CN114069044B - Positive electrode material and lithium ion battery containing same - Google Patents
Positive electrode material and lithium ion battery containing same Download PDFInfo
- Publication number
- CN114069044B CN114069044B CN202111257939.2A CN202111257939A CN114069044B CN 114069044 B CN114069044 B CN 114069044B CN 202111257939 A CN202111257939 A CN 202111257939A CN 114069044 B CN114069044 B CN 114069044B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- lithium ion
- ion battery
- 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.)
- Active
Links
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive electrode material and a lithium ion battery containing the positive electrode material, wherein the positive electrode material is based on three-center four-electron [ N … A ] n+ …N]Bridged two-dimensional halo-bonded organic framework molecules, wherein the A + Selected from I + Or an n-valent metal ion; the positive electrode material has a porous structure. The positive electrode material has a large number of redox sites due to the existence of iodide ions or n-valence metal ions and pyridine (or imidazole and the like) groups, so that the positive electrode material has higher specific capacity; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material also has an excellent and stable two-dimensional periodic structure, so that the cycle performance of the battery is improved. The positive electrode material has high oxidation-reduction potential, and can provide a high discharge voltage platform, so that the energy density of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of electrode materials of lithium ion batteries and preparation thereof, and particularly relates to a positive electrode material and a lithium ion battery containing the positive electrode material, in particular to a covalent organic framework positive electrode material, a preparation method thereof and a battery containing the positive electrode material.
Background
The 21 st century energy crisis is attracting more and more attention, and the problems of energy shortage and environmental pollution have forced researchers to find other alternative energy sources, such as solar energy, wind energy, geothermal energy, biological energy, and battery-like storage devices, to be the focus of attention. The battery storage device has the dual roles of energy storage and release, so that the development of a novel lithium ion battery anode material with low cost, high efficiency and stable cycle performance is of great significance in preparing the battery device with high energy density.
However, the market places higher demands on the storage density and flexibility of lithium ion batteries, and thus, development of new electrode materials is required to meet the above demands. The conventional positive electrode material of the lithium ion battery is mainly an inorganic compound, and the development of the lithium ion battery using the inorganic compound as the positive electrode material is limited due to the problem of mining reserves. The organic positive electrode material can avoid the problem of the reserve of the lithium ion battery, has green sustainability and is an ideal positive electrode material of the lithium ion battery in the future. The electroactive organic positive materials at this stage can be broadly divided into the following categories: conductive polymers, organic sulfur compounds, organic radical compounds, and organic carbonyl compounds. Among them, organic carbonyl compounds have received great attention because of their high theoretical specific capacity. However, organic carbonyl compounds have problems of poor conductivity and poor cycle stability. Therefore, development of a novel organic positive electrode material is needed to have the advantages of large capacity and high cycle stability.
Disclosure of Invention
In order to solve the technical problems, the invention provides a positive electrode material, a preparation method and application thereof, wherein the positive electrode material is based on three-center four-electron [ N … A ] n+ …N]Bridged two-dimensional a-bond organic framework molecules and have a porous structure; the positive electrode material of the invention is characterized in that A n+ The existence of ions and pyridine (or imidazole and the like) groups has a large number of redox sites, so that the specific capacity is higher; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material also has an excellent and stable two-dimensional periodic structure, so that the cycle performance of the battery is improved. Therefore, the technical problems of poor conductivity and poor circulation stability of the organic lithium ion battery when the carbonyl material is used as the positive electrode material are solved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a positive electrode material based on three-center four-electron [ N … A ] n+ …N]A bridged two-dimensional a-bond organic framework molecule, wherein the a n+ Selected from I + Or an n-valent metal ion; the positive electrode material has a porous structure.
According to the invention, the n-valent metal ion is, for example, a noble metal ion, which may be, in particular, au + 、 Ru 3+ 、Pt 2+ Or other noble metal ions.
According to the invention, the positive electrode material comprises one of the following structural fragments represented by the formulas I to IX:
in the formulas I to IX, A n+ X is as defined above 1 Selected from the group consisting of absent or divalent radicals, X 2 Selected from trivalent radicals, X 3 Selected from tetravalent groups.
According to the invention, when X 1 The positive electrode material comprises one of the following structural fragments shown in formula Ia, formula IIa or formula IIIa when the positive electrode material is not present:
in formula Ia, formula IIa and formula IIIa, A n+ Is as defined above.
