CN108899534B - Preparation method of vanadium oxide as positive electrode material of lithium ion battery capacitor - Google Patents

Preparation method of vanadium oxide as positive electrode material of lithium ion battery capacitor Download PDF

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CN108899534B
CN108899534B CN201810628936.7A CN201810628936A CN108899534B CN 108899534 B CN108899534 B CN 108899534B CN 201810628936 A CN201810628936 A CN 201810628936A CN 108899534 B CN108899534 B CN 108899534B
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vanadium oxide
lithium ion
positive electrode
ion battery
electrode material
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CN108899534A (en
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黄正宏
胡明祥
吕瑞涛
沈万慈
康飞宇
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H01M16/003—Structural combinations of different types of electrochemical generators of fuel cells with other electrochemical devices, e.g. capacitors, electrolysers
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method of vanadium oxide serving as a positive electrode material of a lithium ion battery capacitor, belonging to the technical field of lithium ion energy storage. The invention has the advantages of simple preparation process, low cost and high yield of the prepared material, and shows good electrochemical performance when being applied to the anode material of the lithium ion battery capacitor. The method has wide application prospect.

Description

Preparation method of vanadium oxide as positive electrode material of lithium ion battery capacitor
Technical Field
The invention belongs to the technical field of lithium ion energy storage materials, and particularly relates to a preparation method of a lithium ion battery capacitor positive electrode material vanadium oxide.
Background
Vanadium oxide is a semiconductor oxide material and is widely used in industries such as metallurgy, chemical engineering, energy catalysis and the like. The vanadium oxide has the characteristics of low price and rich reserves, and simultaneously has higher specific capacity. Layered structure of vanadium oxide and V5+To V3+The transformation of (2) makes vanadium oxide hopeful to be an ideal lithium ion battery cathode material. When vanadium oxide is used as the positive electrode of the lithium ion battery, the main energy storage mechanism is intercalation of lithium ions, and when two lithium ions are intercalated, the corresponding theoretical capacity is up to 294mAh g-1Considering that lithium cobaltate and lithium iron phosphate which are most commonly used at present are only 140mAh g-1The vanadium oxide material has great advantages in capacity. However, since some of the intercalated lithium ions cannot be extracted during the charging and discharging process, an irreversible reaction occurs, and thus the material performance is unstable and may be degraded. Meanwhile, as the vanadium oxide is a semiconductor, the conductivity of the vanadium oxide is lower by about 0.01-0.001S cm-1And the cycle performance of vanadium oxide tends to be poor because of the limited diffusion properties of lithium ions therein.
It is noted that the conventional lithium ion battery cathode material has a poor power density due to the slow kinetic process of lithium ion intercalation and deintercalation. As another widely used electrochemical energy storage device, a capacitor has a high power density but a poor energy density. The capacitive treatment of the battery material is one of the effective ways to obtain high energy and high power density simultaneously. Researches find that the battery type material shows obvious capacitive behavior after being subjected to nanocrystallization or interlayer spacing increase, a great deal of researches focus on a bottom-up growth method, and the material with the nanoscale is obtained by controlling the growth process, so that the yield of the material is not high, and the large scale is difficult to realize. Therefore, it is beneficial to develop a top-down treatment process for large-scale material preparation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of vanadium oxide as a positive electrode material of a lithium ion battery capacitor, which is simple and quick in process, low in cost and very suitable for large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of vanadium oxide serving as a positive electrode material of a lithium ion battery capacitor comprises the steps of carrying out intercalation treatment on vanadium oxide serving as a raw material by using an amine material in a liquid phase system, and then carrying out rapid high-temperature thermal expansion treatment to rapidly decompose the amine material to obtain the vanadium oxide. The obtained vanadium oxide material has capacitive electrochemical characteristics, and the electrochemical capacity is more than or equal to 200mAh g-1。
The raw material vanadium oxide is commercial vanadium oxide, has no specificity, is low in price and is easy to obtain.
The liquid phase system is water or liquid alcohol or liquid alkane.
The amine material is an organic substance containing amino, and the mass ratio of the amine material to vanadium oxide is (0-2): 1.
the intercalation treatment process is a direct stirring ultrasonic method or a hydrothermal method, and the reaction time is 0.5-100 hours.
The temperature of the rapid high-temperature thermal expansion treatment is 400-1000 ℃, the time is 1-100 seconds, and the treatment atmosphere is air or argon.
The preparation process mainly comprises the technical processes of stirring intercalation and rapid thermal expansion, is rapid and simple, can be used for preparing the vanadium oxide lithium ion anode material in a large scale, and shows good electrochemical activity in the application of a half-cell. The method is expected to play a role in other functional applications of vanadium oxide.
Compared with the prior art, the invention has the beneficial effects that:
the method can realize the intercalation effect of vanadium oxide in a large scale, and the high-temperature rapid expansion process greatly shortens the preparation time of the material and reduces the preparation difficulty of the pseudocapacitance system material. The obtained material exhibits a significant capacitive behavior compared to the original vanadium oxide.
Drawings
FIG. 1 is a first-loop charge-discharge curve diagram of the positive electrode of the intercalation thermal expansion vanadium oxide lithium ion battery.
FIG. 2 is a graph of commercial vanadium oxide and vanadium oxide obtained in example 3 at 100mA g-1Current density of (a).
FIG. 3 is a graph of commercial vanadium oxide and vanadium oxide obtained in example 3 at 1000mA g-1Current density of (a).
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Example 1:
5g of commercial vanadium oxide raw material is dispersed in 120mL of ethanol and uniformly stirred. And adding 1g of intercalation agent melamine into the solution, stirring the solution for 12 hours by adopting an ultrasonic stirring process, and then filtering, filtering and drying the obtained suspension for later use.
