CN110556537A - Method for improving electrochemical performance of anion-embedded electrode material - Google Patents
Method for improving electrochemical performance of anion-embedded electrode material Download PDFInfo
- Publication number
- CN110556537A CN110556537A CN201910803310.XA CN201910803310A CN110556537A CN 110556537 A CN110556537 A CN 110556537A CN 201910803310 A CN201910803310 A CN 201910803310A CN 110556537 A CN110556537 A CN 110556537A
- Authority
- CN
- China
- Prior art keywords
- anion
- ion battery
- additive
- electrode
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of batteries, and discloses a method for improving the electrochemical performance of an anion-embedded electrode material, which specifically comprises the steps of adding a specific additive into the anion-embedded electrode material; the specific class of additives are covalent organic framework compounds with a cationic center. Compared with the prior art, the method does not follow the traditional strategies of changing the material, improving the conductivity of the material and improving conductive additives, but adjusts the transmission of anions and improves the ionic conductivity of the anions based on the charge coulomb attraction effect by adding a covalent organic framework compound with a cation center as a specific kind of additive, thereby greatly improving the electrochemical performance of the anion-embedded electrode material. The method can be used for improving the performance of lithium ion batteries, sodium ion batteries, potassium ion batteries, aluminum ion batteries, magnesium ion batteries, zinc ion batteries and dual-ion batteries based on anion-embedded type.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a method for improving the electrochemical performance of an anion-embedded electrode material.
background
With the rapid development of portable electronic devices and the popularization of electric vehicles, people's demand for energy storage is increasing day by day. At present, lithium ion batteries are rapidly developed as main energy storage devices. Most of commercial lithium ion batteries use inorganic materials containing transition metal oxides as lithium storage anodes, and the preparation, synthesis and recovery processes are complex; the materials usually need pre-lithiation treatment in the preparation process, such as obtaining lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, binary or ternary positive electrodes and the like, the pre-lithiation materials are subjected to delithiation in the charging process, and then lithium is inserted again in the discharging process to realize reversible cycle; in addition, inorganic cathode materials containing transition metals have the problems of difficult degradation, strong environmental toxicity, difficult recovery, limited resources and the like, which undoubtedly sets obstacles for the further development of lithium ion batteries. Meanwhile, with the continuous deepening of ecological environment construction in China, the environmental protection strength is greater and greater, the requirements are further improved, and the challenge is provided for the green preparation of the lithium ion battery electrode material. Therefore, the research and development of a new generation of energy storage material which is environment-friendly and sustainable has important practical significance.
In recent years, anion-intercalation type electrode materials have attracted much attention because of their advantages such as high redox electrode potential and no need for prelithiation. The energy storage mechanism of the anion-doped electrode material is based on reversible intercalation/deintercalation of electrolyte anions in the anode material, and the electrode material has higher redox potential and can provide a high discharge voltage platform. In addition, when the anion doped electrode material is charged and discharged, the anion of the electrolyte is utilized, so that the material does not need to be pre-lithiated, and the material is a new generation of sustainable energy storage material with great potential, and is particularly favorable for a dual-ion battery (namely, a positive electrode adopts a negative ion intercalation mechanism, and a negative electrode adopts a positive ion intercalation mechanism, so that the high energy density is favorably realized). However, the anion-embedded electrode material still has the practical problems of unsatisfactory cycle stability, low actual specific capacity, poor rate capability and the like, so that the development is slow. Currently, the ideas and measures for solving these problems mainly focus on changing the material itself, increasing the conductivity of the material, and improving the types, contents, etc. of conductive additives, for example, a porous or interlamellar carbon material is used as an electrode, the electrode material is compounded or coated with various types of conductive carbon materials in a certain ratio, etc. This undoubtedly reduces the actual loading of the active material, resulting in a substantial reduction in volumetric energy density, which is not conducive to the portable, miniaturized development of the battery.