According to the invention, X 1 Selected from divalent groups such as polyethylene terephthalate groups, polybutylene terephthalate groups.
According to the invention, a trivalent radical X 2 For example phenyl, the 1,3,5 positions of which are the attachment sites.
According to the invention, tetravalent radical X 3 For example vinyl groups, the 1,2 positions of which are the attachment sites.
According to the present invention, the positive electrode material including the structural fragment represented by formula VIII specifically includes the structural fragment represented by formula VIIIa as follows:
in formula VIIIa, the central ion I + Can also be replaced by Au + 、Ru 3+ 、Pt 2+ And other noble metal ions. In the invention, the structural stability of the material can be improved by introducing metal ions.
The invention also provides a positive plate which comprises the positive electrode material.
The invention also provides a lithium ion battery, which comprises the positive electrode material; alternatively, the positive electrode sheet is included.
The invention has the beneficial effects that:
the invention provides a three-center four-electron-based [ N … A n+ …N]A bridged two-dimensional a-bond organic framework molecule, and a positive electrode material having a porous structure; the positive electrode material of the invention is characterized in that A n+ The existence of ions and pyridine (or imidazole and the like) groups has a large number of redox sites, so that the specific capacity is higher; meanwhile, the lithium ion battery has a porous structure, so that a large amount of electrolyte can be quickly absorbed to quickly transmit lithium ions; the positive electrode material of the invention also has excellent and stable performanceThe two-dimensional periodic structure further improves the cycle performance of the battery. Therefore, the technical problems of poor conductivity and poor circulation stability of the organic lithium ion battery when the carbonyl material is used as the positive electrode material are solved. The positive electrode material has high oxidation-reduction potential, and can provide a high discharge voltage platform, so that the energy density of the battery is improved. The concrete steps are as follows:
(1) The anode material is a high molecular polymer, has a porous structure, can quickly absorb a large amount of electrolyte (the absorption time of the electrolyte on the anode material is 40-70% shorter than that of the conventional electrode material under the same electrode pole piece preparation process), and is insoluble in the current commercialized electrolyte, so that the electrode active material is effectively prevented from shuttling at two poles, and the cycle stability of a battery is improved.
(2) The positive electrode material of the present invention has a large number of redox sites due to the presence of iodide ions and pyridine (or imidazole, etc.) groups, and thus can provide specific capacity of a battery.
(3) The positive electrode material of the present invention also has an excellent, stable two-dimensional periodic structure in which iodine positive ions (I + ) Used as a linking moiety, tends to form stable, linear halogen bond interactions, thereby enhancing the cycling performance of the battery.
(4) I in the cathode material of the present invention + Can be Au-coated + Etc. to improve the cycling stability of the electrode.
(5) The positive electrode material of the invention can also be applied to solid-state batteries, quasi-solid-state batteries, and other positive electrode materials for ion batteries (for example, adding Mg (TFSI) by adjusting additives in the preparation process 2 To be suitable for use in magnesium ion batteries or to add naffsi to be suitable for use in sodium ion batteries).
Drawings
Fig. 1 is a cycle performance chart of lithium ion batteries manufactured in examples 1-2 and comparative examples 1-2.
Detailed Description
The invention also provides a preparation method of the positive electrode material, which comprises the following steps: in a compound containing an =n-groupThe object is a model unit and contains Ag + Is coordinated to form [ N … Ag ] + …N]Bridged organic framework molecules, and thus using A n+ In situ substitution [ N … Ag ] + …N]Ag in bridge + Ion formation to [ N … A n+ …N]Bridged organic framework molecules, i.e. the positive electrode material; a is that n+ Is as defined above.
According to the invention, the compound containing an =n-group is selected from one of the compounds represented by the following structural formulae: 4,4 '-bipyridine, 2' -bipyridine, imidazole (such as N-ethylimidazole, N-propylimidazole, 2,4, 5-triiodoimidazole, etc.) which is unsubstituted or optionally substituted by one or more alkyl groups, halogen, TPPE, etc., said TPPE having the following structural formula:
according to the invention, the compound containing an =n-group is mixed with Ag + Compound (A) n+ The dosage ratio of (2) is 1:1-1:5, and the ratio is 1:1, 1:2, 1:3, 1:4 and 1:5.
According to the invention, the Ag-containing material + The compound of (2) may be AgPF, for example 6 、AgSbF 6 、AgAsF 6 At least one of the following.
