CN115458336A - Preparation method of super capacitor anode material - Google Patents
Preparation method of super capacitor anode material Download PDFInfo
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- CN115458336A CN115458336A CN202211145460.4A CN202211145460A CN115458336A CN 115458336 A CN115458336 A CN 115458336A CN 202211145460 A CN202211145460 A CN 202211145460A CN 115458336 A CN115458336 A CN 115458336A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003990 capacitor Substances 0.000 title claims abstract description 9
- 239000010405 anode material Substances 0.000 title claims abstract description 8
- 239000011669 selenium Substances 0.000 claims abstract description 94
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000007772 electrode material Substances 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011888 foil Substances 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000005036 potential barrier Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 9
- 150000003346 selenoethers Chemical class 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- 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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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a super capacitor anode material, which comprises the following steps: preparing 0.1-0.15 g of selenium dioxide, 0.2-0.3 g of nickel chloride and 0.2-0.3 g of lithium chloride uniform solution, using foamed nickel as a working electrode, using a platinum wire and a saturated calomel electrode as a counter electrode and a reference electrode respectively, setting voltage, and depositing to obtain Ni 3 Se 2 An electrode material; mixing Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; pre-lithium intercalation is carried out, cut-off voltage is selected respectively, the intercalation amount of lithium ions is realized by controlling the voltage, and further Ni with controllable selenium vacancy content is obtained 3 Se 2 An electrode material. Has the advantages that: simple prelithiation technology for preparing Ni with controllable selenium vacancy content 3 Se 2 A positive electrode material; quickening the ion migration rate, reducing the ion diffusion potential barrier and promoting the rapid reaction kinetics and multiplying powerEnergy is saved; the specific capacity is improved.
Description
Technical Field
The invention relates to the field of new energy storage, in particular to a preparation method of a super capacitor anode material.
Background
The super capacitor is a novel energy storage device developed in recent years, has the advantages of high power density, high charging speed, long cycle service life, wide working temperature range, good safety performance, environmental protection and the like, and has wide application prospect in the fields of new energy automobiles, micro communication equipment, heavy machinery, aerospace and the like (Chinese invention patent, application number 201810202685.6). It is well known that the performance of a supercapacitor is completely dependent on its electrode material. However, compared with rechargeable batteries, supercapacitors still lack high-performance electrode materials, which severely restricts the industrial production process (Energy & Environmental Science,2016,9,102-106.Advanced Energy materials,2019,9, 1802928). Therefore, designing and constructing a novel electrode material with excellent electrochemical performance is of great significance for improving the performance of the supercapacitor.
In recent years, researchers tend to improve the charge storage capacity of supercapacitors by designing new cathode materials, and they attempt to use various transition metal compounds, especially nickel-based selenides, as cathode materials mainly due to their advantages of high theoretical specific capacitance, excellent redox properties and electrochemical activity, various valence states, abundant raw materials, environmental friendliness, and low price (Electrochimica Acta,2021,393,139049.Acs appl. Mater. Interfaces,2019,11, 7946-7953). However, these compounds all have disadvantages of poor electron transport ability and low rate. In order to overcome the above problems, researchers have proposed a series of solutions such as combining a carbonaceous skeleton having excellent conductivity, constructing electrode Materials having different morphologies, and adjusting the size of the electrode Materials, etc. (Advanced Energy Materials,2018,8,1702247.Nano Energy,2017,35,331-340.Energy and environmental science,2016,9,1299-1307.Adv. Energy material.2016, 6, 1600341). Although the electrochemical performance of the Ni-based selenide is improved to a certain extent, the specific capacity and rate of the Ni-based selenide under high current density can not meet the requirement of a high-performance supercapacitor. Therefore, how to reasonably design and construct a large-capacity and high-rate Ni-based selenide electrode material still is a very challenging problem.