Disclosure of Invention
In view of the above drawbacks or needs for improvement of the prior art, an object of the present invention is to provide a method for improving electrochemical properties of an anion-intercalation type electrode material, wherein the electrochemical properties of the anion-intercalation type electrode material can be improved by introducing a covalent organic framework compound having a cation center as a specific kind of additive, adjusting anion transport based on charge coulombic attraction, improving the ionic conductivity of anions, and so forth. Moreover, based on the invention, a small amount of covalent organic framework compound with a cation center can be added into the electrode homogenate in the process of preparing the electrode homogenate (the added specific additive and the battery active material in the electrode homogenate are both electrode materials, and the mass percentage of the additive in the electrode material is preferably 1-50 percent), so that the rate capability of the material can be greatly improved, and the method is simple and practical, and the operation is convenient and easy.
To achieve the above object, according to one aspect of the present invention, there is provided a method for improving electrochemical properties of an anion-intercalation type electrode material, characterized by adding a specific kind of additive to the anion-intercalation type electrode material; wherein the specific kind of additive is in particular a covalent organic framework compound with a cationic centre.
As a further preferred aspect of the present invention, the covalent organic framework compound having a cationic center is prepared by condensation reaction of an aromatic polyaldehyde with an aromatic amine having a cationic center, or an aromatic polyaldehyde having a cationic center with an aromatic amine;
Preferably, the covalent organic framework compound bearing a cationic centre has the chemical formula shown below in formula COF-1 or formula COF-2:
in the formula COF-1 and the formula COF-2, the anion X is preferably ClO 4 - 6 - - 4 - 3 SO 3 - .
According to another aspect of the present invention, there is provided an anion intercalation type-based lithium ion battery, sodium ion battery, potassium ion battery, aluminum ion battery, magnesium ion battery, zinc ion battery or bi-ion battery containing a specific kind of additive, the battery comprising an electrode, an electrolyte, a separator and a current collector, characterized in that the electrode contains a specific kind of additive, in particular a covalent organic framework compound with a cation center.
In a further preferred embodiment of the present invention, the electrode contains a specific type of additive, specifically, the positive electrode of the battery contains the specific type of additive.
as a further preferable aspect of the present invention, the electrolyte is a solution obtained by dissolving an inorganic salt containing the target metal element in an organic solvent, and the concentration thereof is 0.1 to 2.0 mol/L; the solvent adopted by the electrolyte is one or a mixed solution of more than two of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolane, 1, 3-dioxolane and ethylene glycol dimethyl ether in any proportion; preferably, the target metal element is lithium element, and the inorganic salt is one or a mixture of more than two of lithium perchlorate, lithium hexafluorophosphate and lithium bis (trifluoromethanesulfonyl) imide in any proportion;
The diaphragm is polypropylene, polyethylene, polytetrafluoroethylene or glass fiber;
the current collector is aluminum foil, aluminum mesh, copper foil, copper mesh, foam copper, stainless steel foil, stainless steel mesh and foam nickel.
According to still another aspect of the present invention, there is provided a method for producing the above additive-containing anion intercalation type-based lithium ion battery, sodium ion battery, potassium ion battery, aluminum ion battery, magnesium ion battery, zinc ion battery and bi-ion battery, characterized in that the production method comprises a step of adding a specific kind of additive to a homogenate of a battery active material in an electrode production process, and allowing the additive to be used together with the battery active material to form a battery electrode; the specific class of additives is in particular covalent organic framework compounds with a cationic centre.
in a further preferred embodiment of the present invention, the specific additive and the battery active material are both an electrode material, and the mass percentage of the specific additive in the electrode material is 1% to 50%, preferably 10%.
As a further preferable aspect of the present invention, the battery active material is an anion-intercalation type organic electrode material or an anion-intercalation type inorganic electrode material; preferably, the first and second liquid crystal materials are,
the anion-embedded organic electrode material is selected from polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyaniline and derivatives thereof, polyphenyl and derivatives thereof, conjugated condensed rings and polymers thereof, polyphenazine, polyphenthiazine and derivatives thereof, TEMPO and TEMPO radical-based polymers, covalent organic grid materials and metal coordination polymer materials;
The anion-embedded inorganic electrode material is Prussian blue or a carbon material, wherein the carbon material is selected from natural graphite, amorphous graphite, hard carbon, soft carbon, graphene oxide, carbon nanotubes, carbon nanofibers and doped carbon materials.