According to the invention, the A n+ Can be A-containing n+ At least one of the elements or compounds of (a) is provided.
According to the invention, the compound containing an =n-group is mixed with Ag + The compounds of (a) are added into the reaction system in the form of solution. For example, CHCl of the compound containing the=n-group is prepared separately 3 Mixed solution of MeOH and Ag-containing solution + The two solutions are mixed to obtain a reaction mixture. Preferably, CHCl 3 In a mixed solvent of MeOH and CHCl 3 The mixing volume ratio of MeOH is (50-150): (0-1), exemplary 50:0, 80:1, 100:1, 150:1.
According to the invention, the A n+ Is added into the reaction system in the form of solution. For example, A is prepared first n+ Is then mixed with the methanol solution of (C)Will contain A n+ Is added into the reaction system. Preferably, the said A-containing n+ The concentration of the methanol solution is 0.01 to 0.05mol/L, and exemplary is 0.01mol/L, 0.03mol/L, 0.05mol/L.
According to the invention, the A n+ In situ substitution [ N … Ag ] + …N]Ag in bridge + The reaction temperature of the ions is 140 to 180 ℃, and is exemplified by 140 ℃, 160 ℃ and 180 ℃. Further, the reaction time is 4 to 8 hours, and is exemplified by 4 hours, 6 hours, and 8 hours.
According to the invention, the preparation method of the positive electrode material further comprises the steps of decompressing the reaction mixture to remove the solvent, and drying the precipitate overnight to obtain the positive electrode material.
According to an exemplary embodiment of the invention, the A n+ Is I + . For example, the I + Provided by elemental iodine.
According to an exemplary embodiment of the present invention, the TPPE is prepared by reacting a feedstock comprising 1, 2-tetrakis (4-bromophenyl) ethylene and 4-pyridineboronic acid in the presence of palladium acetate, potassium phosphate, tricyclohexylphosphine.
Preferably, the using percentages of the raw materials of the 1, 2-tetra (4-bromophenyl) ethylene and 4-pyridine boric acid, the palladium acetate, the potassium phosphate and the tricyclohexylphosphine are 15-30%: 20-35%: 0.5 to 5 percent: 40-60%: 2-10%.
Preferably, the preparation of the TPPE is carried out in a solvent system. For example, the solvents are DMF and H 2 Mixed solvent of O. Further, in the mixed solvent, DMF and H 2 The mixing volume ratio of O is (5-15): 1, and exemplary are 5:1, 8:1, 10:1, and 15:1.
Preferably, the temperature of the reaction during the preparation of the TPPE is 120-160 ℃, and is exemplified by 120 ℃, 145 ℃ and 160 ℃. Further, the reaction time is 48 hours or more.
Preferably, the preparation of the TPPE further comprises concentrating the above mixture under reduced pressure, and grinding the resulting slurry. For example, the milling media is methylene chloride.
Preferably, the preparation of the TPPE alsoComprises washing and drying the ground product. For example, use H 2 The product was washed with O and dried over anhydrous sodium sulfate to purify the residue.
According to an exemplary embodiment of the present invention, the method for preparing the positive electrode material includes the steps of:
s1: adding 1, 2-tetra (4-bromophenyl) ethylene and 4-pyridineboronic acid, palladium acetate, potassium phosphate, tricyclohexylphosphine into DMF and H under argon atmosphere 2 O in a mixed solvent;
s2: heating and stirring the mixed solution for more than 48 hours;
s3: concentrating the mixture under reduced pressure, adding the obtained slurry into dichloromethane, and grinding;
s4: using H 2 Washing the product with O, drying with anhydrous sodium sulfate, and purifying the residue;
s5: adding the product into CHCl 3 In a mixed solution of MeOH, agBF 4 Adding the mixture into methanol, respectively and uniformly stirring, mixing, and stirring for more than 1 h;
s6: dropwise adding a methanol solution of iodine, and stirring for 6 hours after degassing treatment;
s7: the solvent was removed under reduced pressure and the precipitate was dried in vacuo overnight to give product XOF.
The invention also provides application of the positive electrode material as a positive electrode active material of a lithium ion battery.
The invention also provides a positive plate which comprises the positive electrode material.
According to the invention, the positive electrode sheet comprises a current collector and an active material layer positioned on at least one side surface of the current collector, wherein the active material layer comprises the positive electrode material.