Research finds that vacancy engineering is considered to be an ideal technology for improving the electrochemical performance of the transition metal compound. On the one hand, the introduction of vacancies in the transition metal compound may generate defect levels in the forbidden region, resulting in a reduction of the forbidden band and a shift of the fermi level. Thus, the anion vacancies can act as shallow donors, effectively modulating the electronic structure, enhancing the conductivity of the transition metal compound (adv. Mater, 2020,32,1905923.Acs nano,2018,12, 1894). On the other hand, the presence of vacancy defects interferes to some extent with the surrounding atoms, resulting in a reduction in their coordination number, inevitably producing a large number of exposed unsaturated dangling bonds in the vacancy portion, which can serve as strong adsorption sites for foreign ions or intermediate species to reach a more stable state of the system; meanwhile, a large number of VI element vacancy defects can be found, and all the defects have positive charges (proton states), so that abundant anions can be smoothly captured (adv. Mater.2020,32,1905923). Thus, vacancies more readily trap electrolyte ions, and then provide a wide space for ion storage, further facilitating redox reactions. In addition, the vacancy defect can generate a profound influence on ion intercalation/delamination in the active material, reduce stress concentration and electrostatic repulsion between adjacent layers, directly serve as a 'highway' channel for accelerating ion migration, and effectively overcome diffusion barriers in the charge/discharge process. Therefore, it greatly improves the reaction kinetics and rate capability of the electrode material. In addition, the generated vacancy defects can increase the surface energy of the system, so that a large number of active centers are generated, more electrode materials are contacted with electrolyte ions to perform redox reaction, and the specific capacity of the electrode materials is improved. In previous researches, researchers generally adopt high-temperature calcination, strong reducing agent reduction and low-temperature plasma to introduce vacancies into active materials (chem.eng.j., 2022,427,131711.j. Mater.chem.a., 2021,9,11563.j. Mater.chem.a., 2020,8, 9278), and the methods are either high in energy consumption or complicated in operation steps, and more importantly, the content of the introduced vacancies cannot be controlled (the electrochemical performance of the active materials is greatly influenced by too much or too little content of the vacancies). Therefore, how to develop a proper method to greatly improve the specific capacity and the multiplying power of the Ni-based selenide under the condition of ensuring the controllable vacancy content becomes the current primary task.
Disclosure of Invention
In order to comprehensively solve the problems, particularly the defects in the prior art, the invention provides a preparation method of a super capacitor anode material, which can comprehensively solve the problems.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of a super capacitor anode material comprises the following specific steps:
1) And mixing raw materials:
dissolving 0.1-0.15 g of selenium dioxide, 0.2-0.3 g of nickel chloride and 0.2-0.3 g of lithium chloride in 45-55 ml of water, and stirring for 20-30 min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.6-1.0V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 3.0-2.0V, 3.0-1.0V and 3.0-0.0V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 An electrode material.
Further, the specific method is as follows:
1) And mixing raw materials:
dissolving 0.111g selenium dioxide, 0.2377g nickel chloride and 0.212g lithium chloride in 50ml water, and stirring for 25min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.8V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foils are respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 2.5V, 2.0V and 1.5V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 An electrode material.
Further, the water in the step 1 is deionized water.
Further, the deposition time in the step 2 is not less than 400s.
Further, the concentration of lithium hexafluorophosphate in the step 3 is 1mol.
Further, the specific method is as follows:
1) And mixing raw materials:
dissolving 0.1g of selenium dioxide, 0.2g of nickel chloride and 0.2g of lithium chloride in 45ml of water, and stirring for 20min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.6V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting cut-off voltage ranges of 2.0V, 1.0V and 0.5V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 And (3) an electrode material.
Further, the specific method is as follows:
1) And mixing raw materials:
dissolving 0.15g of selenium dioxide, 0.3g of nickel chloride and 0.3g of lithium chloride in 55ml of water, and stirring for 30min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 1.0V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 3.0V, 3.0V and 3.0V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 And (3) an electrode material.