As a further preferred aspect of the present invention, both the specific additive and the battery active material are electrode materials, the electrode materials are further mixed and dispersed in a solvent together with a conductive additive and a binder, and the mass ratio of the electrode materials to the conductive additive and the binder satisfies (30-90): (5-60): (1-15); wherein the content of the first and second substances,
The conductive additive is one or a mixture of more than two of acetylene black, Super-P, graphene and graphite in any proportion; the adhesive is PVDF or PTFE, sodium carboxymethyl cellulose and carboxylic styrene-butadiene latex; the solvent is one or a mixture of more than two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide in any proportion.
Compared with the prior art, the technical scheme of the invention does not use the traditional strategies of changing the material, improving the material conductivity and improving the conductive additive and the content thereof, but uses the improvement of the ionic conductivity as a breakthrough, and regulates the transmission of anions with larger volume in the anode material by introducing the additive of a specific type based on the coulomb attraction effect of opposite charge attraction, thereby achieving the purpose of improving the electrochemical performance of the anion-embedded electrode material. The invention is suitable for all anion-embedded organic electrode materials or anion-embedded inorganic electrode materials, correspondingly provides a method for improving the performance of the battery based on the anion-embedded electrode materials, and provides a new way for obtaining high-performance anion-embedded lithium ion batteries, sodium ion batteries, potassium ion batteries, aluminum ion batteries, magnesium ion batteries, zinc ion batteries or double-ion batteries.
A particular class of additives employed in the present invention are covalent organic framework compounds with a cationic center. Preferably, the aromatic polyaldehyde is prepared by condensation reaction of aromatic polyaldehyde and aromatic amine with a cation center or aromatic polyaldehyde with a cation center and aromatic amine; taking 6 units as an example, the covalent organic framework compound with a cationic center has a chemical structure represented by formula COF-1 or formula COF-2 (of course, the actual number of units may be other integers greater than or equal to 3, and the corresponding structural formula is a modified structure of formula COF-1 or formula COF-2):
the research on the electrochemical performance and the performance improvement method of the anion-embedded material is relatively less, and an effective means is not available at present. The conventional lithium ion battery performance improvement methods are mostly used, for example, the conductivity of the material is increased, the material is subjected to nanocrystallization, the specific surface area of the electrode material is increased, and the porosity and content of the conductive additive are improved. The invention adjusts the transmission of anions based on the opposite charge attraction effect by adding a small amount of specific additives based on the charge coulomb attraction effect for the first time, improves the ionic conductivity of the anions and improves the electrochemical performance of the material. The covalent organic framework compound with the cation center, as a specific kind of additive, can improve the conductivity of anion ions through the attraction of heterogeneous charge coulombs, thereby improving the performance of the battery, especially the rate performance of the battery. In the invention, aiming at an anion-embedded electrode material, in the preparation process of an electrode, a small amount of covalent organic framework compound with a cation center is added (if the added additive and a battery active material in electrode homogenate are jointly used as the electrode material, the mass percentage of the additive in the electrode material is preferably 1-50%, more preferably 10%), and the ionic conductivity is improved, so that the battery performance, especially the rate capability is improved.
Taking a lithium ion battery as an example, the preparation method of the battery containing the additive can be specifically as follows: taking an organic anion-embedded positive electrode material as an example, a covalent organic framework compound (i.e., an additive) with a cation center, the positive electrode material, a conductive additive and a binder are uniformly dispersed in a solvent, coated on a current collector, and then vacuum-dried to form an electrode film. And then, the prepared electrode film is used as a positive electrode, the metal lithium or lithium alloy is used as a negative electrode, the positive electrode and the negative electrode are separated by a diaphragm, electrolyte is injected, and the lithium ion secondary battery can be assembled in a dry argon environment. Other types of batteries, such as sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, zinc ion batteries, and bi-ion batteries, are manufactured in a similar manner to lithium ion batteries by merely changing the positive and negative electrode active materials, the conductive additive, the adhesive, and the electrolyte (e.g., by changing the electrolyte to a corresponding metal salt).
In general, the present invention can achieve the following advantageous effects.