According to the invention, the active material layer further comprises a conductive agent and a binder. Preferably, the mass ratio of the positive electrode material, the conductive additive and the binder is (6-8): (1-13): 1, exemplary 6:1: 1. 7:13: 1. 8:7: 1. 8:1: 1. 8:13:1.
the invention also provides a preparation method of the positive plate, which comprises the steps of uniformly dispersing the positive electrode material, the conductive agent and the adhesive in a solvent, coating the positive electrode material, the conductive agent and the adhesive on a current collector, and then vacuum drying the current collector to prepare the positive electrode film.
The invention also provides a lithium ion battery, which comprises the positive electrode material; alternatively, the positive electrode sheet is included.
According to the invention, the lithium ion battery further comprises a negative plate.
According to the invention, the lithium ion battery further comprises a separator.
According to the invention, the lithium ion battery further comprises an electrolyte. The type of electrolyte is not particularly limited in the present invention, and for example, a conventional commercial LiPF in the art can be used 6 A series of electrolytes.
The invention also provides a preparation method of the lithium ion battery, which comprises the following steps: the positive plate and the negative plate are separated by a diaphragm, electrolyte is injected, and the lithium ion battery is obtained through assembly.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the invention.
The invention is further illustrated by the following examples.
Example 1
Preparing a positive electrode material:
under an argon atmosphere, 648mg of 1, 2-tetrakis (4-bromophenyl) ethylene and 737mg of 4-pyridineboronic acid, 67mg of palladium acetate, 1.4g of potassium phosphate, 140mg of tricyclohexylphosphine were added to 20ml of DMF and 2ml of H 2 O in a mixed solvent;
s2: heating and stirring the mixed solution at 145 ℃ for more than 48 hours;
s3: concentrating the reaction mixture obtained in the step S2 under reduced pressure, adding the obtained slurry into 100ml of dichloromethane, and grinding;
s4: using H 2 Washing the product, drying the product by anhydrous sodium sulfate, and purifying the residue;
s5: the product TPPE (32 mg) was added to CHCl 3 /MeOH(4ml,v：v=1: 3) 19mg of AgBF was mixed with the mixed solution of (C) 4 Adding into 3ml of methanol, respectively stirring uniformly, mixing, and stirring for more than 1 h;
s6: 3ml of a methanol solution of iodine (25 mg) was added dropwise thereto, and the mixture was subjected to degassing treatment and then stirred at 160℃for 6 hours;
s7: the solvent was removed under reduced pressure, and the precipitate was dried in vacuo overnight to give a product XOF-TPPE as a positive electrode material having the structural formula shown below:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
The testing method comprises the following steps:
battery cycle number test: after the battery is assembled, a LAND blue battery test system is used for testing the cycle performance under the condition of 0.2C/0.2C charge-discharge current and 3.0V-4.4V charge-discharge voltage.
Comparative example 1
Preparing a positive electrode material:
under an argon atmosphere, 648mg of 1, 2-tetrakis (4-bromophenyl) ethylene and 737mg of 4-pyridineboronic acid, 67mg of palladium acetate, 1.4g of potassium phosphate, 140mg of tricyclohexylphosphine were added to 20ml of DMF and 2ml of H 2 O in a mixed solvent;
s2: heating and stirring the mixed solution at 145 ℃ for more than 48 hours;
s3: concentrating the mixture under reduced pressure, adding the obtained slurry into 100ml of dichloromethane, and grinding;
s4: using H 2 Washing the product, drying the product by anhydrous sodium sulfate, and purifying the residue;
s5: the above products are producedTPPE (32 mg) was added to CHCl 3 In a mixed solution of/MeOH (4 ml, v: v=1:3), 19mg of AgBF was added 4 Adding into 3ml of methanol;
s6: stirring for 6h at 160 ℃ after degassing treatment;
s7: the solvent was removed under reduced pressure, and the precipitate was dried in vacuo overnight to give a product MOF-TPPE having a structural formula as a positive electrode material represented by the following formula:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF binder (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode sheet (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF) is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
Example 2
S1: agBF 4 (19 mg)/methanol (3 ml) was added dropwise 4,4' -bipyridine (15.6 g)/CHCl 3 (12 ml) in solution;
s2: the solution was stirred at room temperature for 1 hour and I was added 2 (25mg)/CHCl 3 (3 ml) of a solution;
s3: the mixture was stirred for an additional 1 hour and the solvent was removed under reduced pressure (without heating);
s4: the precipitate was dried under vacuum overnight to give the product XOF-BPy as a positive electrode material of the formula:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; will be spentThe positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF) is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery.
