CN111146018B - Electrode active material for supercapacitor, preparation method of electrode active material, electrode material for supercapacitor, supercapacitor and electric device - Google Patents
Electrode active material for supercapacitor, preparation method of electrode active material, electrode material for supercapacitor, supercapacitor and electric device Download PDFInfo
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- CN111146018B CN111146018B CN202010017568.XA CN202010017568A CN111146018B CN 111146018 B CN111146018 B CN 111146018B CN 202010017568 A CN202010017568 A CN 202010017568A CN 111146018 B CN111146018 B CN 111146018B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
Abstract
The invention provides an electrode active material for a supercapacitor, a preparation method of the electrode active material, an electrode material for the supercapacitor, the supercapacitor and an electric device, and relates to the technical field of supercapacitors. The electrode active material for the supercapacitor is a bimetallic sulfide which has abundant reaction sites and high conductivity; the invention also provides a preparation method of the electrode active material for the supercapacitor, which comprises the steps of firstly preparing the pyridine carboxylic acid ligand, the nickel source, the vanadium source and the first solvent into a Ni-V-MOF precursor by adopting a solvent evaporation method, and then carrying out solvothermal reaction on the Ni-V-MOF precursor, the sulfur source and the second solvent to prepare the electrode active material for the supercapacitor; the preparation method is simple to operate and stable in process, and the prepared electrode material for the super capacitor is uniform in particle distribution, regular in morphology and good in conductivity. The invention also provides an electrode material for a supercapacitor, which comprises the electrode active material for the supercapacitor.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to an electrode active material for a super capacitor, a preparation method of the electrode active material, an electrode material for the super capacitor, the super capacitor and an electric device.
Background
As environmental pollution continues to increase and non-renewable energy sources such as petroleum are in short supply, based on this situation, a great deal of research is being conducted to find alternative, renewable energy supplies to slow down the consumption of petroleum reserves. The super capacitor is a novel energy storage material and is distinguished by a series of characteristics such as long cycle life, high power density, wide working temperature range and the like. The performance of supercapacitors depends to a large extent on the composition of the electrode material and the design of the electrode structure. The performance of the super capacitor can be effectively improved by changing the components of the electrode material and regulating the appearance and the size of the active material of the super capacitor.
Metal Organic Frameworks (MOFs) are porous materials with a periodic network structure formed by a coordination bond assembly process of Metal ions and organic ligands. The MOFs have the characteristics of high specific surface area, abundant pore structures, easily-regulated appearance, easily-obtained and cheap raw materials, and the like, so that the MOFs can be widely applied to the fields of separation, sensing, catalysis, gas storage and the like. The ordered pore channel structure of MOFs is beneficial to the permeation of electrolyte ions, and on the other hand, the metal organic framework has a metal ion or ion cluster center and provides rich and effective active sites, so that the metal organic framework is an ideal template agent or precursor of the supercapacitor. The metal organic framework can be derived from electrode materials such as metal oxides, phosphides, sulfides or carbon materials. Among the numerous energy storage materials, transition metal sulfides have been the focus of research. Currently, more studies are made on single metal sulfides, and less studies are made on multi-metal sulfides. And the conductivity of the single metal sulfide is general, and the overall performance needs to be further improved.
In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first purpose of the present invention is to provide a novel electrode active material for a supercapacitor, wherein the electrode active material is a bimetallic sulfide, has abundant reaction sites and high electrical conductivity, and solves the technical problem of poor electrical conductivity of a single metal sulfide in the prior art.
The second object of the present invention is to provide a method for preparing the electrode active material for a supercapacitor.
The third purpose of the invention is to provide an electrode material for a supercapacitor.
A fourth object of the present invention is to provide a supercapacitor.
A fifth object of the present invention is to provide an electric apparatus.
The chemical molecular formula of the electrode active material for the super capacitor is NixVySzWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and z is more than or equal to 1.2 and less than or equal to 1.3;
the electrode active material has a rod-like structure.
Further, on the basis of the above technical solution of the present invention, the electrode active material for the supercapacitor is mainly prepared from the following raw materials:
pyridine carboxylic acid ligand, nickel source, vanadium source, first solvent, sulfur source and second solvent;
wherein the mass ratio of the pyridine carboxylic acid ligand, the nickel source, the vanadium source, the first solvent, the sulfur source and the second solvent is (3-7): (4-8): (1-3): (40-80): (1-6): (30-80).
Further, on the basis of the above technical solution of the present invention, the pyridine carboxylic acid ligand includes any one of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, or 2, 6-pyridinedicarboxylic acid, or a combination of at least two thereof;
preferably, the nickel source comprises nickel nitrate and/or nickel chloride;
preferably, the source of vanadium comprises ammonium metavanadate;
preferably, the first solvent comprises any one of water, methanol or ethanol or a combination of at least two thereof;
preferably, the sulphur source comprises thioacetamide and/or thiourea;
preferably, the second solvent comprises methanol and/or ethanol.