1. The principle of the invention lies in improving the transmission of anions in the anode material system, and the invention is essentially different from the prior technical scheme;
2. the method provided by the invention can greatly improve the rate capability and the cycling stability of the battery, and has remarkable effect;
3. the additive used in the invention has the advantages of small usage amount, simple and easy operation, no volume change of the electrode and no influence on the electrochemical properties of the material;
4. The additive used in the invention is an organic material without transition metal, the synthetic raw materials are low in price and wide in source, and the preparation process is green and environment-friendly.
in conclusion, the method provided by the invention is green, efficient, simple and feasible, and can be applied to lithium ion batteries, sodium ion batteries, potassium ion batteries, aluminum ion batteries, magnesium ion batteries, zinc ion batteries and dual-ion batteries based on anion intercalation.
Drawings
Fig. 1 is a graph of the discharge curve and coulombic efficiency of an assembled battery without a specific type of additive.
Fig. 2 is a graph of the discharge curve and coulombic efficiency of the assembled battery of example 1 containing the specific type of additive.
FIG. 3 is a graph comparing the cycle stability of example 1 with and without the specific type of additive at a current density of 100 mA/g.
FIG. 4 is a graph comparing the cycle stability of example 1 with and without the specific type of additive at a current density of 1000 mA/g.
FIG. 5 is a graph of the cycling stability of example 2 containing 1% of a particular type of additive at a current density of 100 mA/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
example 1
On the basis of an organic cathode material with perchlorate anions reversibly inserted/removed, the electrochemical performance of the organic cathode material is improved by adopting the method disclosed by the invention, and a covalent organic framework compound containing the perchlorate anions needs to be prepared. The specific process is as follows:
Preparation of the additive:
42mg of 1,3, 5-trimethylacylphloroglucinol and 118mg of ethidium bromide were put into a 15mL quartz tube, and 2mL of a mixed solution of dioxane and mesitylene (volume ratio: 1) and 0.2mL of a 6.0mol/L acetic acid solution were added thereto. The quartz tube was cooled with liquid nitrogen, evacuated, degassed, and sealed after repeating three times, and reacted in an oven at 120 ℃ for three days. After the reaction is finished, taking out the quartz tube, cooling to room temperature, breaking the seal to obtain a dark red precipitate, performing suction filtration, and washing a filter cake with tetrahydrofuran for three times. Purifying the obtained powder with a Soxhlet extraction device, sequentially extracting with tetrahydrofuran, methanol and acetone for 12 hours, and finally vacuum drying at 100 ℃ for 12 hours to obtain the bromine-containing covalent organic framework compound. Dispersing the powder in 1.0-6.0 mol/L lithium perchlorate acetonitrile solution, and stirring. During the period, the lithium perchlorate acetonitrile solution is replaced every 24 hours, and the operation is repeated for five times. After the exchange is finished, centrifuging, washing with acetonitrile and acetone for several times in sequence, and drying in vacuum at 120 ℃ for 12 hours to obtain the covalent organic framework compound containing perchlorate anions.
The battery is equipped with:
30mg of anion-embedded organic electrode material polypyrene thioether, 1.5mg of specific additive 1, 25mg of Super-P conductive additive and 6mg of polyvinylidene fluoride are fully and uniformly mixed, 0.5mL of N-methylpyrrolidone is added, the mixture is fully and uniformly ground again to prepare homogenate, the homogenate is uniformly coated on an aluminum foil, and then the homogenate is dried in vacuum at 80 ℃ for 24 hours to prepare an electrode film. In a glove box filled with dry argon, the prepared electrode film is used as a positive electrode, glass fiber is used as a diaphragm, 1.0mol/L of lithium perchlorate and propylene carbonate solution are used as electrolyte, and metal lithium is used as a negative electrode to assemble the button cell. The assembled battery is subjected to constant current charging and discharging under the current densities of 100mA/g and 1000mA/g respectively, the voltage range is 2.0-4.3V, and the discharging curve and the coulombic efficiency are shown in figures 1-4. As shown in FIG. 1, the discharge capacity stabilized at a current density of 100mA/g without the specific additive 1 was 105mAh/g, the average discharge voltage was 3.0V, and the coulombic efficiency was 97%; as shown in FIG. 2, when the specific additive 1 was added, the discharge capacity was 145mAh/g, the average discharge voltage was 3.0V, and the coulombic efficiency was 98%, which was stable at a current density of 100 mA/g. In addition, as can also be seen from fig. 3 and 4, after the specific kind of additive is added, the specific discharge capacity of the battery is obviously improved, and the activation process is obviously shortened, which indicates that the introduction of a small amount of the specific kind of additive can effectively improve the electrochemical performance of the anion-intercalation type electrode material.