The invention has the beneficial effects that:
in the invention, ni with controllable selenium vacancy content is prepared by a simple prelithiation technology 3 Se 2 And (3) a positive electrode material.
In the invention, the generated vacancy defects effectively and greatly accelerate the ion migration rate, reduce the ion diffusion potential barrier and promote the rapid reaction kinetics and the rate capability.
According to the invention, a large number of Se vacancies are introduced into the prepared electrode material, so that the electronic structure of the electrode material is regulated, the conductivity is improved, the ion adsorption capacity is increased, a rapid channel is provided for the diffusion of ions, and the reaction kinetics and the rate capability of the electrode material are greatly improved; in addition, the generated vacancy defects can increase the surface energy of the system, so that a large number of active centers are generated, more electrode materials are contacted with electrolyte ions to perform redox reaction, and the specific capacity of the electrode materials is improved.
Drawings
FIG. 1 shows Ni enriched with optimal selenium vacancy content according to the invention 3 Se 2 Scanning electron microscope photographs of (a);
FIG. 2 shows Ni enriched with optimal selenium vacancy content according to the invention 3 Se 2 And Ni 3 Se 2 An XRD pattern of (a);
FIG. 3 shows Ni enriched with optimum selenium vacancy content according to the invention 3 Se 2 And Ni 3 Se 2 (ii) a Ni 2p XPS spectrum of (a);
FIG. 4 shows Ni enriched with optimum selenium vacancy content according to the invention 3 Se 2 Specific capacity and rate capability.
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.
Example 1
A preparation method of a super capacitor anode material comprises the following specific steps:
firstly, dissolving 0.111g of selenium dioxide, 0.2377g of nickel chloride and 0.212g of lithium chloride in deionized water, and stirring for 15min to obtain a transparent and uniform solution; then using foamed nickel as working electrode, using platinum wire and saturated calomel electrode as counter electrode and reference electrode respectively, setting voltage 0.8V, settlingProduct time 400s; finally, washing with deionized water and absolute ethyl alcohol for multiple times, and drying at 60 ℃ for 12 hours to obtain Ni 3 Se 2 And (3) a positive electrode material.
Preparation of Ni with controllable selenium vacancy content 3 Se 2 ：
Ni to be prepared 3 Se 2 The lithium ion battery is assembled by taking ethyl carbonate/dimethyl carbonate/diethyl carbonate (volume ratio: 1 3 Se 2 Electrode material enriched with Ni, the optimum selenium vacancy 3 Se 2 See fig. 1, fig. 2, and fig. 3 for SEM, XRD, and Ni XPS, respectively.
Ni rich in optimum selenium vacancy content 3 Se 2 Electrochemical performance test of electrode material:
firstly, 3M potassium hydroxide is prepared as electrolyte solution, and Ni rich in optimum selenium vacancy content is used 3 Se 2 The platinum electrode and the mercury/mercury oxide are respectively used as a working electrode, a counter electrode and a reference electrode, and an electrochemical workstation is used for testing the cyclic voltammetry and constant current charge and discharge of the obtained electrode material respectively to obtain the specific capacity and the multiplying power of the electrode material, which are shown in figure 4. As can be seen from FIG. 4, the current density was 1Ag -1 The specific capacity is up to 1630F g -1 Even at 100Ag -1 Under the condition of large current, 52 percent of the original specific capacity can be still maintained, which fully indicates that the electrode material has large specific capacity and excellent rate performance.
The present invention is illustrated by way of example and not by way of limitation. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing disclosure without departing from the spirit or essential characteristics of all embodiments, and that all changes and modifications apparent from the above teachings are within the scope of the invention.
Claims (7)
1. A preparation method of a super capacitor anode material is characterized by comprising the following steps:
1) And mixing raw materials:
dissolving 0.1-0.15 g of selenium dioxide, 0.2-0.3 g of nickel chloride and 0.2-0.3 g of lithium chloride in 45-55 ml of water, and stirring for 20-30 min to obtain a uniform transparent solution;
2) And preparing Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.6-1.0V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foils are respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 3.0-2.0V, 3.0-1.0V and 3.0-0.0V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 An electrode material.