The invention also provides a preparation method of the electrode active material for the supercapacitor, which comprises the following steps:
(a) mixing a pyridine carboxylic acid ligand, a nickel source, a vanadium source and a first solvent, and crystallizing to obtain a Ni-V-MOF precursor;
(b) and mixing the Ni-V-MOF precursor, a sulfur source and a second solvent, and carrying out solvothermal reaction to obtain the electrode material for the super capacitor.
Further, in the step (a), based on the above technical solution of the present invention, the pyridine carboxylic acid ligand includes any one or a combination of at least two of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, and 2, 6-pyridinedicarboxylic acid;
preferably, in step (a), the nickel source comprises nickel nitrate and/or nickel chloride;
preferably, in step (a), the source of vanadium comprises ammonium metavanadate;
preferably, in step (a), the first solvent comprises any one of water, methanol or ethanol, or a combination of at least two thereof.
Further, on the basis of the above technical solution of the present invention, in the step (a), the molar ratio between the pyridine carboxylic acid ligand, the nickel source and the vanadium source is (1-2): (1-2): (1-2), preferably (1.2-2): (1-1.8): (1-1.8), more preferably (1.5-2): (1-1.5): (1-1.5).
Further, on the basis of the above technical solution of the present invention, in the step (b), the sulfur source includes thioacetamide and/or thiourea;
preferably, in step (b), the second solvent comprises methanol and/or ethanol;
preferably, in step (b), the mass ratio of the Ni-V-MOF precursor to the sulfur source to the second solvent is (1-3): (5-50), preferably (1-2): (10-45), and more preferably 1.5:1.5: 40.
Further, on the basis of the above technical scheme of the present invention, in the step (b), the temperature of the solvothermal reaction is 110-;
preferably, in the step (b), the solvent is removed from the reaction solution obtained after the solvothermal reaction, and then the reaction solution is washed and dried to obtain the electrode material for the supercapacitor.
The invention also provides an electrode material for the super capacitor, which comprises the electrode active material for the super capacitor or the electrode active material for the super capacitor prepared by the preparation method of the electrode active material for the super capacitor;
preferably, the electrode material for the supercapacitor comprises the following components in percentage by mass:
60-90% of electrode active material, 5-30% of conductive agent and 5-10% of binder.
The invention also provides a super capacitor, which comprises the electrode material for the super capacitor.
The electrode active material for the supercapacitor, the preparation method thereof, the electrode material for the supercapacitor, the supercapacitor and the electric device provided by the invention have the following beneficial effects:
(1) the electrode active material for the super capacitor is a bimetallic sulfide with a chemical molecular formula of NixVySzWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and z is more than or equal to 1.2 and less than or equal to 1.3, the electrode active material is in a rod-shaped structure, has abundant reaction sites and higher electrical conductivity, and is one of ideal energy storage materials at present.
(2) The invention provides a preparation method of an electrode active material for a supercapacitor, which comprises the steps of firstly preparing a pyridine carboxylic acid ligand, a nickel source, a vanadium source and a first solvent into a Ni-V-MOF precursor by adopting a solvent evaporation method, and then carrying out solvothermal reaction on the Ni-V-MOF precursor, a sulfur source and a second solvent to prepare the electrode active material for the supercapacitor; the preparation method is simple to operate and stable in process, and the obtained electrode material for the super capacitor is uniform in particle distribution, regular in appearance and good in conductivity.
(3) The invention provides an electrode material for a supercapacitor, which comprises the electrode active material for the supercapacitor. In view of the advantages of the electrode active material, the electrode material for the supercapacitor has the same advantages.
(4) The invention provides a supercapacitor, which contains the electrode active material for the supercapacitor or the electrode material for the supercapacitor. In view of the advantages of the electrode active material for the super capacitor or the electrode material for the super capacitor, the super capacitor has excellent cycling stability and higher specific capacitance.
(5) The invention provides an electric device which comprises the super capacitor. In view of the advantages of the supercapacitor, the same advantages are also provided for the electric device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM image of a Ni-V-MOF precursor provided in example 1 of the present invention;
FIG. 2 is an SEM photograph of an electrode active material for a Ni-V-S supercapacitor provided in example 1 of the present invention;
FIG. 3 is a charge/discharge diagram of an electrode material for a supercapacitor provided in example 8 of the present invention;
fig. 4 is a cycle life chart of the electrode material for a supercapacitor provided in example 8 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, 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.
According to a first aspect of the present invention, there is provided an electrode active material for a supercapacitor, the electrode active material having a chemical formula of NixVySzWherein 0.5 is less than or equal tox≤0.75，0.25≤y≤0.5，x+y＝1，1.2≤z≤1.3；
The electrode active material has a rod-like structure.