Example 2
when a small amount of a specific kind of additive, for example, the proportion of the additive is 1%, is added, the battery performance is also improved. At this time, the battery assembly method was similar to that of example 1. As shown in fig. 5, the performance of the battery can be improved even when the ratio of the specific type of additive is 1.0%. The discharge capacity of 94mAh/g was stabilized at a current density of 100mA/g, and the average discharge voltage and the coulombic efficiency were the same as those in example 1. In the aspect of cycling stability, after 200 cycles, the specific capacity of the battery is attenuated to 60 mAh/g.
In addition, the proportion of the specific additives is gradually increased, and when the proportion reaches 10%, a better effect can be obtained; and when the dosage of the specific additive is further increased, the effect is basically maintained. Considering that too much additive affects energy density of the battery and cost factors, a small amount of a specific kind of additive should be used as much as possible on the premise of satisfying good effects.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A method for improving the electrochemical performance of an anion-intercalation type electrode material is characterized in that a specific kind of additive is added into the anion-intercalation type electrode material; wherein the specific kind of additive is in particular a covalent organic framework compound with a cationic centre.
2. The method for improving electrochemical properties of an anion-intercalation type electrode material according to claim 1, wherein the covalent organic framework compound having a cationic center is preferably prepared by condensation reaction of an aromatic polyaldehyde with an aromatic amine having a cationic center, or an aromatic polyaldehyde with a cationic center with an aromatic amine;
More preferably, the covalent organic framework compound bearing a cationic centre has the chemical formula shown below in formula COF-1 or formula COF-2:
in the formula COF-1 and the formula COF-2, the anion X is preferably ClO 4 - 6 - - 4 - 3 SO 3 - .
3. An anion intercalation-based lithium ion, sodium, potassium, aluminum, magnesium, zinc or bi-ion battery containing a specific kind of additive, the battery comprising an electrode, an electrolyte, a separator and a current collector, characterized in that the electrode contains a specific kind of additive, in particular a covalent organic framework compound with a cationic centre.
4. The anion-intercalation-based lithium ion battery, sodium ion battery, potassium ion battery, aluminum ion battery, magnesium ion battery, zinc ion battery, or bi-ion battery according to claim 3, wherein the specific type of additive contained in the electrode is specifically contained in the positive electrode of the battery.
5. the anion intercalation type-based lithium ion battery, sodium ion battery, potassium ion battery, aluminum ion battery, magnesium ion battery, zinc ion battery or bi-ion battery according to claim 3, wherein the electrolyte is a solution obtained by dissolving an inorganic salt containing the target metal element in an organic solvent at a concentration of 0.1 to 2.0 mol/L; the solvent adopted by the electrolyte is one or a mixed solution of more than two of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolane, 1, 3-dioxolane and ethylene glycol dimethyl ether in any proportion; preferably, the target metal element is lithium element, and the inorganic salt is one or a mixture of more than two of lithium perchlorate, lithium hexafluorophosphate and lithium bis (trifluoromethanesulfonyl) imide in any proportion;
The diaphragm is polypropylene, polyethylene, polytetrafluoroethylene or glass fiber;
The current collector is aluminum foil, aluminum mesh, copper foil, copper mesh, foam copper, stainless steel foil, stainless steel mesh and foam nickel.
6. The method for preparing the anion intercalation type-based lithium ion battery, sodium ion battery, potassium ion battery, aluminum ion battery, magnesium ion battery, zinc ion battery or bi-ion battery according to any one of claims 3 to 5, wherein the preparation method comprises the step of adding a specific kind of additive to a battery active material homogenate in the electrode preparation process, and allowing the additive to be used together with the battery active material to form a battery electrode; the specific class of additives is in particular covalent organic framework compounds with a cationic centre.
7. The preparation method according to claim 6, wherein the specific kind of additive and the battery active material are both an electrode material in which the mass percentage of the specific kind of additive is 1% to 50%, preferably 10%.
