the following steps: s1) soaking the three-dimensional conductive current collector substrate in a solution containing a nickel source, a precipitating agent and a morphology regulator to carry out hydrothermal reaction or solvothermal reaction to obtain an intermediate; s2), in a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other, and heat treatment is carried out, so that the binderless electrode material is obtained. Compared with the prior art, the method directly grows Ni (OH) on the three-dimensional conductive current collector substrate through a simple two-step method2/Ni2The P composite material not only avoids the use of a binder and a conductive agent, but also Ni in the composite material2P has high conductivity, Ni (OH)2The preparation method has the advantages of high theoretical capacity, good electrochemical activity and low cost, so that the obtained binderless electrode material has high performance and good application prospect in the field of supercapacitors.
Drawings
Fig. 1 is an XRD spectrum of the binderless electrode material obtained in example 1 of the present invention;
FIG. 2 is a plot of cyclic voltammetry curves of the binderless electrode material obtained in example 1 of the present invention as a supercapacitor electrode material at different scan rates;
FIG. 3 is a graph showing the charge and discharge curves of the binderless electrode material obtained in example 1 of the present invention as an electrode material for a supercapacitor at different current densities;
FIG. 4 is a graph showing the relationship between specific capacity and current density of the binderless electrode material obtained in example 1 of the present invention as a supercapacitor electrode material;
FIG. 5 is a plot of cyclic voltammetry curves at different scan rates for the binderless electrode material obtained in example 2 of the present invention as a supercapacitor electrode material;
FIG. 6 is a graph showing the charge and discharge curves of the binderless electrode material obtained in example 2 of the present invention as a supercapacitor electrode material at different current densities;
fig. 7 is a graph showing the relationship between the specific capacity and the current density of the binderless electrode material obtained in example 2 of the present invention as a supercapacitor electrode material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The invention provides a preparation method of an adhesive-free electrode material, which comprises the following steps: s1) soaking the three-dimensional conductive current collector substrate in a solution containing a nickel source, a precipitating agent and a morphology regulator to carry out hydrothermal reaction or solvothermal reaction to obtain an intermediate; s2), in a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other, and heat treatment is carried out, so that the binderless electrode material is obtained.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
In the present invention, the three-dimensional conductive current collector substrate is preferably a foamed metal or a metal mesh, more preferably a foamed nickel or a metal nickel mesh; the area of the three-dimensional conductive current collector substrate is preferably (1-3) × (4-6) cm2More preferably 2X 5cm2(ii) a Preferably, the three-dimensional conductive current collector substrate is firstly subjected to ultrasonic cleaning and drying to remove impurities on the surface; the ultrasonic cleaning is preferably carried out by sequentially adopting acetone, deionized water and absolute ethyl alcohol; the time of ultrasonic cleaning for each time is preferably 20-40 min, and more preferably 30 min; the drying temperature is preferably 70-90 ℃, and more preferably 80 ℃; the drying time is preferably 10-15 h, and more preferably 12 h.
Soaking the three-dimensional conductive current collector substrate subjected to ultrasonic cleaning and drying in a solution containing a nickel source, a precipitating agent and a morphology regulator to perform hydrothermal reaction or solvothermal reaction; the nickel source is preferably nickel nitrate; the precipitating agent is preferably urea; the morphology regulator is preferably ammonium fluoride; the solvent of the solution is preferably water and/or ethanol; the concentration of the nickel source in the solution is preferably 0.02 g/ml-0.04 g/ml, more preferably 0.022 g/ml-0.04 g/ml, still more preferably 0.025 g/ml-0.035 g/ml, and most preferably 0.03 g/ml; the concentration of the precipitant in the solution is preferably 0.005-0.02 mg/ml, more preferably 0.009-0.02 mg/ml, still more preferably 0.009-0.015 mg/ml, and most preferably 0.01-0.015 mg/ml; the concentration of the morphology regulator in the solution is preferably 0.001-0.005 g/ml, more preferably 0.002-0.004 g/ml, further preferably 0.0025-0.0035 g/ml, and most preferably 0.0025-0.003 g/ml; the solution is preferably carried out according to the following steps: mixing a nickel source, a precipitator and a morphology regulator in a solvent, and magnetically stirring to obtain a solution; the magnetic stirring time is preferably 10-15 min; the hydrothermal or solvothermal reaction is preferably carried out in an autoclave; the volume ratio of the solution to the autoclave is preferably (30-50): 100, more preferably (35-45): 100, more preferably 40: 100, respectively; the temperature of the hydrothermal reaction or the solvothermal reaction is preferably 150-170 ℃, more preferably 155-165 ℃, and further preferably 160 ℃; the time of the hydrothermal reaction or the solvothermal reaction is preferably 3.5-4.5 h, and more preferably 4 h.