In particular, x is typically, but not limited to, 0.50, 0.52, 0.54, 0.55, 0.58, 0.6, 0.62, 0.64, 0.65, 0.68, 0.7, 0.72, 0.74 or 0.75. y is typically, but not limited to, 0.25, 0.26, 0.28, 0.30, 0.32, 0.34, 0.35, 0.38, 0.40, 0.42, 0.44, 0.45, 0.48 or 0.50. However, the values of x and y should be such that the sum of the two values is equal to 1. z typically, but not by way of limitation, has a value of 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29 or 1.30.
The typical but non-limiting chemical formula of the electrode active material for the super capacitor is Ni0.5V0.5S1.2、Ni0.5V0.5S1.25、Ni0.5V0.5S1.3、Ni0.52V0.48S1.2、Ni0.52V0.48S1.25、Ni0.52V0.48S1.3、Ni0.55V0.45S1.2、Ni0.55V0.45S1.25、Ni0.58V0.42S1.3、Ni0.58V0.42S1.2、Ni0.58V0.42S1.25、Ni0.58V0.42S1.3、Ni0.6V0.4S1.2、Ni0.6V0.4S1.25、Ni0.6V0.4S1.3、Ni0.62V0.38S1.2、Ni0.62V0.38S1.25、Ni0.62V0.38S1.3、Ni0.65V0.35S1.2、Ni0.65V0.35S1.25、Ni0.65V0.35S1.3、Ni0.68V0.32S1.2、Ni0.68V0.32S1.25、Ni0.68V0.32S1.3、Ni0.7V0.3S1.2、Ni0.7V0.3S1.25、Ni0.7V0.3S1.3、Ni0.72V0.28S1.2、Ni0.72V0.28S1.25、Ni0.72V0.28S1.3、Ni0.75V0.25S1.2、Ni0.75V0.25S1.25Or Ni0.75V0.25S1.3。
The Ni-V-S is taken as a bimetallic sulfide and presents a rod-shaped structure, so that the Ni-V-S not only has abundant reaction sites, but also has higher conductivity, and is one of ideal energy storage materials at present.
As an alternative embodiment of the present invention, the electrode active material for a supercapacitor is mainly made of the following raw materials:
pyridine carboxylic acid ligand, nickel source, vanadium source, first solvent, sulfur source and second solvent;
wherein the mass ratio of the pyridine carboxylic acid ligand, the nickel source, the vanadium source, the first solvent, the sulfur source and the second solvent is (3-7): (4-8): (1-3): (40-80): (1-6): (30-80), preferably (4-6.8): (4.5-7): (1.5-2.5): (45-70): (1.5-4): (35-70).
Typical but non-limiting mass ratios of the pyridinecarboxylic acid ligand, the nickel source, the vanadium source, the first solvent, the sulfur source, and the second solvent are 3:4:1:40:1:30, 4:4:1:40:1:30, 5:4:1:40:1:30, 6:4:1:40:1:30, 3:5:1:40:1:30, 4:6:1:40:1:30, 5:7:1:40:1:30, 6:8:1:40:1:30, 3:4:2:40:1:30, 4:4:3:40:1:30, 5:4:2:40:1:30, 6:4:3:40:1:30, 3:4:1:50:1:30, 4:4:1:60:1:30, 5:4:1:70:1:30, 6:4:1: 30, 3:4: 40:1:30, 4:1: 30: 4:30, 5:4:1: 30: 4:30, 6:4:1: 30: 4:30, 4:4: 30: 1:30, 4: 30: 4:1: 30, 4:4: 30, 4, 6:4:1:40:6:30, 3:4:1:40:1:40, 4:4:1:40:1:50, 5:4:1:40:1:60, 6:4:1:40:1:80, 6:5:2:50:3:40, 6.68:5.8:2.32:50:3:40, 7:4:1:40:1:30, 7:6:3:60:3:50 or 7:8:3:80:6: 80.
As an alternative embodiment of the present invention, the pyridine carboxylic acid ligand includes any one of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, or 2, 6-pyridinedicarboxylic acid, or a combination of at least two thereof.
As an alternative embodiment of the present invention, the nickel source comprises nickel nitrate and/or nickel chloride, and the term "and/or" in the present invention means that the nickel source may comprise only nickel nitrate, only nickel chloride, and a combination of nickel nitrate and nickel chloride.
As an alternative embodiment of the invention, the source of vanadium comprises ammonium metavanadate.
As an alternative embodiment of the present invention, the first solvent comprises any one of water, methanol or ethanol or a combination of at least two thereof.
As an alternative embodiment of the present invention, the sulfur source comprises thioacetamide and/or thiourea, and "and/or" in the present invention means that the sulfur source may comprise only thioacetamide, or only thiourea, and may also comprise a combination of thioacetamide and thiourea.