8. The production method according to claim 6, wherein the battery active material is an anion-intercalation type organic electrode material or an anion-intercalation type inorganic electrode material; preferably, the first and second liquid crystal materials are,
The anion-embedded organic electrode material is selected from polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyaniline and derivatives thereof, polyphenyl and derivatives thereof, conjugated condensed rings and polymers thereof, polyphenazine, polyphenthiazine and derivatives thereof, TEMPO and TEMPO radical-based polymers, covalent organic grid materials and metal coordination polymer materials;
the anion-embedded inorganic electrode material is Prussian blue or a carbon material, wherein the carbon material is selected from natural graphite, amorphous graphite, hard carbon, soft carbon, graphene oxide, carbon nanotubes, carbon nanofibers and doped carbon materials.
9. The preparation method according to claim 6, wherein the specific additive and the battery active material are both electrode materials, the electrode materials are further mixed and dispersed in a solvent together with a conductive additive and a binder, and the mass ratio of the electrode materials to the conductive additive and the binder satisfies (30-90): (5-60): (1-15); wherein the content of the first and second substances,
the conductive additive is one or a mixture of more than two of acetylene black, Super-P, graphene and graphite in any proportion; the adhesive is PVDF or PTFE, sodium carboxymethyl cellulose and carboxylic styrene-butadiene latex; the solvent is one or a mixture of more than two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide in any proportion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910803310.XA CN110556537B (en) | 2019-08-28 | 2019-08-28 | Method for improving electrochemical performance of anion-embedded electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910803310.XA CN110556537B (en) | 2019-08-28 | 2019-08-28 | Method for improving electrochemical performance of anion-embedded electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110556537A true CN110556537A (en) | 2019-12-10 |
| CN110556537B CN110556537B (en) | 2021-04-20 |
Family
ID=68736822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910803310.XA Active CN110556537B (en) | 2019-08-28 | 2019-08-28 | Method for improving electrochemical performance of anion-embedded electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110556537B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029579A (en) * | 2019-12-12 | 2020-04-17 | 深圳先进技术研究院 | Calcium ion battery positive electrode material, positive electrode and calcium ion battery |
| CN114242927A (en) * | 2021-12-22 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474693A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Lithium ion battery and preparation method thereof |
| CN104538596A (en) * | 2014-12-22 | 2015-04-22 | 哈尔滨工业大学 | Carbon material/covalent organic two-dimensional gird composite electrode material as well as preparation method and application thereof |
| CN107180968A (en) * | 2017-03-24 | 2017-09-19 | 北京理工大学 | A kind of raising COFs materials as electrode active material performance method |
| WO2018013682A1 (en) * | 2016-07-12 | 2018-01-18 | University Of Central Florida Research Foundation, Inc. | Mechanically shaped 2-dimensional covalent organic frameworks |
| CN108063217A (en) * | 2017-12-26 | 2018-05-22 | 深圳先进技术研究院 | Potassium base Dual-ion cell and preparation method thereof |
| CN108155408A (en) * | 2017-12-26 | 2018-06-12 | 深圳先进技术研究院 | Dual-ion cell and preparation method thereof |
| CN108470940A (en) * | 2018-03-19 | 2018-08-31 | 上海交通大学 | A kind of full stress-strain Magnesium ion battery and preparation method thereof |
| CN109148165A (en) * | 2018-08-01 | 2019-01-04 | 曲阜师范大学 | A kind of preparation and application of covalent organic frame/graphene composite material |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN109755534A (en) * | 2019-01-21 | 2019-05-14 | 中国科学院宁波材料技术与工程研究所 | A kind of electrode material and its preparation and application based on organic covalent frame material |
| CN109904519A (en) * | 2019-01-18 | 2019-06-18 | 北京理工大学 | A kind of all solid state electrolyte material and its preparation method and application |
-
2019
- 2019-08-28 CN CN201910803310.XA patent/CN110556537B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474693A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Lithium ion battery and preparation method thereof |
| CN104538596A (en) * | 2014-12-22 | 2015-04-22 | 哈尔滨工业大学 | Carbon material/covalent organic two-dimensional gird composite electrode material as well as preparation method and application thereof |