2. The preparation method of the supercapacitor positive electrode material according to claim 1, which is characterized by comprising the following steps:
1) And mixing raw materials:
dissolving 0.111g selenium dioxide, 0.2377g nickel chloride and 0.212g lithium chloride in 50ml water, and stirring for 25min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.8V,depositing for a period of time to obtain Ni 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 2.5V, 2.0V and 1.5V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 An electrode material.
3. The method for preparing the positive electrode material of the supercapacitor according to claim 2, wherein the water in the step 1 is deionized water.
4. The method for preparing the positive electrode material of the supercapacitor according to claim 2, wherein the deposition time in the step 2 is not less than 400s.
5. The method for preparing the positive electrode material of the supercapacitor according to claim 2, wherein the concentration of the lithium hexafluorophosphate in the step 3 is 1mol.
6. The preparation method of the supercapacitor positive electrode material according to claim 1, which is characterized by comprising the following steps:
1) And mixing raw materials:
dissolving 0.1g of selenium dioxide, 0.2g of nickel chloride and 0.2g of lithium chloride in 45ml of water, and stirring for 20min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 0.6V, and the nickel is deposited for a period of timeThen Ni is obtained 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 2.0V, 1.0V and 0.5V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 And (3) an electrode material.
7. The preparation method of the supercapacitor positive electrode material according to claim 1, which is characterized by comprising the following steps:
1) And mixing raw materials:
dissolving 0.15g of selenium dioxide, 0.3g of nickel chloride and 0.3g of lithium chloride in 55ml of water, and stirring for 30min to obtain a uniform transparent solution;
2) Preparation of Ni 3 Se 2 Electrode material:
in the solution obtained in the step 1, foamed nickel is used as a working electrode, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, the voltage is set to be 1.0V, and Ni is obtained after deposition for a period of time 3 Se 2 An electrode material;
3) Preparing Ni with controllable selenium vacancy content 3 Se 2 Electrode material:
mixing the Ni obtained in step 2 3 Se 2 Cleaning and drying the electrode material, dried Ni 3 Se 2 And commercial lithium foil is respectively used as a positive electrode and a negative electrode, lithium hexafluorophosphate is used as electrolyte, and the button lithium battery is assembled; then discharging and pre-embedding lithium, respectively selecting the cut-off voltage ranges of 3.0V, 3.0V and 3.0V, realizing the embedding amount of lithium ions by controlling the voltage, and further obtaining Ni with controllable selenium vacancy content 3 Se 2 An electrode material.
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| CN103680972A (en) * | 2012-09-10 | 2014-03-26 | 中国科学院金属研究所 | High-energy high-power density lithium ion supercapacitor and assembling method thereof |
| CN104538194A (en) * | 2014-12-18 | 2015-04-22 | 天津大学 | Preparation method of lithium ion capacitor (LIC) adopting pre-lithiation hard carbon negative electrode |
| CN106868563A (en) * | 2015-12-11 | 2017-06-20 | 中国海洋大学 | A kind of preparation method and applications of selenide thin film modifying foam nickel electrode |
| CN113470983A (en) * | 2020-03-30 | 2021-10-01 | 天津大学 | Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103680972A (en) * | 2012-09-10 | 2014-03-26 | 中国科学院金属研究所 | High-energy high-power density lithium ion supercapacitor and assembling method thereof |
| CN104538194A (en) * | 2014-12-18 | 2015-04-22 | 天津大学 | Preparation method of lithium ion capacitor (LIC) adopting pre-lithiation hard carbon negative electrode |
| CN106868563A (en) * | 2015-12-11 | 2017-06-20 | 中国海洋大学 | A kind of preparation method and applications of selenide thin film modifying foam nickel electrode |
| CN113470983A (en) * | 2020-03-30 | 2021-10-01 | 天津大学 | Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof |
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