Firstly, heating a muffle furnace to 600 ℃ at high temperature, firstly heating a crucible to the furnace temperature in the air atmosphere, then quickly adding the dried sample in the step, placing the sample in the furnace for heat preservation for 40s, taking out the crucible, cooling the crucible to room temperature, and collecting the sample to be subjected to subsequent characterization test and application. Vanadium oxide obtained by rapid expansionThe anode material, the conductive carbon black and the adhesive PVDF are mixed according to the mass ratio of 80: 10: 10, uniformly mixing, and adding an organic solvent NMP to obtain the anode slurry. Coating the anode slurry on an aluminum foil, drying, rolling a film and punching to obtain a lithium ion capacitor anode plate, forming a lithium ion half-cell with the lithium plate, and using LiPF with the concentration of 1mol/L6(EC: DEC ═ 1: 1) as organic electrolyte, assembling to 2032 type button cell, at 100mAg-1Has a capacity of 209mAh g at a current density of-1。
Example 2:
5g of commercial vanadium oxide raw material is dispersed in 120mL of ethanol and uniformly stirred. And then 2g of intercalation agent melamine is added into the solution, and the solution is stirred for 12 hours by adopting an ultrasonic stirring process, and then the obtained suspension is filtered, filtered and dried for later use.
Firstly, heating a muffle furnace to 800 ℃, heating a crucible to the furnace temperature in the air atmosphere, then quickly adding the dried sample in the step, placing the sample in the furnace for heat preservation for 20s, taking out the crucible, cooling the crucible to room temperature, and collecting the sample to be subjected to subsequent characterization test and application. And (2) mixing the vanadium oxide positive electrode material obtained by rapid expansion, conductive carbon black and PVDF as a binder according to a mass ratio of 80: 10: 10, uniformly mixing, and adding an organic solvent NMP to obtain the anode slurry. Coating the anode slurry on an aluminum foil, drying, rolling a film and punching to obtain a lithium ion capacitor anode plate, forming a lithium ion half-cell with the lithium plate, and using LiPF with the concentration of 1mol/L6(EC: DEC ═ 1: 1) as organic electrolyte, assembling to 2032 type button cell, at 100mAg-1Has a capacity of 200mAh g at a current density of-1。
Example 3:
2g of commercial vanadium oxide raw material is dispersed in 80mL of ethanol and uniformly stirred. Adding 1g of intercalation agent melamine into the mixture, uniformly mixing the mixture to form suspension, putting the suspension into a 100mL hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, reacting the mixture for 4 hours at 180 ℃, and filtering, separating and drying the precipitate after the reaction kettle is cooled for later use.
Firstly, heating a muffle furnace to 800 ℃, heating a crucible to the furnace temperature in the air atmosphere, and then quickly adding the crucible into the baking in the stepAnd (4) placing the dried sample in a furnace, preserving the heat for 20s, taking out the crucible, cooling the crucible to room temperature, and collecting the sample for subsequent characterization test and application. And (2) mixing the vanadium oxide positive electrode material obtained by rapid expansion, conductive carbon black and PVDF as a binder according to a mass ratio of 80: 10: 10, uniformly mixing, and adding an organic solvent NMP to obtain the anode slurry. Coating the anode slurry on an aluminum foil, drying, rolling a film and punching to obtain a lithium ion capacitor anode plate, forming a lithium ion half-cell with the lithium plate, and using LiPF with the concentration of 1mol/L6(EC: DEC ═ 1: 1) as organic electrolyte, assembling to 2032 type button cell, at 100mAg-1Has a capacity of 210mAh g at a current density of-1。
Example 4:
2g of commercial vanadium oxide raw material is dispersed in 100mL of n-hexane and uniformly stirred and dispersed. Then 20mL of liquid intercalation agent n-octylamine is added into the mixture to be mixed evenly into suspension, and the suspension is stirred for about 2 hours and then is filtered and dried for standby.
Firstly, heating a muffle furnace to 800 ℃, heating a crucible to the furnace temperature in the air atmosphere, then quickly adding the dried sample in the step, placing the sample in the furnace for heat preservation for 20s, taking out the crucible, cooling the crucible to room temperature, and collecting the sample to be subjected to subsequent characterization test and application. And (2) mixing the vanadium oxide positive electrode material obtained by rapid expansion, conductive carbon black and PVDF as a binder according to a mass ratio of 80: 10: 10, uniformly mixing, and adding an organic solvent NMP to obtain the anode slurry. Coating the anode slurry on an aluminum foil, drying, rolling a film and punching to obtain a lithium ion capacitor anode plate, forming a lithium ion half-cell with the lithium plate, and using LiPF with the concentration of 1mol/L6(EC: DEC ═ 1: 1) as an organic electrolyte, and assembled into a 2032 type button cell at 100mA g-1Has a capacity of 205mAh g at a current density of-1。
Example 5:
3g of commercial vanadium oxide starting material was dispersed in 120mL of distilled water and uniformly dispersed with stirring. And adding 1g of intercalation agent melamine into the solution, stirring the solution for 12 hours by adopting an ultrasonic stirring process, and then filtering, filtering and drying the obtained suspension for later use.
Firstly, the muffle furnace is heated to 600 ℃ and is in the air atmosphereFirstly, heating a crucible to a furnace temperature, then quickly adding the dried sample in the step, placing the crucible in the furnace for heat preservation for 20s, taking out the crucible, cooling the crucible to the room temperature, and collecting the crucible for subsequent characterization test and application. And (2) mixing the vanadium oxide positive electrode material obtained by rapid expansion, conductive carbon black and PVDF as a binder according to a mass ratio of 80: 10: 10, uniformly mixing, and adding an organic solvent NMP to obtain the anode slurry. Coating the anode slurry on an aluminum foil, drying, rolling a film and punching to obtain a lithium ion capacitor anode plate, forming a lithium ion half-cell with the lithium plate, and using LiPF with the concentration of 1mol/L6And (EC: DEC ═ 1: 1) is an organic electrolyte, and the 2032 type button cell is assembled. As shown in FIG. 1, at 100mA g-1Has a capacity of 292mAh g in the first turn at a current density of-1The first effect reaches 91.31%, and the obvious capacitance property is shown. As shown in fig. 2 and 3, at 100mAg compared to commercial vanadium oxide-1And 1000mA g-1The samples of example 3 all showed much superior performance at 100mA g at current density-1The capacity is 281mAh g-1(ii) a At 1000mA g-1The capacity is 182mAh g-1And exhibits capacitive behavior.

Claims (4)

1. A preparation method of vanadium oxide serving as a lithium ion battery capacitor positive electrode material is characterized in that a volatile precursor is inserted into a vanadium oxide raw material by utilizing an amine material in a liquid phase system, and then the vanadium oxide raw material is subjected to intercalation treatment, and is subjected to rapid high-temperature thermal expansion treatment, wherein the rapid high-temperature thermal expansion treatment temperature is 400-plus-one temperature and is 1-100 seconds, the treatment atmosphere is air or argon, the liquid phase system is water or liquid alcohol or liquid alkane, the intercalation treatment process is a direct stirring method ultrasonic method or a hydrothermal method, and the reaction time is 0.5-100 hours.
2. The method for preparing vanadium oxide as the positive electrode material of lithium ion battery capacitor as claimed in claim 1, wherein the raw material vanadium oxide is commercial vanadium oxide.
3. The preparation method of the vanadium oxide as the positive electrode material for the lithium ion battery capacitor as claimed in claim 1, wherein the vanadium oxide material has capacitive electrochemical characteristics, and has an electrochemical capacity of 200mAh g or more-1。
4. The preparation method of vanadium oxide serving as the positive electrode material of the lithium ion battery capacitor according to claim 1, wherein the amine material is an amino-containing organic substance, and the mass ratio of the amino-containing organic substance to the vanadium oxide is (0-2): 1.
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CN103022457A (en) * 2012-12-19 2013-04-03 同济大学 High-performance nano granular vanadium pentoxide lithium ion battery cathode material and preparation method thereof
CN103723712A (en) * 2013-11-22 2014-04-16 盐城纳新天地新材料科技有限公司 Preparation method of single-layer graphene dimethylformamide solution
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