As an alternative embodiment of the invention, the second solvent comprises methanol and/or ethanol.
Through the limitation on the specific types of the raw materials, the compatibility among the raw materials is better, and the performance of the prepared electrode active material for the super capacitor is better.
According to a second aspect of the present invention, there is also provided a method for preparing the above electrode active material for a supercapacitor, comprising the steps of:
(a) mixing a pyridine carboxylic acid ligand, a nickel source, a vanadium source and a first solvent, and crystallizing to obtain a Ni-V-MOF precursor;
(b) and mixing the Ni-V-MOF precursor, a sulfur source and a second solvent, and carrying out solvothermal reaction to obtain the electrode material for the super capacitor.
Specifically, in the step (a), the pyridine carboxylic acid ligand, the selected metal salt nickel source and the selected metal salt vanadium source are dissolved in a first solvent to form a saturated solution, and then the saturated solution is crystallized to obtain the Ni-V-MOF precursor.
The solvothermal reaction is a synthetic method in which an original mixture is reacted in a closed system by using an organic or non-aqueous solvent as a solvent at a certain temperature and under the autogenous pressure of the solution. And (b) reacting the Ni-V-MOF precursor with a sulfur source by adopting a solvothermal reaction so as to realize the vulcanization of the Ni-V-MOF precursor.
The preparation method of the electrode active material for the super capacitor, provided by the invention, comprises the steps of firstly preparing a Ni-V-MOF precursor by adopting a solvent evaporation method, and then carrying out solvothermal reaction on the Ni-V-MOF precursor, a sulfur source and a second solvent to obtain the electrode material for the super capacitor.
As an alternative embodiment of the present invention, in the step (a), the pyridine carboxylic acid ligand includes any one or a combination of at least two of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, and 2, 6-pyridinedicarboxylic acid. The pyridine carboxylic acid ligand is limited by specific types, so that the pyridine carboxylic acid ligand can form a stable coordination configuration with metal.
As an alternative embodiment of the present invention, in step (a), the nickel source comprises nickel nitrate and/or nickel chloride, which means that the nickel source may comprise only nickel nitrate, or only nickel chloride, and may also comprise a combination of nickel nitrate and nickel chloride.
As an alternative embodiment of the present invention, in step (a), the source of vanadium comprises ammonium metavanadate.
As an alternative embodiment of the present invention, in the step (a), the first solvent includes any one of water, methanol or ethanol or a combination of at least two thereof.
In an alternative embodiment of the present invention, in the step (a), the molar ratio between the pyridine carboxylic acid ligand, the nickel source and the vanadium source is (1-2): (1-2): (1-2), preferably (1.2-2): (1-1.8): (1-1.8), more preferably (1.5-2): (1-1.5): (1-1.5).
Typical but non-limiting molar ratios between the pyridinecarboxylic acid ligand, the nickel source, and the vanadium source are 1:1:1, 1.2:1:1, 1.5:1:1, 1.8:1:1, 2:1:1, 1:1.2:1, 1:1.5:1, 1:1.8:1, 1:2:1, 1:1:1.2, 1:1:1.5, 1:1:1.8, 1:1:2, 1.2:1:1.2, 1.2:1:1.5, 1.2:1:1.8, 1.2:1:2, 1.5:1.5, 1.8:1:1.5, 2:1.2:1, 2:1.8:1, or 2:2: 1:1:1.
As an alternative embodiment of the present invention, in step (b), the sulphur source comprises thioacetamide and/or thiourea. By "and/or" in the present invention is meant that the sulfur source may comprise thioacetamide alone, or thiourea alone, and may also comprise a combination of thioacetamide and thiourea.
As an alternative embodiment of the present invention, in step (b), the second solvent comprises methanol and/or ethanol.
The second solvent is mainly used as a reaction solvent in the solvothermal reaction. The second solvent is defined to have good dissolving capacity for Ni-V-MOF precursors and sulfur sources under solvothermal conditions, and meanwhile, the electrode material for the super capacitor is formed, and the size and the morphology of the structure are controlled.
As an alternative embodiment of the present invention, in the step (b), the mass ratio of the Ni-V-MOF precursor, the sulfur source and the second solvent is (1-3): 5-50, preferably (1-2): 10-45, and more preferably 1.5:1.5: 40. Typical but non-limiting mass ratios of the Ni-V-MOF precursor, the sulfur source, and the second solvent are 1:1:5, 2:1:5, 3:1:5, 1:2:5, 1:3:5, 1:1:10, 2:1:15, 3:1:20, 1:2:30, 1:3:40, 1:3:50, 2:2:45, 2:3:5, 2:3:10, 2:3:20, 2:3:30, 2:3:40, 2:3:50, or 3:3: 50.
Through the limitation of the specific types of the raw materials in the step (a) and the step (b), the compatibility among the raw materials is better, and the performance of the prepared electrode active material for the supercapacitor is better.
