CN108899534A - A kind of preparation method of lithium ion battery capacitor positive electrode vanadium oxide - Google Patents
A kind of preparation method of lithium ion battery capacitor positive electrode vanadium oxide Download PDFInfo
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- CN108899534A CN108899534A CN201810628936.7A CN201810628936A CN108899534A CN 108899534 A CN108899534 A CN 108899534A CN 201810628936 A CN201810628936 A CN 201810628936A CN 108899534 A CN108899534 A CN 108899534A
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- vanadium oxide
- lithium ion
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- ion battery
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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
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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
- 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
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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
- Y02E60/10—Energy storage using batteries
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of preparation methods of lithium ion battery capacitor positive electrode vanadium oxide, belong to lithium-ion energy storage technical field, this method is using commercial oxidation vanadium as presoma, using between the strong hydrogen bond action insertion vanadium oxide layer of amine and oxygen, then obtained at high temperature using production breakdown amine extruding oxidation of precursor vanadium is rapidly heated.Low in cost it is an advantage of the invention that preparation process is simple, the material yield of preparation is high, applied to showing good chemical property in lithium ion battery capacitor positive electrode.This method is with a wide range of applications.
Description
Technical field
The invention belongs to lithium-ion energy storage field of material technology, in particular to a kind of lithium ion battery capacitor positive electrode oxygen
Change the preparation method of vanadium.
Background technique
Vanadium oxide is a kind of semiconductor oxide materials, is widely used in industries such as chemical metallurgy energy catalysis.Oxygen
Changing vanadium has the characteristics that cheap rich reserves, while specific capacity with higher.The layer structure and V of vanadium oxide5+To V3+
Transformation so that vanadium oxide is expected to as a kind of ideal anode material for lithium-ion batteries.When vanadium oxide is used as lithium ion battery
When positive, main energy storage mechanism is that the intercalation of lithium ion is embedded in, and when being embedded in two lithium ions, corresponding theoretical capacity is high
Up to 294mAh g-1, it is contemplated that presently the most common cobalt acid lithium and LiFePO4 only 140mAh g-1Capacity, vanadium oxide material tool
There is very big advantage.But the lithium ion due to being partially submerged into charge and discharge process can not deviate to result in irreversible reaction hair
It is raw, thus material property is unstable, performance can be decayed.Simultaneously because vanadium oxide is a kind of semiconductor, the conductivity of itself
It is lower about to only have 0.01-0.001S cm-1, and because of the circulation of lithium ion is limited in diffusion wherein vanadium oxide
Performance is often bad.
It needs to be concerned with, common anode material for lithium-ion batteries is embedding with the slow dynamics of deintercalation since lithium ion enters
Process, thus power density is poor.And as another widely used electrochemical energy storing device, capacitor possesses higher function
Rate density, but energy density is poor.It is to obtain to be provided simultaneously with high-energy and high power by the capacitorization processing to battery material
One of effective way of density.Research finds that apparent capacitor can be shown after cell type material nano or interlamellar spacing increase
Change behavior, numerous research focus on growing method from bottom to top, and being obtained by control growth course has nanoscale
Material, often the yield of material is not high, and scale is relatively difficult to achieve.It thus probes into a kind of top-down treatment process and advises to realizing
The preparation of modelling material will be of great advantage.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of lithium ion battery capacitor anodes
The preparation method of material oxidation vanadium, using the distinctive layer structure of vanadium oxide, intercalation is inserted into effumability presoma, then after passing through
Continuous step is prepared using the method that heated fast completes removing, simple process, quickly, low in cost, is very suitable for
Large-scale production.
To achieve the goals above, the technical solution adopted by the present invention is that：
A kind of preparation method of lithium ion battery capacitor positive electrode vanadium oxide utilizes amine material pair in liquid-phase system
Raw material vanadium oxide carry out intercalation processing after, then quick high-temp thermal expansion processing so that amine material sharply decompose to get.Institute
It obtains vanadium oxide material and shows capacitive electrochemical properties, electrochemistry capacitance >=200mAh g-1。
The raw material vanadium oxide is commercial oxidation vanadium, cheap without any specificity, is easy to obtain.
The liquid-phase system is water or liquid alcohol or liquid alkane.
The amine material is the organic substance containing amino, and the mass ratio of vanadium oxide is (0-2)：1.
The intercalation processing technique is direct paddling process ultrasonic method or hydro-thermal method, and the reaction time is 0.5-100 hours.
The temperature of the quick high-temp thermal expansion processing is at 400-1000 DEG C, and the time is between 1-100 seconds, and processing atmosphere is
Air or argon gas.