After the hydrothermal reaction or the solvothermal reaction is finished, preferably, the three-dimensional conductive current collector substrate after the reaction is subjected to ultrasonic treatment in water, washed and dried to obtain an intermediate; more preferably, the three-dimensional conductive current collector substrate is cooled to room temperature, and then the three-dimensional conductive current collector substrate after reaction is subjected to ultrasonic treatment in water, washed and dried to obtain an intermediate; the water is preferably deionized water; the ultrasonic treatment time is 15-20 min, so as to remove loose substances on the surface of the three-dimensional conductive current collector substrate after reaction; the washing preferably adopts deionized water and absolute ethyl alcohol; the washing frequency is preferably 2-4 times; the drying temperature is preferably 70-90 ℃, and more preferably 80 ℃; the drying time is preferably 20-30 h, and more preferably 24 h.
In a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other for heat treatment, so that a binderless electrode material is obtained; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and argon is preferred in the present invention; the phosphorus source is preferably sodium hypophosphite; the mass ratio of the mass difference between the intermediate and the three-dimensional conductive current collector substrate (i.e., the amount of the load in step S1) to the phosphorus source is 1: (10-20), more preferably 1: (12-18), and more preferably 1: (14-16), most preferably 1: 15; the heat treatment is preferably carried out in a tube furnace; the phosphorus source is preferably located upstream of the tube furnace; the distance between the phosphorus source and the intermediate is preferably 4-5 cm, and more preferably 4.5 cm; the temperature of the heat treatment, namely the heat preservation temperature, is preferably 300-400 ℃, more preferably 320-380 ℃, further preferably 340-360 ℃, and most preferably 350 ℃; the heat treatment time, namely the heat preservation time, is preferably 1-3 h, more preferably 1.5-2.5 h, and further preferably 2 h; the heating rate of the heat treatment is preferably 1.5-2.5 ℃/min, and more preferably 2 ℃/min.
The binderless electrode material obtained by the invention can be directly used as a working electrode of a supercapacitor without a binder and a conductive agent.
The invention directly grows Ni (OH) on a three-dimensional conductive current collector substrate by a simple two-step method2/Ni2The P composite material not only avoids bondingUse of agents and conductive agents, and Ni in composite materials2P has high conductivity, Ni (OH)2The preparation method has the advantages of high theoretical capacity, good electrochemical activity and low cost, so that the obtained binderless electrode material has high performance and good application prospect in the field of supercapacitors.
The invention also provides an adhesive-free electrode material prepared by the method, which comprises a three-dimensional conductive current collector substrate and Ni (OH) loaded on the three-dimensional conductive current collector substrate2/Ni2P composite material. Ni2P is transition metal phosphide, shows excellent physical and chemical properties due to the existence of multiple electron orbitals, has metal characteristics and high conductivity, is beneficial to improving the electrochemical performance of a low-conductivity electrode material, and is an ideal choice for an advanced electrode material in an energy storage device. Furthermore, adding Ni (OH)2/Ni2The P composite material directly grows on the three-dimensional conductive current collector substrate, so that the use of a binder and a conductive agent is avoided, electrochemical reaction sites are increased, the effective contact area of an electrode material and electrolyte is increased, the contact between an active material and the conductive substrate is enhanced, and the rapid diffusion of the electrolyte is facilitated.
The invention also provides a super capacitor, which comprises the binderless electrode material prepared by the method.
In order to further illustrate the present invention, the following will describe in detail a binderless electrode material, its preparation method and application in conjunction with the examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 cutting a large piece of foam nickel into an area of 2X 5cm2The small nickel foam blocks are sequentially cleaned by acetone, deionized water and absolute ethyl alcohol for 30min in an ultrasonic mode, dried in an oven at 80 ℃ for 12h, and the mass of the nickel foam before reaction is recorded.
1.2 weighing 1.164g of nickel nitrate hexahydrate, 0.45g of urea and 0.11g of ammonium fluoride, dissolving in 40ml of deionized water, and magnetically stirring for 10min to obtain a precursor solution.
1.3 general comparison of 1.2The precursor solution was transferred to a 100ml teflon liner and immersed in two 1.1 cleaned 2 x 5cm strips2The nickel foam is sealed in a stainless steel autoclave and is subjected to hydrothermal reaction for 4 hours in an oven at 160 ℃.
1.4 after the autoclave in 1.3 is cooled to room temperature, taking out the foam nickel after the hydrothermal reaction, immersing the foam nickel in deionized water for ultrasonic treatment for 20min to remove loose substances on the surface, washing the foam nickel with the deionized water and absolute ethyl alcohol for three times, drying the foam nickel in an oven for 24h at 80 ℃, and recording the quality of the foam nickel after the reaction. The sample loading amount is measured to obtain the mass difference before and after the foam nickel hydrothermal reaction.