| WO2018013682A1 (en) * | 2016-07-12 | 2018-01-18 | University Of Central Florida Research Foundation, Inc. | Mechanically shaped 2-dimensional covalent organic frameworks |
| CN107180968A (en) * | 2017-03-24 | 2017-09-19 | 北京理工大学 | A kind of raising COFs materials as electrode active material performance method |
| CN108063217A (en) * | 2017-12-26 | 2018-05-22 | 深圳先进技术研究院 | Potassium base Dual-ion cell and preparation method thereof |
| CN108155408A (en) * | 2017-12-26 | 2018-06-12 | 深圳先进技术研究院 | Dual-ion cell and preparation method thereof |
| CN108470940A (en) * | 2018-03-19 | 2018-08-31 | 上海交通大学 | A kind of full stress-strain Magnesium ion battery and preparation method thereof |
| CN109148165A (en) * | 2018-08-01 | 2019-01-04 | 曲阜师范大学 | A kind of preparation and application of covalent organic frame/graphene composite material |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN109904519A (en) * | 2019-01-18 | 2019-06-18 | 北京理工大学 | A kind of all solid state electrolyte material and its preparation method and application |
| CN109755534A (en) * | 2019-01-21 | 2019-05-14 | 中国科学院宁波材料技术与工程研究所 | A kind of electrode material and its preparation and application based on organic covalent frame material |
Non-Patent Citations (5)
| Title |
|---|
| HEPING MA等: "Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| HONGWEI CHEN等: "Cationic Covalent Organic Framework Nanosheets for Fast Li-Ion Conduction", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| QIUJU ZHANG等: "Insights into High Conductivity of the Two-Dimensional Iodine-Oxidized sp2-c-COF", 《ACS APPLIED MATERIALS AND INTERFACES》 * |
| 吴辉煌: "《应用电化学基础》", 31 March 2006, 厦门大学出版社 * |
| 周婷 等: "共价有机骨架的设计、制备及应用", 《功能高分子学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029579A (en) * | 2019-12-12 | 2020-04-17 | 深圳先进技术研究院 | Calcium ion battery positive electrode material, positive electrode and calcium ion battery |
| CN111029579B (en) * | 2019-12-12 | 2020-12-25 | 深圳先进技术研究院 | Calcium ion battery positive electrode material, positive electrode and calcium ion battery |
| CN114242927A (en) * | 2021-12-22 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
| CN114242927B (en) * | 2021-12-22 | 2023-07-18 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110556537B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN105680091B (en) | A kind of high-performance all-solid lithium-ion battery and preparation method thereof | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN110429279B (en) | Organic anode material of lithium ion battery and application thereof | |
| CN101562244A (en) | Method for preparing elemental sulfur composite material used by lithium secondary battery | |
| CN103579590A (en) | Preparation method for coating anode material of lithium battery | |
| CN102280656A (en) | Preparation method of lithium ion battery with positive electrode covered by conductive polymer | |
| CN103367791B (en) | A kind of new type lithium ion battery | |
| CN102088086A (en) | High-voltage lithium ion battery anode, lithium ion battery using same and preparation method of high-voltage lithium ion battery anode | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN105185958A (en) | Novel electrode material of sodium-ion battery and application of electrode material | |
| CN108539196A (en) | A kind of high-performance sulfur-based composite anode material and preparation method thereof | |
| WO2012163186A1 (en) | Lithium phosphorus secondary battery | |
| CN105355903A (en) | Nickel lithium manganate-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN110556537B (en) | Method for improving electrochemical performance of anion-embedded electrode material | |
| CN102569724B (en) | Preparation method for composite material used for anode of lithium ion battery | |
| CN109786751A (en) | A kind of negative current collector and preparation method thereof and solid state battery | |
| CN104979534B (en) | A kind of iodine sulphur/carbon composite and preparation method and application | |
| CN102315481A (en) | High specific energy lithium-rich multi-element lithium ion battery and preparation method thereof | |
| CN104078678A (en) | Sulfur-carbon conductive polymer positive electrode and secondary aluminium battery using same | |
| CN105428634A (en) | Lithium ion battery negative electrode material and preparation method of lithium sulfide battery | |
| CN105161689A (en) | Preparing method and application of polypyrrole/multi-wall carbon nanotube/sulfur composite material | |
| CN107799700A (en) | A kind of preparation method and applications of the barrier film of the Prussian blue modification of fabricated in situ | |
| CN1835262A (en) | Anode active material compsns anode sheet and Li ion cell | |
| JP2014216211A (en) | Electrode and nonaqueous secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |