CN117757068A - Conjugated polyimide positive electrode material and preparation method thereof - Google Patents
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 239000004642 Polyimide Substances 0.000 title claims abstract description 29
- 229920001721 polyimide Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 125000004427 diamine group Chemical group 0.000 claims abstract description 5
- 125000006159 dianhydride group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 229920005575 poly(amic acid) Polymers 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- VUVVIURXJWHENR-UHFFFAOYSA-N 2,5-diaminocyclohexa-2,5-diene-1,4-dione Chemical compound NC1=CC(=O)C(N)=CC1=O VUVVIURXJWHENR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEKVBIXIBCYLRT-RSAXXLAASA-N [4-[(2e)-2-[3-[(2s)-2-amino-2-carboxyethyl]-6-oxocyclohexa-2,4-dien-1-ylidene]hydrazinyl]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C1=CC([N+](C)(C)C)=CC=C1N\N=C/1C(=O)C=CC(C[C@H](N)C(O)=O)=C\1 XEKVBIXIBCYLRT-RSAXXLAASA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- -1 1,4,5, 8-naphthalene tetracarboxylic anhydride Chemical class 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to the field of battery anode materials, and provides a conjugated polyimide anode material and a preparation method thereof, aiming at the problem of low specific capacity of an organic electrode material. The molecular structure of the conjugated polyimide positive electrode material is as follows:
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a conjugated polyimide positive electrode material and a preparation method thereof.
Background
The electrode material is a key material for influencing the energy density of the secondary battery, the traditional inorganic electrode material contains a large amount of transition metal elements, the cost is high and the material is not environment-friendly, the organic electrode material only consists of C, H, N, O, S and other elements, the elements are abundant in nature and easy to obtain, and compared with the inorganic electrode material, the organic electrode material formed by the organic electrode material is lighter and has a multi-electron redox reaction process. Among organic electrode materials, conjugated carbonyl compounds have an attractive theoretical specific capacity (typically above 300 mAh/g), high redox reversibility and a clear reaction mechanism, and are considered to be one of the most promising organic electrode materials. However, organic electrode materials are readily soluble in electrolytes and have poor electrical conductivity, practical capacity is far less than theoretical capacity, and cyclic capacity decays rapidly.
Current organic electrode materials generally have several methods to remedy the above-mentioned drawbacks: scheme 1, preparing small molecules containing redox active functional groups into polymers by polymerization means, decreasing solubility in electrolytes. For example, patent CN107437467a discloses hybrid supercapacitors with increased service life, electrolyte additives forming oligomeric and/or polymeric structures on the surface of the positive and/or negative electrode and thereby forming a coating layer when a voltage is applied across the positive and/or negative electrode of the hybrid supercapacitor. In scheme 2, the small molecules are fixed on the solid substrate through chemical or physical means, so that the small molecule active materials are prevented from being dissolved in the electrolyte, for example, other conductive materials such as (carbon nano tube and graphene) are compounded, the solubility of the conductive materials in the electrolyte is reduced, and meanwhile, the conductive substrate can be used as a conductive network, so that the conductivity of the electrode is increased.
For scheme 1, the polymer is prepared by polymerizing small molecules containing active functional groups, and as the polymer is insulated, the rate performance and the cycle stability of the polymer are limited, and the polymer is usually used as a positive electrode material, and is required to be matched with other conductive agents, and the conductive agents are used as substances without electrochemical activity (dead structures), so that the specific capacity of an electrode is reduced, the more the conductive agents are added, the lower the specific capacity of the electrode is, and for the organic electrode material, the better effect can be achieved by adding more than 30% of the conductive agents in the electrode manufacturing process, and the specific capacity of the electrode is greatly reduced. In scheme 2, small molecules are usually fixed on a large conductive substrate, the proportion of electrochemically inactive substances in the electrode is large, and even if functionalized materials such as graphene oxide are used as the substrate, most of the molecular structures are dead structures and the specific capacity is not ideal. Additional processing techniques are also required to immobilize the small molecules to the substrate by physical or chemical means. There is a need for an ideal solution.
Disclosure of Invention
In order to overcome the problem of low specific capacity of an organic electrode material, the invention provides a conjugated polyimide positive electrode material, which is prepared by introducing active functional groups (carbonyl groups) and the like into polyimide molecular chains to provide active sites for oxidation-reduction reaction, then increasing conjugation of polyimide through molecular structure design to reduce HOMO-LUMO gap, and realizing high electron conductivity only by a small amount of doping, and simultaneously solving the problems that the organic positive electrode material is easily dissolved in electrolyte and has poor conductivity. Can be used as a high-performance organic positive electrode material for secondary batteries.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a conjugated polyimide positive electrode material has a molecular structure shown as follows:wherein A is a dianhydride residue and B is a diamine residue.
The main chain of the positive electrode material contains groups with electrochemical activity and has a large conjugated structure. Polyimide is a high molecular polymer with imide ring structure in the main chain, and has excellent high temperature resistance, chemical stability and mechanical performance, and the performance of the polyimide is positioned at the top of a pyramid of a high molecular material. Generally prepared by polymerizing diamine and dianhydride into PAA and then dehydrating and imidizing. PI has extremely high structural designability due to the diversity of diamine and dianhydride structural designs. According to the invention, the redox active groups such as carbonyl are introduced into the PI main chain, and the HOMO-LUMO gap of PI is reduced by constructing a large conjugated structure, so that the large conjugated PI positive electrode material is prepared, and the electron conductivity is improved. Meanwhile, the problems that the organic positive electrode material is dissolved in an organic solvent and has poor conductivity are solved.
Preferably, a is an aromatic or alicyclic tetracarboxylic dianhydride residue; b is a diamine residue containing a carbonyl group and a conjugated system.
Preferably, n ranges from 10 to 1000.
Preferably, the positive electrode material has a structure of
The invention also provides a preparation method of the positive electrode material, which comprises the following steps: under the protection of inert gas, diamine monomer containing carbonyl and conjugated system is dissolved in polar aprotic solvent, dianhydride monomer is added and stirred at 0-50 ℃ for 3-48 hours to obtain homogeneous polyamic acid precursor, and then imidization dehydration is carried out on the polyamic acid precursor by a thermal method or a chemical method to obtain the anode material.
Preferably, the amount ratio of diamine monomer to dianhydride monomer is 1 (0.9-1.1).
Preferably, the inert gas is one or more of nitrogen, helium and argon; the polar aprotic solvent is one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfone, sulfolane and 1, 4-dioxane.
Preferably, the positive electrode materialThe preparation method of (2) comprises the following steps: mixing 2, 5-diaminocyclohexane-2, 5-diene-1, 4-dione and DMF under the protection of inert gas, adding pyromellitic anhydride, stirring at 0-50 ℃ for reaction for 7-9h, and then heating and refluxing for reaction for 7-9h; and after the reaction is finished, washing, drying and baking to obtain the anode material.
Preferably, the positive electrode materialThe preparation method of (2) comprises the following steps: TAPT (2, 3,7, 8-tetraaminophenyl-1, 4,6,9-tetraone, CAS number 2857099-14-8) and DMF are mixed under the protection of inert gas, 3,4,9, 10-tetracarboxylic anhydride is added to be stirred for 7-9 hours at the temperature of 0-50 ℃ and then heated for reflux reaction for 7-9 hours; and after the reaction is finished, washing, drying and baking to obtain the anode material.
Preferably, the washing is to wash the precipitate three times with methanol and acetone, the drying is to vacuum dry at 110-130 ℃ for 10-14h, and the baking is to bake at 300-400 ℃ for 5-7h under nitrogen atmosphere.
Therefore, the invention has the beneficial effects that: (1) Compared with the existing inorganic anode, the organic anode material is more environment-friendly, can be developed in a sustainable way and has low mass production cost. (2) Compared with inorganic materials, the polymer electrode material has the advantages of flexibility, good ion transmission characteristic and obvious advantages especially for elements with large ion radius. (3) Through molecular structure design, the PI of the invention improves the electronic conductivity, combines the high ion transmission characteristic, chemical stability, excellent mechanical property, high temperature resistance and flame retardance of the PI, can be used as a high-performance organic positive electrode material, and can realize the aims of safety, long service life and sustainable development when used for large-scale energy storage.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
A conjugated polyimide positive electrode material has the structural formula of
The preparation method comprises the following steps: 1.3812g (10 mmol) of 2, 5-diaminocyclohexane-2, 5-diene-1, 4-dione and 27mL of dry DMF are introduced into a 50mL round-bottomed flask under argon, dissolved by stirring, 2.1812g (10 mmol) of pyromellitic anhydride are added, the solid content is about 13%, and after stirring for 8 hours at 0℃the reaction mixture is reacted under reflux for 8 hours at 180 ℃. After the reaction was completed, the precipitate was washed three times with methanol and acetone. And then dried in a vacuum oven at 120 c for 12h. And finally, baking the prepared product for 6 hours at 350 ℃ in a nitrogen atmosphere to obtain the conjugated polyimide anode material.
Example 2
A conjugated polyimide positive electrode material has the structural formula of
The preparation method comprises the following steps: 3.0023g (10 mmol) TAPT and 46mL dry DMF are added to a 50mL round bottom flask under argon protection in a clean room, dissolved by stirring, 3.9232g (10 mmol) 3,4,9, 10-tetracarboxylic anhydride is added, the solid content is about 13%, and after stirring reaction at 0℃for 8h, reflux reaction at 180℃for 8h is carried out. After the reaction was completed, the precipitate was washed three times with methanol and acetone. And then dried in a vacuum oven at 120 c for 12h. And finally, baking the prepared product for 6 hours at 350 ℃ in a nitrogen atmosphere to obtain the conjugated polyimide anode material.
Comparative example 1
The structural formula of the polyimide positive electrode material is as follows:
the preparation method comprises the following steps: 0.6010g (10 mmol) of ethylenediamine and 20mL of dry DMF are added to a 50mL round bottom flask under argon protection in a clean room, and after stirring to dissolve, 2.1812g (10 mmol) of pyromellitic anhydride are added, the solid content is about 13%, and after stirring at 0℃for 8 hours, the reaction is refluxed at 180℃for 8 hours. After the reaction was completed, the precipitate was washed three times with methanol and acetone. And then dried in a vacuum oven at 120 c for 12h. And finally, baking the prepared product for 6 hours at 350 ℃ in a nitrogen atmosphere to obtain the polyimide anode material.
Comparative example 2
The structural formula of the polyimide positive electrode material is as follows:
the preparation method comprises the following steps: 0.7412g (10 mmol) of 1, 3-propanediamine and 24mL of dry DMF are introduced into a 50mL round bottom flask under the protection of argon in a clean room, and after stirring to dissolve, 2.6818g (10 mmol) of 1,4,5, 8-naphthalene tetracarboxylic anhydride are added, the solid content is about 13%, and after stirring to react at 0℃for 8 hours, the reaction is refluxed at 180℃for 8 hours. After the reaction was completed, the precipitate was washed three times with methanol and acetone. And then dried in a vacuum oven at 120 c for 12h. And finally, baking the prepared product for 6 hours at 350 ℃ in a nitrogen atmosphere to obtain the polyimide anode material.
Performance testing
79% by weight of polyimide material, 1% by weight of Sodium Dodecyl Benzene Sulfonate (SDBS), 10% by weight of Super P and 10% by weight of polyvinylidene fluoride are added into NMP and stirred and mixed, then the positive electrode slurry is uniformly coated on carbon-coated aluminum foil with the thickness of 13 microns, sent into a vacuum drying oven and dried for 8 hours at 80 ℃. After rolling and cutting the positive plate, assembling the positive plate into a CR2025 buckling battery in a glove box in an argon environment, taking a metal sodium plate as a negative electrode, adopting Celgard2400 as a diaphragm, and adopting 1mol/L NaPF as electrolyte 6 in EC: DMC (1:1, v/v). Performance tests were performed after making power-down using the polyimide positive electrode materials of example 1, example 2, comparative example 1 and comparative example 2, respectively.
The testing method comprises the following steps: constant current and constant voltage charge and discharge under 0.5C, the voltage range is 1.5V-3.5V, and the cut-off current is 0.05C; and (3) pole piece resistance test: cutting the rolled positive plate into 4 cm-by-4 cm samples, and measuring the resistance by using a pole piece impedance measuring instrument. The results are shown in the following table.
As can be seen from the table, the PI of the examples achieves a high theoretical capacity exertion compared to the PI of comparative examples 1 and 2, and for the comparative examples, 10% of the conductive carbon doping fails to build a sufficient conductive network, resulting in a lower theoretical capacity exertion.
Both the comparative and example anodes exhibited higher cycle capacity retention in half cells due to PI being poorly soluble in the electrolyte and stable in structure. The capacity retention rate of the examples is higher than that of the comparative examples, because the A group of the examples is dianhydride containing a large conjugated structure, the B group is a structure containing a high density of active functional groups, and the whole structure is more stable and has a larger conjugated structure.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The conjugated polyimide positive electrode material is characterized by having the following molecular structure:wherein A is a dianhydride residue and B is a diamine residue.
2. The conjugated polyimide positive electrode material according to claim 1, wherein a is an aromatic or alicyclic tetracarboxylic dianhydride residue; b is a diamine residue containing a carbonyl group and a conjugated system.
3. A conjugated polyimide positive electrode material according to claim 1 or 2, wherein n is in the range of 10 to 1000.
4. The conjugated polyimide positive electrode material according to claim 1, wherein the positive electrode material has a structure of
5. The method for preparing the conjugated polyimide positive electrode material according to claim 1-4, which is characterized in that diamine monomer containing carbonyl and conjugated system is dissolved in polar aprotic solvent under the protection of inert gas, dianhydride monomer is added to react for 3-48 hours at 0-50 ℃ under stirring to obtain homogeneous polyamic acid precursor, and imidization dehydration is carried out on the polyamic acid precursor by a thermal method or a chemical method to obtain the positive electrode material.
6. The process according to claim 5, wherein the ratio of the amount of diamine monomer to the amount of dianhydride monomer is 1 (0.9 to 1.1).
7. The method according to claim 5 or 6, wherein the inert gas is one or more of nitrogen, helium, and argon; the polar aprotic solvent is one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfone, sulfolane and 1, 4-dioxane.
8. The method according to claim 5, wherein the positive electrode materialThe preparation method of (2) comprises the following steps: mixing 2, 5-diaminocyclohexane-2, 5-diene-1, 4-dione and DMF under the protection of inert gas, adding pyromellitic anhydride, stirring at 0-50 ℃ for reaction for 7-9h, and then heating and refluxing for reaction for 7-9h; and after the reaction is finished, washing, drying and baking to obtain the anode material.
9. The method according to claim 5, wherein the positive electrode materialThe preparation method of (2) comprises the following steps: idler wheelTAPT (2, 3,7, 8-tetraaminophenyl-1, 4,6,9-tetraone, CAS number 2857099-14-8) and DMF are mixed under the protection of the sex gas, 3,4,9, 10-tetracarboxylic anhydride is added to be stirred for 7-9 hours at the temperature of 0-50 ℃ and then heated for reflux reaction for 7-9 hours; and after the reaction is finished, washing, drying and baking to obtain the anode material.
10. The preparation method according to claim 8 or 9, wherein the washing is washing the precipitate three times with methanol and acetone, the drying is vacuum drying at 110-130 ℃ for 10-14h, and the baking is baking at 300-400 ℃ for 5-7h under nitrogen atmosphere.
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