Comparative example 2
S1: agBF 4 (19 mg)/methanol (3 ml) was added dropwise 4, 4-bipyridine (15.6 g)/CHCl 3 (12 ml) in solution;
s2: the solution was stirred at room temperature for 1 hour;
s3: removing the solvent under reduced pressure without heating;
s4: the precipitate was dried under vacuum overnight to give product XOF-Bpy, a positive electrode material having the structural formula shown below:
preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), conductive carbon black (Super-P) conductive agent (50 mg) and PVDF adhesive (50 mg) in a solvent, coating the mixture on a current collector, and then drying the mixture in vacuum to prepare a positive electrode film; the positive electrode film and the negative electrode material (metallic lithium) are separated by a separator (polyolefin porous film), and an electrolyte (1M LiPF is injected 6 /(ec+dec, 1:1)), and assembling to obtain the lithium ion battery. Fig. 1 is a graph showing cycle performance of the batteries manufactured in examples 1-2 and comparative examples 1-2. As can be seen from the figures: table 1 list of performance test data for batteries
As can be seen from the battery cycle performance diagram of FIG. 1, the cycle performance of the positive electrode material prepared by the invention is obviously improved (up to 51.8 percent) compared with that of the conventional positive electrode material, so that the positive electrode material can obviously improve the battery cycle performance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A positive electrode material is characterized by being based on three-center four-electron [ N … A ] n+ …N]A bridged two-dimensional a-bond organic framework molecule, the positive electrode material having one of the structural fragments represented by the following formulas I, II, IV to IX:
the positive electrode material including the structural fragment represented by formula VIII specifically includes the structural fragment represented by formula VIIIa below:
wherein in the formulas I, II, IV and IX, X 1 Selected from the group consisting of absent or divalent groups, said divalent groups being poly (terephthalate) groups; x is X 2 Selected from trivalent radicals, X 3 Selected from tetravalent groups; the A is n+ Selected from I + Or n-valent metal ion of Au + 、Ru 3+ 、Pt 2+ And other noble metal ionsOne less;
in formula VIIIa, I + Also replaced by Au + 、Ru 3+ 、Pt 2+ Other noble metal ions;
the positive electrode material has a porous structure.
2. The positive electrode material according to claim 1, wherein X 1 Is selected from the non-existent positive electrode material, and the positive electrode material comprises one of the following structural fragments shown in the formulas Ia and IIa:
in formula Ia, formula IIa, A n+ Selected from I + Or n-valent metal ion of Au + 、Ru 3+ 、Pt 2+ And at least one of other noble metal ions.
3. The positive electrode material according to claim 1, wherein the trivalent group X 2 Is phenyl, and the 1,3 and 5 positions are connecting sites.
4. The positive electrode material according to claim 1, wherein the tetravalent group X 3 Is vinyl, and the 1,2 and 2 positions are connecting sites.
5. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 4.
6. The positive electrode sheet according to claim 5, wherein the positive electrode sheet comprises a current collector and an active material layer on at least one side surface of the current collector, and the active material layer comprises the positive electrode material.