1.5 with NaH2PO2·H2O is a phosphorus source, and the mass ratio of the phosphorus source to the sample load is 15: 1, placing the foamed nickel obtained in 1.4 at the center of a tube furnace at a distance of 4.5cm from a phosphorus source and under an argon atmosphere at 2 ℃ for min-1Heating to 350 ℃ at the heating rate of (1) and carrying out heat treatment for 2 h. And cooling to room temperature to obtain the binderless electrode material.
The binderless electrode material obtained in example 1 was analyzed by X-ray diffraction to obtain an XRD spectrum, as shown in fig. 1. From FIG. 1, it can be seen that in addition to three sharp diffraction peaks of the foamed nickel substrate, the rest diffraction peaks can be indexed to Ni (OH)2(JCPDS PDF #13-0128) and Ni2Characteristic diffraction peaks of the P (JCPDS PDF #03-0953) crystalline phase, indicating successful preparation of Ni (OH)2/Ni2P composite, which is consistent with the expected results.
In a three-electrode test system, the binderless electrode material obtained in example 1 was used as a working electrode of a supercapacitor, a 3M KOH solution was used as an electrolyte, mercury/mercury oxide was used as a reference electrode, and a platinum sheet was used as a counter electrode. The electrochemical workstation CHI660E is adopted to perform cyclic voltammetry test and charge-discharge test to investigate the electrochemical performance of the binderless electrode material as the working electrode of the supercapacitor, a cyclic voltammetry curve graph of the binderless electrode material at different scanning rates is obtained and shown in figure 2, a charge-discharge curve graph of the binderless electrode material at different current densities is obtained and shown in figure 3, and a relation curve graph of the specific capacity and the current density is obtained and shown in figure 4. The voltage range of the cyclic voltammetry test is 0 to 07V, scan rate of 5, 10, 15, 20, 25mV s-1The voltage range of the charge and discharge test is 0-0.5V, and the current density is 1, 2, 3, 4, 5, 10A g-1. Fig. 2 shows that a group of obvious redox peaks exist in the graph, which indicates that the prepared binderless electrode material has reversible redox reaction in the electrochemical process and has good electrochemical activity. The response current density of the cyclic voltammogram increased with the increase of the scan rate, indicating that the prepared binderless electrode material has a good electrochemical response rate. From fig. 3, it can be observed that the shape of the charge and discharge curve is not seriously changed with the increase of the current density and is almost symmetrical, indicating that the binderless electrode material prepared in example 1 has high coulombic efficiency and good rate capability. In addition, the charge and discharge curves exhibit a clear charge and discharge plateau, indicating Ni (OH)2/Ni2The P composite material has reversible oxidation-reduction reaction in the charging and discharging processes, which is consistent with the analysis result of cyclic voltammetry. FIG. 4 shows the specific capacity versus current density for binderless electrode materials as supercapacitor electrode materials, showing that at each current density the binderless electrode materials exhibit a high specific capacity, at 1A g-1The specific capacity is highest and reaches 2265C g-1When the current density increased to 10A g-1The specific capacity is up to 1137C g-1The specific capacity retention rate was 50.2%. The binderless electrode material obtained in the embodiment 1 has good electrochemical activity, high specific capacity and good rate performance, and the binderless electrode material provided by the invention has good application prospect in the electrode material of the supercapacitor.
Example 2
2.1 cutting a large piece of foam nickel into an area of 2X 5cm2The small nickel foam blocks are sequentially cleaned by acetone, deionized water and absolute ethyl alcohol for 30min in an ultrasonic mode, dried in an oven at 80 ℃ for 12h, and the mass of the nickel foam before reaction is recorded.
2.2 weighing 1.164g of nickel nitrate hexahydrate, 0.45g of urea and 0.11g of ammonium fluoride, dissolving in 40ml of deionized water, and magnetically stirring for 10min to obtain a precursor solution.
2.3 transfer the precursor solution from 2.2 to 100ml Teflon liner and dip into two 2.1 cleaned 2X 5cm strips2The nickel foam is sealed in a stainless steel autoclave and is subjected to hydrothermal reaction for 4 hours in an oven at 160 ℃.
And 2.4 after the autoclave in the 2.3 is cooled to room temperature, taking out the foam nickel after the hydrothermal reaction, immersing the foam nickel into deionized water for ultrasonic treatment for 20min to remove loose substances on the surface, washing the foam nickel with the deionized water and absolute ethyl alcohol for three times, drying the foam nickel in an oven for 24h at the temperature of 80 ℃, and recording the quality of the foam nickel after the reaction. The sample loading amount is measured to obtain the mass difference before and after the foam nickel hydrothermal reaction.
