CN117143335A - Polyquinone amine organic positive electrode material and preparation method thereof - Google Patents
Polyquinone amine organic positive electrode material and preparation method thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 73
- 150000001412 amines Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 33
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 229940005561 1,4-benzoquinone Drugs 0.000 claims abstract description 15
- LNXVNZRYYHFMEY-UHFFFAOYSA-N 2,5-dichlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C(Cl)=CC1=O LNXVNZRYYHFMEY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 239000012065 filter cake Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- WEHGJIBEACNWRM-UHFFFAOYSA-N cyclohexa-2,5-diene-1,4-dione;ethane-1,2-diamine Chemical compound NCCN.O=C1C=CC(=O)C=C1 WEHGJIBEACNWRM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
The application provides a polyquinone amine organic positive electrode material and a preparation method thereof, wherein the polyquinone amine organic positive electrode material is insoluble in electrolyte, can effectively inhibit active material loss when applied to an ion battery, has a configuration structure for stably embedding multivalent ions, and is suitable for the multivalent ion battery. The preparation method comprises the following two steps: the method comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken as reaction raw materials to be dissolved in a reaction solvent for oxidation addition reaction to prepare the catalyst; the second method is as follows: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken as reaction raw materials to be dissolved in a reaction solvent, and the condensation reaction is carried out under the protection of inert gas. The polyquinone amine organic positive electrode material is used in zinc ion battery,shows good capacity performance and cycle performance, and is 0.02Ag ‑1 The highest specific discharge capacity under the current density can reach 138mAh g ‑1 The specific discharge capacity is maintained to be 78mAh g after 200 charge and discharge cycles ‑1 。
Description
Technical Field
The application relates to the technical field of batteries, in particular to a polyquinone amine organic positive electrode material and a preparation method thereof.
Background
The positive electrode material is a key component of the ion battery and determines the electrochemical performance of the ion battery. The anode materials with wider application are mainly inorganic anode materials such as iron-based, manganese-based and vanadium-based compounds. The organic positive electrode material is an emerging energy storage material, has the advantages of wide resources, designable structure, easiness in large-scale production, convenience in degradation and recovery and the like, and is an important means for replacing metal mineral resources and developing novel energy storage equipment by developing the organic positive electrode material to meet the requirements and application trend of the current novel energy storage technology. The organic positive electrode material is expected to become an ideal positive electrode material of an ion battery, and has great application potential in the field of energy storage.
At present, the organic positive electrode material mainly has certain application performance in batteries such as lithium ion, sodium ion and potassium ion, but the organic positive electrode material structure suitable for multivalent ion batteries is relatively less. In multivalent ion batteries, the actual specific capacity of the organic positive electrode material is low, the charge-discharge capacity decays rapidly, and the like. The organic material has rich structure and relatively complex three-dimensional configuration, and development of the organic positive electrode material with a new structure is more suitable for the insertion and extraction of multivalent ions, so that the development and application of the organic positive electrode material are promoted.
Disclosure of Invention
In order to solve the technical problems, the application provides a polyquinone amine organic positive electrode material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the application provides a polyquinone amine organic positive electrode material, which has the structural formula:
wherein n is a natural number of 1 or more.
The application also provides a preparation method of the polyquinone amine organic positive electrode material, which comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken and dissolved in a reaction solvent A to carry out an oxidation addition reaction; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
Further, the method specifically comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent A according to the proportion that each gram of 1, 4-benzoquinone and 0.3 to 1.3 grams of 1, 2-cyclohexanediamine are dissolved in 10 to 200mL of reaction solvent A; introducing 0mL of the reaction solvent A for 0mL of the reaction solvent A per milliliter -1 ～4mL min -1 Introducing the oxidizing gas flow and reacting for 2-48 h at 20-150 ℃; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
Further, the reaction solvent A is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
Further, the oxidizing gas stream is an oxygen gas stream or an air stream.
The application also provides another preparation method of the polyquinone amine organic positive electrode material, which comprises the following steps: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B, and condensation reaction is carried out under the protection of inert gas; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
Further, the method specifically comprises the following steps: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B according to the proportion that each gram of 2, 5-dichloro-1, 4-benzoquinone and 1.2-cyclohexanediamine are dissolved in 10-200 mL of the reaction solvent B, and the reaction is carried out for 1-48 h at 20-150 ℃ under the protection of inert gas; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
Further, the reaction solvent B is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
Further, the washing solvent is one or more of methanol, ethanol, isopropanol, N-butanol, N-dimethylformamide and water.
The application also provides application of the polyquinone amine organic positive electrode material in the field of ion batteries.
Compared with the prior art, the technical scheme provided by the application has at least the following advantages:
the application provides a polyquinone amine organic positive electrode material and a preparation method thereof, wherein the polyquinone amine organic positive electrode material has a specific microstructure, can be more stably embedded with multivalent ions, is difficult to dissolve in electrolyte, and effectively inhibits active material loss. The preparation of the polyquinone amine organic positive electrode material comprises the following two methods: the method comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken as reaction raw materials to be dissolved in a reaction solvent for oxidation addition reaction to prepare the catalyst; the second method is as follows: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken as reaction raw materials to be dissolved in a reaction solvent, and the condensation reaction is carried out under the protection of inert gas, so that the preparation method is simple and feasible. Experiments prove that the polyquinone amine organic positive electrode material applied to zinc ion batteries shows good cycle reversibility and multiplying power performance, and is 0.02Ag -1 The highest specific discharge capacity under the current density can reach 138mAh g -1 The specific discharge capacity is maintained to be 78mAh g after 200 charge and discharge cycles -1 。
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, which are not to be construed as limiting the embodiments unless specifically indicated otherwise.
FIG. 1 is an X-ray diffraction chart of a polyquinone amine organic positive electrode material prepared in example 1 of the present application;
FIG. 2 is a scanning electron microscope image of the organic positive electrode material of the polyquinone amine prepared in example 1 of the present application;
FIG. 3 is an infrared spectrum of the organic positive electrode material of polyquinone amine prepared in example 1 of the present application;
FIG. 4 is a thermogram of a polyquinolamine organic positive electrode material prepared in example 1 of the present application;
FIG. 5 is a cyclic voltammogram of the organic positive electrode material of polyquinone amine in a zinc ion battery prepared in example 1 of the present application;
FIG. 6 shows that the organic positive electrode material of the polyquinone amine prepared in example 1 of the present application is 0.02Ag in zinc ion battery -1 、0.03Ag -1 、0.05Ag -1 、0.1Ag -1 、0.2Ag -1 、0.3Ag -1 、0.5Ag -1 、1Ag -1 、2Ag -1 、5Ag -1 And 0.02Ag -1 Rate capability at current density;
FIG. 7 shows 0.1Ag of the organic positive electrode material of polyquinone amine prepared in example 1 of the present application in a zinc ion battery -1 Long cycle chart of 1000 charges and discharges at current density.
Detailed Description
As is clear from the background art, in the multivalent ion battery, the organic positive electrode material has the problems of unsatisfactory electrochemical performance such as specific capacity utilization rate, multiplying power, long cycle and the like, low practical specific capacity, rapid attenuation of charge and discharge capacity and the like.
The application provides a polyquinone amine organic positive electrode material, which has the structural formula:
wherein n is a natural number of 1 or more.
The application also provides a preparation method of the polyquinone amine organic positive electrode material, which comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken and dissolved in a reaction solvent A to carry out an oxidation addition reaction; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
The synthetic route for this reaction is as follows:
further, the method specifically comprises the following steps: 1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent A according to the proportion that each gram of 1, 4-benzoquinone and 0.3 to 1.3 grams of 1, 2-cyclohexanediamine are dissolved in 10 to 200mL of reaction solvent A; introducing 0mL of the reaction solvent A for 0mL of the reaction solvent A per milliliter -1 ～4mL min -1 Introducing the oxidizing gas flow and reacting for 2-48 h at 20-150 ℃; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
Further, the reaction solvent A is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
Further, the oxidizing gas stream is an oxygen gas stream or an air stream.
The application also provides a preparation method of the polyquinone amine organic positive electrode material, which comprises the following steps: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B, and condensation reaction is carried out under the protection of inert gas; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
The synthetic route for this reaction is as follows:
further, the method specifically comprises the following steps: 2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B according to the proportion that each gram of 2, 5-dichloro-1, 4-benzoquinone and 1.2-cyclohexanediamine are dissolved in 10-200 mL of the reaction solvent B, and the reaction is carried out for 1-48 h at 20-150 ℃ under the protection of inert gas; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
Further, the reaction solvent B is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
Further, the inert gas is nitrogen, helium or argon.
Further, the washing solvent is one or more of methanol, ethanol, isopropanol, N-butanol, N-dimethylformamide and water.
The application also provides application of the polyquinone amine organic positive electrode material in the field of ion batteries.
The present application will be described in detail with reference to the following embodiments.
Example 1
0.302g (i.e., 2.86 mmol) of 1, 4-benzoquinone and 0.184g (i.e., 1.61 mmol) of 1, 2-cyclohexanediamine were dissolved in 25mL of N, N-dimethylformamide and reacted at 78℃for 24 hours; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and (3) washing the filter cake with ethanol and water for 3 times in sequence, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
FIG. 1 is an X-ray diffraction pattern of the organic positive electrode material of the present application, wherein the main diffraction peak is a broad peak at 23℃and illustrates that the organic positive electrode material of the present application is amorphous.
Fig. 2 is a scanning electron microscope image of the organic positive electrode material of the polyquinone amine prepared in this example, which is in irregular particles at the micrometer scale.
FIG. 3 is an infrared spectrum of a polyquinone amine organic positive electrode material prepared in the present example, in which the main absorption peak range is 1075cm -1 、1228cm -1 、1450cm -1 、1625cm -1 、2900cm -1 、2987cm -1 And 3230cm -1 ～3355cm -1 。
FIG. 4 is a thermogram of a polyquinone amine organic positive electrode material prepared in this example, literThe temperature rate is 10 ℃ for min -1 In the figure, the weight loss is 3.7% in the range of 30-130 ℃, 17.88% in the range of 130-280 ℃, and a large weight loss occurs after 280 ℃.
The organic positive electrode material of the polyquinone amine prepared in the embodiment is used as an active substance of a positive electrode of a zinc ion battery, and the organic positive electrode material is prepared by the following steps: acetylene black: mixing and grinding polyvinylidene fluoride according to the mass ratio of 6:3:1, dropwise adding N-methyl pyrrolidone for grinding, coating on a stainless steel net, vacuum drying to prepare a positive plate, taking a zinc plate as a negative electrode, and 1mol L -1 ZnSO of (2) 4 The solution was an electrolyte and glass fiber was a separator, assembled into CR2032 coin cells, and tested for electrochemical performance.
FIG. 5 is a graph showing that the organic positive electrode material of polyquinolamine prepared in example 1 of the present application was used in zinc ion batteries at 0.1mV s -1 、0.2mV s -1 、0.3mV s -1 、0.4mV s -1 、0.5mV s -1 、0.6mV s -1 、0.8mV s -1 And 1mV s -1 Cyclic voltammogram at sweep rate. In the figure, the main oxidation peak position is about 0.7V, and the main reduction peak position is about 0.5V.
FIG. 6 shows that the organic positive electrode material of the polyquinone amine prepared in the present example is 0.02Ag in a zinc ion battery -1 、0.05Ag -1 、0.1Ag -1 、0.2Ag -1 、0.5Ag -1 And 1Ag -1 Rate capability at current density of 0.02Ag -1 The specific capacity of the first discharge under the current density is 148mAh g -1 。
FIG. 7 is a graph showing that the organic positive electrode material of polyquinone amine prepared in this example is 0.02Ag in zinc ion battery -1 The capacity retention rate of the long cycle chart at current density after 200 times of charge and discharge was 53%.
The electrochemical properties of the discharge specific capacity, the stability of the rate capability, the long-cycle capacity retention rate and the like obtained by the test are superior to those of the positive electrode materials such as poly (1, 4-benzoquinone-4, 4' -diaminobiphenyl), poly (1, 4-benzoquinone-ethylenediamine) and the like in the prior art. For example, the poly (1, 4-benzoquinone-ethylenediamine) positive electrode material is compared with 0.02Ag -1 The specific discharge capacity of the first coil under the current density is 102mAh g -1 Polyquinone amines of the present applicationThe organic positive electrode material has obvious performance advantages.
Example 2
0.324g (i.e. 3 mmol) of 1, 4-benzoquinone and 0.421g (i.e. 3.6 mmol) of 1, 2-cyclohexanediamine were dissolved in 60mL of methanol and 20mL of the mixture was introduced -1 And reacting at 30 ℃ for 48 hours; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and (3) washing the filter cake with N, N-dimethylformamide and ethanol for 3 times, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
Example 3
0.324g (i.e., 3 mmol) of 1, 4-benzoquinone and 0.389g (i.e., 3.6 mmol) of 1, 2-cyclohexanediamine were dissolved in 10mL of N, N-dimethylformamide and 40mL of the mixture was introduced -1 And reacting at 120 ℃ for 2 hours; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and (3) washing the filter cake with ethanol and water for 3 times in sequence, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
Example 4
0.324g (i.e., 3 mmol) of 1, 4-benzoquinone and 0.114g (i.e., 1 mmol) of 1, 2-cyclohexanediamine were dissolved in 50mL of isopropanol and reacted at 80℃for 24 hours; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and (3) washing the filter cake with N, N-dimethylformamide for 3 times, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
Example 5
0.176g (i.e., 1 mmol) of 2, 5-dichloro-1, 4-benzoquinone and 0.125g (i.e., 1.1 mmol) of 1, 2-cyclohexanediamine were dissolved in 20mL of ethanol and reacted under nitrogen at 110℃for 12h; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake with ethanol and N, N-dimethylformamide for 3 times, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
Example 6
0.176g (i.e., 1 mmol) of 2, 5-dichloro-1, 4-benzoquinone and 0.352g (i.e., 0.3 mmol) of 1, 2-cyclohexanediamine were dissolved in 10mL of N, N-dimethylformamide and reacted under argon at 140℃for 12h; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake with ethanol for 3 times, and drying to obtain black solid powder, namely the polyquinone amine organic positive electrode material.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of carrying out the application and that various changes in form and details may be made therein without departing from the spirit and scope of the application. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the application, and the scope of the application is therefore intended to be limited only by the appended claims.
Claims (10)
1. The organic positive electrode material of polyquinone amine is characterized in that the structural formula of the organic positive electrode material of polyquinone amine is as follows:
wherein n is a natural number of 1 or more.
2. The method for preparing a polyquinone amine organic positive electrode material according to claim 1, comprising the steps of:
1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken and dissolved in a reaction solvent A to carry out an oxidation addition reaction; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
3. The method for preparing the polyquinone amine organic positive electrode material according to claim 2, wherein the method specifically comprises the following steps:
1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent A according to the proportion that each gram of 1, 4-benzoquinone and 0.3 to 1.3 grams of 1, 2-cyclohexanediamine are dissolved in 10 to 200mL of reaction solvent A; introducing 0ml of reaction solvent A into the reactor -1 ～4mL min -1 Is introduced into the oxidizing gas flow and is heated to 200-1500 DEG CReacting for 2-48 h; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
4. The method for preparing a polyquinone amine organic positive electrode material according to claim 3, wherein the reaction solvent a is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
5. The method for producing a polyquinone amine organic positive electrode material according to claim 3, wherein the oxidizing gas stream is an oxygen gas stream or an air stream.
6. The method for preparing a polyquinone amine organic positive electrode material according to claim 1, comprising the steps of:
2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B, and condensation reaction is carried out under the protection of inert gas; after the reaction is finished, carrying out suction filtration to obtain a filter cake; and washing the filter cake with a washing solvent, and drying to obtain the polyquinone amine organic positive electrode material.
7. The method for preparing the organic positive electrode material of polyquinone amine according to claim 6, wherein the method specifically comprises the following steps:
2, 5-dichloro-1, 4-benzoquinone and 1, 2-cyclohexanediamine are taken to be dissolved in a reaction solvent B according to the proportion that each gram of 2, 5-dichloro-1, 4-benzoquinone and 1.2-cyclohexanediamine are dissolved in 10-200 mL of the reaction solvent B, and the reaction is carried out for 1-48 h at 20-150 ℃ under the protection of inert gas; after the reaction is finished and cooled, carrying out suction filtration to obtain a filter cake; and washing the filter cake by using a washing solvent, and drying to obtain black solid powder, thus obtaining the polyquinone amine organic anode material.
8. The method for preparing a polyquinone amine organic positive electrode material according to claim 7, wherein the reaction solvent B is methanol, ethanol, isopropanol, N-butanol or N, N-dimethylformamide.
9. The method for preparing a polyquinone amine organic positive electrode material according to claim 3 or 7, wherein the washing solvent is one or more of methanol, ethanol, isopropanol, N-butanol, N-dimethylformamide, and water.
10. The use of the polyquinone amine organic positive electrode material according to claim 1 in the field of ion batteries.
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