7. A lithium ion battery comprising the positive electrode material of any one of claims 1-4; alternatively, a positive electrode sheet comprising any one of claims 5 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111257939.2A CN114069044B (en) | 2021-10-27 | 2021-10-27 | Positive electrode material and lithium ion battery containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111257939.2A CN114069044B (en) | 2021-10-27 | 2021-10-27 | Positive electrode material and lithium ion battery containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114069044A CN114069044A (en) | 2022-02-18 |
| CN114069044B true CN114069044B (en) | 2023-06-13 |
Family
ID=80236353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111257939.2A Active CN114069044B (en) | 2021-10-27 | 2021-10-27 | Positive electrode material and lithium ion battery containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114069044B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239779A (en) * | 2022-09-06 | 2023-06-09 | 武汉大学 | Two-dimensional halogen bond organic framework material for iodination reagent, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022496A (en) * | 2012-12-28 | 2013-04-03 | 南开大学 | Aromatic condensed ring quinones compound positive pole material for one-class lithium secondary battery |
| CN103904329A (en) * | 2012-12-27 | 2014-07-02 | 清华大学 | Lithium ion battery |
| CN113066992A (en) * | 2021-03-08 | 2021-07-02 | 常州大学 | Alkaline aqueous single flow battery based on double-metal MOF positive electrode and organic matter negative electrode |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102277906B1 (en) * | 2013-11-28 | 2021-07-15 | 삼성전자주식회사 | Cathode active material, secondary battery comprising the same, and preparation method thereof |
| KR101983099B1 (en) * | 2015-11-30 | 2019-05-29 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, and positive electrode for secondary battery and secondary battery comprising the same |
| CN110429279B (en) * | 2019-07-12 | 2021-05-18 | 华中科技大学 | Organic anode material of lithium ion battery and application thereof |
| CN110931865A (en) * | 2019-11-20 | 2020-03-27 | 珠海市赛纬电子材料股份有限公司 | Novel additive-containing electrolyte for lithium ion battery and lithium 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 |
| JP7483222B2 (en) * | 2020-02-07 | 2024-05-15 | 時空化学株式会社 | Positive electrode active material precursor for secondary battery, positive electrode active material for secondary battery, catholyte for secondary battery, positive electrode for secondary battery, and secondary battery |
| CN113321786B (en) * | 2021-05-28 | 2022-06-28 | 南京理工大学 | Sulfonic conjugated microporous polymer, preparation method and application |
| CN113328093B (en) * | 2021-05-31 | 2023-04-28 | 湖北大学 | Organic electrode material of metal ion battery, electrode, battery and preparation method |
-
2021
- 2021-10-27 CN CN202111257939.2A patent/CN114069044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904329A (en) * | 2012-12-27 | 2014-07-02 | 清华大学 | Lithium ion battery |
| CN103022496A (en) * | 2012-12-28 | 2013-04-03 | 南开大学 | Aromatic condensed ring quinones compound positive pole material for one-class lithium secondary battery |
| CN113066992A (en) * | 2021-03-08 | 2021-07-02 | 常州大学 | Alkaline aqueous single flow battery based on double-metal MOF positive electrode and organic matter negative electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114069044A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101740754B (en) | Preparation method of composite anode material for lithium element sulphur secondary battery | |
| CN111261872B (en) | Organic electrode material and preparation method and application thereof | |
| CN104558540B (en) | Polytetratriphenylamine and application thereof as lithium ion battery positive pole material | |
| CN111342047B (en) | High-performance organic positive electrode material and application thereof in potassium ion battery | |
| CN111235595B (en) | TEMPO-based polypyrrole for mixed liquid flow battery cathode and preparation method | |
| CN113328093A (en) | Organic electrode material of metal ion battery, electrode, battery and preparation method | |
| CN114069044B (en) | Positive electrode material and lithium ion battery containing same | |
| CN114497547A (en) | Conjugated quinozine organic electrode material and preparation method and application thereof | |
| CN112271314B (en) | Flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and preparation method thereof | |
| CN112409364B (en) | Hexaazanaphthalene derivative and preparation method and application thereof | |
| CN102263264A (en) | Free radical polymer/graphene composite material and preparation method thereof as well as application thereof | |
| CN116925308A (en) | Covalent organic framework containing anthraquinone structure and application of covalent organic framework in water-based zinc ion battery | |
| CN115557955B (en) | Hexaazatrinaphthalene monomer and preparation method thereof, porous organic polymer and preparation method and application thereof | |
| CN114315704B (en) | Bipyridine compound and synthetic method and application thereof | |
| CN113501956B (en) | D-A type perylene conjugated polymer lithium ion battery positive electrode material with high rate performance and preparation method thereof | |
| CN100495776C (en) | Secondary battery and capacitor using indole compound | |
| CN107093731B (en) | Polyvanadyl compound, preparation method and application thereof, and lithium ion battery containing same | |
| CN111211327B (en) | Compound for lithium ion battery anode material and preparation method and application thereof | |
| CN114497662A (en) | Application of multi-electron hexaazanaphthalene compound in aqueous flow battery | |
| CN114105907A (en) | Pyrrolidine ionic liquid and preparation method and application thereof | |
| CN114409894A (en) | Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof | |
| CN115057862B (en) | Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery | |
| CN114479078B (en) | Naphthalimide polymer, preparation method thereof and application thereof in lithium/sodium battery | |
| CN115873242B (en) | Preparation method of organic polymer based on hexaazanaphthalene and application of organic polymer as positive electrode material of water-based aluminum ion battery | |
| CN116496495B (en) | Crown ether group covalent organic polymer and light-assisted lithium battery cell device thereof |
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 |