2.5 with NaH2PO2·H2O is a phosphorus source, and the mass ratio of the phosphorus source to the sample load is 20: 1, placing the foamed nickel obtained in 2.4 at the center of a tube furnace at a distance of 4.5cm from a phosphorus source at 2 ℃ for min under an argon atmosphere-1Heating to 350 ℃ at the heating rate of (1) and carrying out heat treatment for 2 h. And cooling to room temperature to obtain the binderless electrode material.
In a three-electrode test system, the binderless electrode material obtained in example 2 was used as a working electrode of a supercapacitor, a 3M KOH solution was used as an electrolyte, mercury/mercury oxide was used as a reference electrode, and a platinum sheet was used as a counter electrode. The electrochemical workstation CHI660E is adopted to perform cyclic voltammetry test and charge-discharge test to investigate the electrochemical performance of the binderless electrode material as the working electrode of the supercapacitor, a cyclic voltammetry curve graph of the binderless electrode material at different scanning rates is obtained and shown in FIG. 5, a charge-discharge curve graph of the binderless electrode material at different current densities is obtained and shown in FIG. 6, and a relation curve graph of the specific capacity and the current density is obtained and shown in FIG. 7. The voltage range of the cyclic voltammetry test is 0 to 0.7V, and the scanning rate is 5, 10, 15, 20 and 25mV s-1The voltage range of the charge and discharge test is 0-0.5V, and the current density is 1, 2, 3, 4, 5, 10A g-1. The existence of a group of redox peaks in the graph can be observed from fig. 5, which shows that the prepared binderless electrode material has reversible redox reaction in the electrochemical process and has good electrochemical activity. From FIG. 6, the charge and discharge curves were observedThe line shows an obvious charge-discharge platform, which indicates that the electrode material undergoes reversible redox reaction in the charge-discharge process, which is consistent with the analysis result of cyclic voltammetry. FIG. 7 shows the specific capacity versus current density curve for binderless electrode materials as supercapacitor electrode materials at 1A g-1When the specific capacity is high, the specific capacity reaches 1029C g-1When the current density increased to 10A g-1Specific capacity of 135C g-1。
Claims (10)
1. A preparation method of the binderless electrode material is characterized by comprising the following steps of:
s1) soaking the three-dimensional conductive current collector substrate in a solution containing a nickel source, a precipitating agent and a morphology regulator to carry out hydrothermal reaction or solvothermal reaction to obtain an intermediate;
s2), in a protective atmosphere, the intermediate and a phosphorus source are not contacted with each other, and heat treatment is carried out, so that the binderless electrode material is obtained.
2. The method for preparing according to claim 1, wherein the three-dimensional conductive current collector substrate is selected from a foamed metal or a metal mesh; the nickel source is selected from nickel nitrate; the precipitating agent is selected from urea; the morphology modifier is selected from ammonium fluoride; the phosphorus source is selected from sodium hypophosphite.
3. The method according to claim 1, wherein the concentration of the nickel source in the solution is 0.02g/ml to 0.04 g/ml; the concentration of the precipitant in the solution is 0.005-0.02 mg/ml; the concentration of the morphology regulator in the solution is 0.001-0.005 g/ml; the solvent of the solution is water and/or ethanol.
4. The method according to claim 1, wherein the temperature of the hydrothermal reaction or the solvothermal reaction is 150 ℃ to 170 ℃; the time of the hydrothermal reaction or the solvothermal reaction is 3.5-4.5 h.
5. The preparation method according to claim 1, wherein the three-dimensional conductive current collector substrate is subjected to ultrasonic cleaning and drying, and then is soaked in a solution containing a nickel source, a precipitating agent and a morphology regulator to perform a hydrothermal reaction or a solvothermal reaction;
and after the hydrothermal reaction or the solvothermal reaction, carrying out ultrasonic treatment on the three-dimensional conductive current collector substrate after the reaction in water, washing and drying to obtain an intermediate.
6. The preparation method according to claim 1, wherein the mass ratio of the mass difference of the intermediate body to the three-dimensional conductive current collector substrate to the phosphorus source is 1: (10-20).
7. The method according to claim 1, wherein the temperature of the heat treatment is 300 ℃ to 400 ℃; the heat treatment time is 1-3 h; the heating rate of the heat treatment is 1.5-2.5 ℃/min.
8. The method according to claim 1, wherein the heat treatment is performed in a tube furnace; the phosphorus source is located upstream of the tube furnace; the distance between the phosphorus source and the intermediate is 4-5 cm.
9. The binderless electrode material is characterized by comprising a three-dimensional conductive current collector substrate and Ni (OH) loaded on the three-dimensional conductive current collector substrate2/Ni2P composite material.
10. A supercapacitor, characterized by comprising the binderless electrode material prepared by the preparation method of any one of claims 1 to 8.
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