As an optional embodiment of the present invention, in the step (b), the temperature of the solvothermal reaction is 110-160 ℃, and the reaction time is 4-6 h;
typical but non-limiting temperatures are 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃; typical but non-limiting reaction times are 4h, 4.5h, 5h, 5.5h or 6 h.
The solvothermal reaction is more fully performed by limiting the temperature and time of the solvothermal reaction.
In an alternative embodiment of the present invention, in the step (b), the solvent is removed from the reaction solution obtained after the solvothermal reaction, and then the reaction solution is washed and dried to obtain the electrode material for a supercapacitor.
As a preferred embodiment of the present invention, a method for preparing an electrode active material for a supercapacitor, comprising the steps of:
(a) stirring and mixing a pyridine carboxylic acid ligand, a nickel source, a vanadium source and water, then heating for 30-60min, cooling, sealing a preservative film, placing in a refrigerator (below 0 ℃) for a week, and drying the generated green crystals in an oven at 50-80 ℃ to obtain a Ni-V-MOF precursor;
(b) mixing the Ni-V-MOF precursor, a sulfur source and ethanol, and placing the mixture in a closed reaction kettle for solvothermal reaction at the reaction temperature of 110 ℃ and 160 ℃ for 4-6h to obtain the electrode active material for the supercapacitor.
In the step (a), after the pyridine carboxylic acid ligand, the nickel source, the vanadium source and water are fully stirred, heating and standing are carried out, nickel ions and metavanadate ions are combined with oxygen atoms and nitrogen atoms on pyridine diacid to form Ni-V-MOF, the Ni-V-MOF is not separated out in hot water, the Ni-V-MOF can be slowly separated out in a crystal form along with the slow reduction of the temperature, and then the crystal is separated and dried to obtain the Ni-V-MOF precursor.
The overall performance of the electrode active material for the super capacitor is better by further limiting the steps of the preparation method and the process parameters.
According to a third aspect of the present invention, there is also provided an electrode material for a supercapacitor, comprising the electrode active material for a supercapacitor described above or an electrode active material for a supercapacitor produced by the method for producing the electrode active material for a supercapacitor described above.
In view of the advantages of the electrode active material, the electrode material for the supercapacitor has the same advantages.
As an optional embodiment of the invention, the invention also provides an electrode material for the supercapacitor, which comprises the following components in percentage by mass:
60-90% of electrode active material, 5-30% of conductive agent and 5-10% of binder.
Typical but non-limiting mass fractions of electrode active material are 60%, 65%, 70%, 75%, 80%, 85% or 90%; typical but not limiting mass fractions of conductive agent are 5%, 10%, 15%, 20%, 25% or 30%; typical but not limiting mass fractions of binders are 5%, 6%, 7%, 8%, 9% or 10%.
The conductive agent and the binder may be selected from those commonly used in the art.
In the present invention, "including" means that other components, in addition to the electrode active material, the conductive agent and the binder, which may impart different characteristics to the electrode material for a supercapacitor, may be included, and "including" may be replaced with "being" enclosed "or" consisting of … … ".
The electrochemical performance of the prepared electrode material for the super capacitor is better by limiting the components of the electrode material for the super capacitor.
According to a fourth aspect of the present invention, there is also provided a supercapacitor comprising the above electrode material for a supercapacitor.
In view of the advantages of the electrode active material for the supercapacitor or the electrode material for the supercapacitor, the supercapacitor has excellent cycling stability and high specific capacitance.
According to a fifth aspect of the present invention, there is also provided an electric device comprising the above-described supercapacitor.
In view of the advantages of the supercapacitor described above, the same effects can be obtained in an electric device using the supercapacitor according to the embodiment of the present invention. The electric device is an electric device that moves a component (e.g., a drill bit) using a super capacitor as a driving power source.
It should be noted that the super capacitor provided by the invention is not limited to be applied in the field of electric devices, and can also be applied to electronic devices, electric vehicles or power storage systems. An electronic device is an electronic device that performs various functions (e.g., playing music) using a super capacitor as a power source for operation. The electric vehicle is an electric vehicle that runs on a supercapacitor as a driving power source, and may be an automobile (including a hybrid vehicle) equipped with other driving sources in addition to the supercapacitor. The power storage system is a power storage system that uses an ultracapacitor as a power storage source. For example, in a home electric power storage system, electric power is stored in an ultracapacitor serving as an electric power storage source, and the electric power stored in the ultracapacitor is consumed as needed to enable use of various devices such as home electronic products.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor comprises the following steps:
(a) 2, 6-pyridinedicarboxylic acid (0.04mol), NH4VO3(0.02mol)、Ni(NO3)2·6H2Adding O (0.02mol) into a beaker, adding 50mL of deionized water, mixing, stirring to uniformly mix, placing the beaker in a water bath at 80 ℃ for heating for 30min, sealing a preservative film after the beaker is cooled, placing the beaker in a refrigerator (below 0 ℃) for one week, and placing the obtained green crystal in an oven for drying at 60 ℃ to obtain a Ni-V-MOF precursor;
(b) transferring the Ni-V-MOF precursor into a Thioacetamide (TAA) ethanol solution (0.04mol,40mL), then placing the mixture into a reaction kettle for solvothermal reaction at the reaction temperature of 120 ℃ for 5h, cooling the reaction solution after the reaction is finished, removing the solvent from the obtained reaction solution, adding water for centrifugation once, then adding ethanol for centrifugation twice, and finally drying the obtained product in a 60 ℃ oven to obtain the electrode active material for the Ni-V-S supercapacitor.
Example 2
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor comprises the following steps:
(a) 2, 6-pyridinedicarboxylic acid (0.02mol), NH4VO3(0.01mol)、Ni(NO3)2·6H2Adding O (0.01mol) into a beaker, adding 50mL of deionized water, mixing, stirring to uniformly mix, placing the beaker in a water bath at 80 ℃ for heating for 30min, stirring all the time by using a glass rod, cooling, sealing a preservative film, placing the preservative film in a refrigerator (below 0 ℃) for one week, and placing the obtained green crystal in an oven for drying at 50 ℃ to obtain a Ni-V-MOF precursor;
(b) transferring the Ni-V-MOF precursor into a Thioacetamide (TAA) ethanol solution (0.04mol,40mL), then placing the mixture into a reaction kettle for solvothermal reaction at the reaction temperature of 110 ℃ for 4h, cooling the reaction solution after the reaction is finished, removing the solvent from the obtained reaction solution, adding water for centrifugation once, then adding ethanol for centrifugation twice, and finally drying the obtained product in a 50 ℃ oven to obtain the electrode active material for the Ni-V-S supercapacitor.
Example 3
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor comprises the following steps:
(a) 2, 6-pyridinedicarboxylic acid (0.02mol), NH4VO3(0.01mol)、Ni(NO3)2·6H2Adding O (0.01mol) into a beaker, adding 50mL of deionized water, mixing, stirring to uniformly mix, placing the beaker in a water bath at 80 ℃ for heating for 30min, stirring all the time by using a glass rod, cooling, sealing a preservative film, placing the preservative film in a refrigerator (below 0 ℃) for one week, and placing the obtained green crystal in an oven for drying at 80 ℃ to obtain a Ni-V-MOF precursor;
(b) transferring the Ni-V-MOF precursor into a Thioacetamide (TAA) ethanol solution (0.04mol,40mL), then placing the mixture into a reaction kettle for solvothermal reaction at the reaction temperature of 160 ℃ for 6h, cooling the reaction solution after the reaction is finished, removing the solvent from the obtained reaction solution, adding water for centrifugation once, then adding ethanol for centrifugation twice, and finally drying the obtained product in an oven at the temperature of 80 ℃ to obtain the electrode active material for the Ni-V-S supercapacitor.
Example 4
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor comprises the following steps:
(a) 2, 3-pyridinedicarboxylic acid (0.04mol), NH4VO3(0.02mol)、NiCl2·6H2Adding O (0.02mol) into a beaker, adding 50mL of deionized water, mixing, stirring to uniformly mix, placing the beaker in a water bath at 80 ℃ for heating for 60min, sealing a preservative film after the beaker is cooled, placing the beaker in a refrigerator (below 0 ℃) for one week, and placing the obtained green crystal in an oven for drying at 60 ℃ to obtain a Ni-V-MOF precursor;
(b) transferring the Ni-V-MOF precursor into a methanol solution (0.04mol,40mL) of thiourea, then placing the solution into a reaction kettle for solvothermal reaction at the reaction temperature of 140 ℃ for 5h, cooling the reaction solution after the reaction is finished, removing the solvent from the obtained reaction solution, adding water for centrifugation once, adding ethanol for centrifugation twice, and finally drying the reaction solution in a 60 ℃ oven to obtain the electrode active material for the Ni-V-S supercapacitor.
Example 5
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for a supercapacitor was the same as example 1 except that the reaction temperature of the solvothermal reaction in step (b) was 160 ℃.
Example 6
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor was the same as example 1 except that the reaction temperature of the solvothermal reaction in the step (b) was 100 ℃.
Example 7
The present example provides an electrode active material for a supercapacitor, which has a rod-like structure.
The preparation method of the electrode active material for the supercapacitor was the same as example 1 except that the solvothermal reaction time in step (b) was 3 hours.
Example 8
The present example provides an electrode material for a supercapacitor, including the electrode active material for a supercapacitor provided in example 1.