Preparation process of the present invention mainly includes stirring intercalation and rapid thermal expansion technical process, and technique is quick and easy,
Good electro-chemical activity can be shown in half-cell application with prepare with scale vanadium oxide lithium ion anode material.This
Kind method is expected to play a role to the other function application of vanadium oxide.
Compared with prior art, the beneficial effects of the invention are as follows：
This method can with scale realize the intercalation effect of vanadium oxide, and the technique of high temperature rapid expanding highly shortened
The preparation time of material and the preparation difficulty for reducing fake capacitance system material.Material obtained is in compared to native oxide vanadium
Reveal apparent capacitance behavior.
Detailed description of the invention
Fig. 1 is intercalation thermal expansion vanadium oxide lithium ion cell positive first circle charging and discharging curve figure.
Fig. 2 is that vanadium oxide is obtained in commercial oxidation vanadium and embodiment 3 in 100mA g-1Current density under chemical property
Schematic diagram.
Fig. 3 is that vanadium oxide is obtained in commercial oxidation vanadium and embodiment 3 in 1000mA g-1Current density under chemical property
Schematic diagram.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1：
It disperses 5g commercial oxidation vanadium raw materials in 120mL ethyl alcohol and is dispersed with stirring uniformly.1g intercalator is added thereto again
Melamine, it is stand-by using suspension obtained is filtered drying after ultrasonic agitation technique stirring 12h.
Muffle furnace is warming up to 600 DEG C of high temperature first, crucible is heated to furnace temperature first in air atmosphere, then rapidly
Be added above-mentioned steps in drying sample, be placed in furnace and keep the temperature 40s, take out crucible after it is cooled to room temperature, collect to
Subsequent characteristic test and application.The vanadium oxide positive electrode that rapid expanding is obtained, conductive black and bonding agent PVDF are according to matter
Measure ratio 80：10：10 are uniformly uniformly mixed, and organic solvent NMP is added and obtains anode sizing agent.Anode sizing agent is coated on aluminium foil,
After drying, rolling film and punching processing, lithium ion capacitor anode plate is obtained, lithium ion half-cell is formed with lithium piece, with 1mol/
The LiPF of L concentration6(EC:DEC=1：1) it is organic electrolyte, 2032 type button cells is assembled into, in 100mAg-1Electric current it is close
Spending lower capacity is 209mAh g-1。
Embodiment 2：
It disperses 5g commercial oxidation vanadium raw materials in 120mL ethyl alcohol and is dispersed with stirring uniformly.2g intercalator is added thereto again
Melamine, it is stand-by using suspension obtained is filtered drying after ultrasonic agitation technique stirring 12h.
Muffle furnace is warming up to 800 DEG C of high temperature first, crucible is heated to furnace temperature first in air atmosphere, then rapidly
Be added above-mentioned steps in drying sample, be placed in furnace and keep the temperature 20s, take out crucible after it is cooled to room temperature, collect to
Subsequent characteristic test and application.The vanadium oxide positive electrode that rapid expanding is obtained, conductive black and bonding agent PVDF are according to matter
Measure ratio 80：10：10 are uniformly uniformly mixed, and organic solvent NMP is added and obtains anode sizing agent.Anode sizing agent is coated on aluminium foil,
After drying, rolling film and punching processing, lithium ion capacitor anode plate is obtained, lithium ion half-cell is formed with lithium piece, with 1mol/
The LiPF of L concentration6(EC:DEC=1：1) it is organic electrolyte, 2032 type button cells is assembled into, in 100mAg-1Electric current it is close
Spending lower capacity is 200mAh g-1。
Embodiment 3：
It disperses 2g commercial oxidation vanadium raw materials in 80mL ethyl alcohol and is dispersed with stirring uniformly.1g intercalator three is added thereto again
It is mixed into suspension after poly cyanamid, which is fitted into sealing in the hydrothermal reaction kettle of 100mL and reacts 4 at 180 DEG C
Hour, sediment is separated by filtration after drying for use after reaction kettle is cooling.
Muffle furnace is warming up to 800 DEG C of high temperature first, crucible is heated to furnace temperature first in air atmosphere, then rapidly
Be added above-mentioned steps in drying sample, be placed in furnace and keep the temperature 20s, take out crucible after it is cooled to room temperature, collect to
Subsequent characteristic test and application.The vanadium oxide positive electrode that rapid expanding is obtained, conductive black and bonding agent PVDF are according to matter
Measure ratio 80：10：10 are uniformly uniformly mixed, and organic solvent NMP is added and obtains anode sizing agent.Anode sizing agent is coated on aluminium foil,
After drying, rolling film and punching processing, lithium ion capacitor anode plate is obtained, lithium ion half-cell is formed with lithium piece, with 1mol/
The LiPF of L concentration6(EC:DEC=1：1) it is organic electrolyte, 2032 type button cells is assembled into, in 100mAg-1Electric current it is close
Spending lower capacity is 210mAh g-1。
Embodiment 4：
It disperses 2g commercial oxidation vanadium raw materials in 100mL n-hexane and is dispersed with stirring uniformly.20mL liquid is added thereto again
State intercalator n-octyl amine is mixed into suspension, which is stirred 2 hours or so rear suction filtrations and is dried for use.
Muffle furnace is warming up to 800 DEG C of high temperature first, crucible is heated to furnace temperature first in air atmosphere, then rapidly
Be added above-mentioned steps in drying sample, be placed in furnace and keep the temperature 20s, take out crucible after it is cooled to room temperature, collect to
Subsequent characteristic test and application.The vanadium oxide positive electrode that rapid expanding is obtained, conductive black and bonding agent PVDF are according to matter
Measure ratio 80：10：10 are uniformly uniformly mixed, and organic solvent NMP is added and obtains anode sizing agent.Anode sizing agent is coated on aluminium foil,
After drying, rolling film and punching processing, lithium ion capacitor anode plate is obtained, lithium ion half-cell is formed with lithium piece, with 1mol/
The LiPF of L concentration6(EC:DEC=1：1) it is organic electrolyte, 2032 type button cells is assembled into, in 100mA g-1Electric current it is close
Spending lower capacity is 205mAh g-1。
Embodiment 5：
It disperses 3g commercial oxidation vanadium raw materials in 120mL distilled water and is dispersed with stirring uniformly.1g intercalation is added thereto again
Agent melamine, it is stand-by using suspension obtained is filtered drying after ultrasonic agitation technique stirring 12h.
Muffle furnace is warming up to 600 DEG C of high temperature first, crucible is heated to furnace temperature first in air atmosphere, then rapidly
Be added above-mentioned steps in drying sample, be placed in furnace and keep the temperature 20s, take out crucible after it is cooled to room temperature, collect to
Subsequent characteristic test and application.The vanadium oxide positive electrode that rapid expanding is obtained, conductive black and bonding agent PVDF are according to matter
Measure ratio 80：10：10 are uniformly uniformly mixed, and organic solvent NMP is added and obtains anode sizing agent.Anode sizing agent is coated on aluminium foil,
After drying, rolling film and punching processing, lithium ion capacitor anode plate is obtained, lithium ion half-cell is formed with lithium piece, with 1mol/
The LiPF of L concentration6(EC:DEC=1：1) it is organic electrolyte, is assembled into 2032 type button cells.As shown in Fig. 1, exist
100mA g-1Current density under its first lap capacity be 292mAh g-1, head effect has reached 91.31%, and is demonstrated by bright
Aobvious capacitive properties.It compares as shown in Figures 2 and 3 with commercial oxidation vanadium in 100mAg-1With 1000mA g-1Under current density,
The sample of example 3 shows more excellent performance, in 100mA g-1Under, capacity is 281mAh g-1；In 1000mA
g-1Under, capacity is 182mAh g-1And show capacitance behavior.
Claims (7)
1. a kind of preparation method of lithium ion battery capacitor positive electrode vanadium oxide, which is characterized in that utilized in liquid-phase system
After amine material carries out intercalation processing to raw material vanadium oxide, then quick high-temp thermal expansion processing, so that amine material sharply divides
Solution to get.
2. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that described
Raw material vanadium oxide is commercial oxidation vanadium.
3. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that gained
Vanadium oxide material shows capacitive electrochemical properties, electrochemistry capacitance >=200mAh g-1。
4. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that described
Liquid-phase system is water or liquid alcohol or liquid alkane.
5. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that described
Amine material is the organic substance containing amino, and the mass ratio of vanadium oxide is (0-2)：1.
6. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that described
Intercalation processing technique is direct paddling process ultrasonic method or hydro-thermal method, and the reaction time is 0.5-100 hours.
7. the preparation method of lithium ion battery capacitor positive electrode vanadium oxide according to claim 1, which is characterized in that described
The temperature of quick high-temp thermal expansion processing is at 400-1000 DEG C, and the time is between 1-100 seconds, and processing atmosphere is air or argon gas.
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| CN101773859A (en) * | 2010-01-12 | 2010-07-14 | 华东师范大学 | Preparation method of ionic liquid intercalation vanadic oxide |
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