The preparation method of the electrode material for the supercapacitor comprises the following steps:
after 16mg of the electrode active material for Ni-V-S supercapacitor, 2mg of PVDF and 2mg of acetylene black were mixed, 1mL of N-methylpyrrolidone was added to obtain an electrode material for supercapacitor in the form of slurry.
Example 9
The present example provides an electrode material for a supercapacitor, including the electrode active material for a supercapacitor provided in example 2.
The preparation method of the electrode material for the supercapacitor comprises the following steps:
14mg of the electrode active material for Ni-V-S supercapacitor, 2mg of PVDF and 2mg of acetylene black were mixed, and 1mL of N-methylpyrrolidone was added to obtain an electrode material for supercapacitor in the form of slurry.
Example 10
The present example provides an electrode material for a supercapacitor, including the electrode active material for a supercapacitor provided in example 3.
The preparation method of the electrode material for the supercapacitor comprises the following steps:
after 18mg of the electrode active material for Ni-V-S supercapacitor, 2mg of PVDF and 2mg of acetylene black were mixed, 1mL of N-methylpyrrolidone was added to obtain an electrode material for supercapacitor in the form of slurry.
Examples 11 to 14
Examples 11 to 14 each provide an electrode material for a supercapacitor, which comprises the electrode active materials for a supercapacitor provided in examples 4 to 7.
Examples 11 to 14 the electrode materials for supercapacitors were prepared in the same manner as in example 8.
Comparative example 1
The comparative example provides an electrode active material for a supercapacitor, which is cobalt sulfide and has a chemical formula of CoS.
Comparative example 2
The comparative example provides an electrode active material for a supercapacitor, which is manganese sulfide and has a chemical formula of MnS.
Comparative examples 3 to 4
Comparative examples 3 to 4 each provide an electrode material for a supercapacitor, comprising the electrode active materials for a supercapacitor provided in comparative example 1 and comparative example 2, respectively.
The preparation method of the electrode material for the supercapacitor is the same as that of example 8.
In order to verify the technical effects of the above examples and comparative examples, the following experimental examples were specifically set.
Experimental example 1
The electrode active materials for Ni-V-S supercapacitors provided in examples 1 to 7 were subjected to an atomic absorption test, and the chemical compositions of the electrode active materials for Ni-V-S supercapacitors were measured, as shown in Table 1.
TABLE 1
In addition, taking example 1 as an example, the Ni-V-MOF precursor and the Ni-V-S supercapacitor electrode active material were subjected to electron microscope scanning, as shown in FIG. 1 and FIG. 2.
As can be seen from FIG. 1, the Ni-V-MOF precursor has a rod-like structure.
As can be seen from FIG. 2, the electrode active material for Ni-V-S supercapacitor exhibits a rod-like structure having pores, which facilitates electron conduction and improves capacitance.
Experimental example 2
In order to examine the electrochemical characteristics of the electrode materials for supercapacitors provided in examples 8 to 14 and comparative examples 3 to 4, the following examinations were performed:
4mg of the electrode materials for supercapacitors as provided in examples 8 to 14 and comparative examples 3 to 4 were coated on foamed nickel (1X 2 cm)2) The coating area is 1 × 1cm2Drying at 60 ℃ to obtain an electrode;
the electrode was used as a working electrode, and a platinum sheet was used as a counter electrode (1X 1 cm)2) The calomel electrode is a reference electrode, 6mol/L KOH is used as electrolyte, the specific capacitance of the electrode when the current density is 1A/g and the capacitance retention rate after the electrode is cycled for 3000 circles under 1A/g are measured, and the specific detection results are shown in Table 2:
TABLE 2
As can be seen from the data in table 2, the electrochemical performance of the electrode material for a supercapacitor provided in each example of the present invention is superior to that of the comparative example as a whole.
Fig. 3 and 4 are a charge/discharge diagram and a cycle life diagram of the electrode material for a supercapacitor according to example 8, respectively. As can be seen from FIG. 3, the capacitances were 400F/g, 190F/g, 50F/g, 16F/g and 7F/g, respectively, at current densities of 1A/g, 2A/g, 5A/g, 8A/g and 10A/g. In FIG. 4, when the current density was 1A/g, the capacity retention was 85% after 3000 cycles.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (27)
1. The electrode active material for the super capacitor is characterized in that the chemical formula of the electrode active material is NixVySzWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and z is more than or equal to 1.2 and less than or equal to 1.3;
the electrode active material has a rod-like structure.
2. The electrode active material for a supercapacitor according to claim 1, which is mainly prepared from the following raw materials:
pyridine carboxylic acid ligand, nickel source, vanadium source, first solvent, sulfur source and second solvent;
wherein the mass ratio of the pyridine carboxylic acid ligand, the nickel source, the vanadium source, the first solvent, the sulfur source and the second solvent is (3-7): (4-8): (1-3): (40-80): (1-6): (30-80).
3. The electrode active material for a supercapacitor according to claim 2, wherein the pyridinecarboxylic acid ligand comprises any one of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, or 2, 6-pyridinedicarboxylic acid, or a combination of at least two thereof.
4. The electrode active material for a supercapacitor according to claim 3, wherein the nickel source comprises nickel nitrate and/or nickel chloride.
5. The electrode active material for a supercapacitor according to claim 3, wherein the vanadium source comprises ammonium metavanadate.
6. The electrode active material for a supercapacitor according to claim 3, wherein the first solvent comprises any one of water, methanol or ethanol, or a combination of at least two thereof.
7. The electrode active material for a supercapacitor according to claim 3, wherein the sulfur source comprises thioacetamide and/or thiourea.
8. The electrode active material for a supercapacitor according to claim 3, wherein the second solvent comprises methanol and/or ethanol.
9. The method for preparing an electrode active material for a supercapacitor according to any one of claims 1 to 8, comprising the steps of:
(a) mixing a pyridine carboxylic acid ligand, a nickel source, a vanadium source and a first solvent, and crystallizing to obtain a Ni-V-MOF precursor;
(b) and mixing the Ni-V-MOF precursor, a sulfur source and a second solvent, and carrying out solvothermal reaction to obtain the electrode material for the super capacitor.
10. The method according to claim 9, wherein in the step (a), the pyridinecarboxylic acid ligand includes any one of 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, and 2, 6-pyridinedicarboxylic acid, or a combination of at least two thereof.
11. The method according to claim 10, wherein in the step (a), the nickel source comprises nickel nitrate and/or nickel chloride.
12. The method according to claim 10, wherein in step (a), the vanadium source comprises ammonium metavanadate.
13. The method according to claim 10, wherein in the step (a), the first solvent comprises any one of water, methanol or ethanol or a combination of at least two thereof.
14. The preparation method according to claim 10, wherein in the step (a), the molar ratio of the pyridine carboxylic acid ligand to the nickel source to the vanadium source is (1-2): (1-2): (1-2).
15. The preparation method according to claim 14, wherein in the step (a), the molar ratio of the pyridine carboxylic acid ligand to the nickel source to the vanadium source is (1.2-2): (1-1.8): (1-1.8).
16. The preparation method according to claim 14, wherein in the step (a), the molar ratio of the pyridine carboxylic acid ligand to the nickel source to the vanadium source is (1.5-2): (1-1.5): (1-1.5).
17. The method according to any one of claims 9 to 16, wherein in step (b), the sulfur source comprises thioacetamide and/or thiourea.
18. The method according to claim 17, wherein in the step (b), the second solvent comprises methanol and/or ethanol.
19. The method of claim 17, wherein in step (b), the mass ratio of the Ni-V-MOF precursor, the sulfur source, and the second solvent is (1-3): (5-50).
20. The method of claim 19, wherein in step (b), the mass ratio of the Ni-V-MOF precursor, the sulfur source, and the second solvent is (1-2): (10-45).
21. A method of preparing according to claim 19, wherein in step (b), the mass ratio of the Ni-V-MOF precursor, the sulphur source and the second solvent is 1.5:1.5: 40.
22. The method as claimed in claim 17, wherein the temperature of the solvothermal reaction in step (b) is 110-160 ℃ and the reaction time is 4-6 h.
23. The method according to claim 17, wherein the solvent is removed from the reaction solution obtained by the solvothermal reaction in the step (b), and the reaction solution is washed and dried to obtain the electrode active material for the supercapacitor.
24. An electrode material for a supercapacitor, comprising the electrode active material for a supercapacitor according to any one of claims 1 to 8 or the electrode active material for a supercapacitor produced by the method for producing the electrode active material for a supercapacitor according to any one of claims 9 to 23.
25. The electrode material for the supercapacitor according to claim 24, comprising the following components in parts by mass:
60-90% of electrode active material, 5-30% of conductive agent and 5-10% of binder.
26. An ultracapacitor comprising the electrode material for an ultracapacitor of claim 24.
27. An electrically powered device comprising the ultracapacitor of claim 26.
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| CN108231430A (en) * | 2018-01-17 | 2018-06-29 | 闽南师范大学 | A kind of vanadate hybrid inorganic-organic materials nanoparticle and preparation method thereof |
| CN110364372A (en) * | 2019-08-02 | 2019-10-22 | 浙江工业大学 | A kind of supercapacitor vanadic acid nickel material, preparation method and application |
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| CN108231430A (en) * | 2018-01-17 | 2018-06-29 | 闽南师范大学 | A kind of vanadate hybrid inorganic-organic materials nanoparticle and preparation method thereof |
| CN110364372A (en) * | 2019-08-02 | 2019-10-22 | 浙江工业大学 | A kind of supercapacitor vanadic acid nickel material, preparation method and application |
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