CN111342047A - High-performance organic positive electrode material and application thereof in potassium ion battery - Google Patents

High-performance organic positive electrode material and application thereof in potassium ion battery Download PDF

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CN111342047A
CN111342047A CN201911377301.5A CN201911377301A CN111342047A CN 111342047 A CN111342047 A CN 111342047A CN 201911377301 A CN201911377301 A CN 201911377301A CN 111342047 A CN111342047 A CN 111342047A
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positive electrode
ptcdi
daq
potassium ion
performance organic
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CN111342047B (en
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樊聪
唐武
赵伟
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Ougeni Material Technology Jiangsu Co ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • 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

Abstract

The invention discloses a high-performance organic anode material which is named as PTCDI-DAQ and has the following structural formula:
Figure DDA0002341294440000011
the invention provides a novel organic micromolecular anode material, which is applied to a potassium ion half battery or a full battery, shows excellent electrochemical performance, and has the characteristics of high specific capacity, high rate capability, excellent stability and the like.

Description

High-performance organic positive electrode material and application thereof in potassium ion battery
Technical Field
The invention relates to the technical field of batteries, in particular to a high-performance organic cathode material and application thereof in a potassium ion battery.
Background
At present, commercial lithium ion batteries have limited lithium resource stock, and the positive electrode material containing lithium and cobalt has high cost and pollutes the environment, so that the large-scale development of energy storage application is difficult. It is urgently required to develop other secondary battery systems having low cost and excellent performance. The potassium ion battery is a novel secondary battery system with potential because the potassium element reserves are very rich and the electrochemical performance is similar to that of the lithium ion battery. Currently, inorganic positive and negative electrode materials suitable for potassium ion batteries are extremely rare. Although there has been little progress in potassium ion batteries based on inorganic electrode materials, the energy density, rate capability, and particularly cycle stability of potassium ion batteries are very distant from practical use.
Because the cost of the organic material is extremely low, the use of the organic electrode material with electrochemical activity in the potassium ion battery can further reduce the production cost of the potassium ion battery. Compared with inorganic electrode materials, the organic electrode materials have more efficient and stable potassium ion storage than inorganic materials due to the fact that the organic electrode materials have more empty solid crystal lattices. Nevertheless, organic positive and negative electrode materials currently suitable for potassium ion batteries are extremely rare.
In addition, the organic potassium ion full-cell prepared based on the organic anode material and the organic cathode material is less reported at present. And the energy density, rate capability and cycling stability of the organic potassium ion full battery need to be further improved.
Disclosure of Invention
Aiming at the technical problems, the invention provides a high-performance organic cathode material for solving the problems and application thereof in a potassium ion battery.
The invention is realized by the following technical scheme:
a high-performance organic cathode material is named as PTCDI-DAQ, and the structural formula is as follows:
Figure BDA0002341294420000011
a preparation method of a high-performance organic cathode material is disclosed, wherein the high-performance organic cathode material PTCDI-DAQ is obtained by reacting 3,4,9, 10-perylenetetracarboxylic dianhydride and 2-aminoanthraquinone as raw materials:
Figure BDA0002341294420000021
further, zinc acetate is used as a catalyst, and 3,4,9, 10-perylenetetracarboxylic dianhydride and 2-aminoanthraquinone are catalyzed in an inert atmosphere to react to prepare the high-performance organic cathode material PTCDI-DAQ.
Further, imidazole is used as a solvent.
Further, adding 3,4,9, 10-perylenetetracarboxylic dianhydride, 2-aminoanthraquinone and a catalyst into a solvent under the condition of inert atmosphere; firstly heating to 100-120 ℃, and keeping for 1-2 h; continuously heating to 130-150 ℃ for continuous reaction.
The high-performance organic cathode material is applied to the potassium ion battery.
A positive electrode sheet uses PTCDI-DAQ as a positive electrode material.
A potassium ion half cell takes PTCDI-DAQ as a positive electrode material or adopts the positive electrode plate.
A potassium ion full battery takes PTCDI-DAQ as a positive electrode material or adopts the positive electrode sheet.
Further, the potassium ion full battery comprises a positive plate and a negative plate, wherein the raw material of the positive plate comprises PTCDI-DAQ; the active organic negative electrode material of the negative electrode plate comprises K4TP; the negative plate is K2TP is taken as a raw material to be prepared into K through electrochemical in-situ reduction after being prepared into an electrode slice4And (3) preparing TP.
The invention has the following advantages and beneficial effects:
the invention provides a novel organic micromolecule anode material, which is applied to a potassium ion half battery or a full battery, shows super-excellent electrochemical performance, and has the characteristics of high specific capacity, high rate capability, excellent stability and the like; an all-organic potassium ion all-battery based on the organic positive electrode is prepared, and the energy density, rate capability and cycling stability of the all-organic potassium ion all-battery are the highest levels in the world at present.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is an infrared spectrum of PTCDI-DAQ;
FIG. 2 is a redox plot of PTCDI-DAQ in a potassium ion half cell;
FIG. 3 is a cycle test chart of a PTCDI-DAQ potassium ion half-cell under a low current condition;
FIG. 4 is a graph of the rate performance of a PTCDI-DAQ potassium ion half-cell;
FIG. 5 is a large current long cycle test chart of a PTCDI-DAQ potassium ion half-cell;
FIG. 6 is a graph of the PTCDI-DAQ potassium ion full cell discharge voltage;
FIG. 7 is a cycle test chart of a PTCDI-DAQ potassium ion full cell under a low current condition;
FIG. 8 is a graph of rate performance of a PTCDI-DAQ potassium ion full cell;
FIG. 9 is a high current cycling test chart of a PTCDI-DAQ potassium ion full cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
The embodiment provides a high-performance organic cathode material, which is named as PTCDI-DAQ and has a structural formula shown as follows:
Figure BDA0002341294420000031
the specific preparation method is as follows:
500mg of 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) (1.28mmol), 716mg of 2-aminoanthraquinone (3.2mmol, at least 2.5 equivalents or more), and 0.1g of zinc acetate (Zn (OAc))2Catalyst (0.46mmol) and 20g of imidazole solvent (294mmo) were added separately to a reaction flask; then, the reaction bottle is pumped and ventilated for 3 times, namely all substances are pumped and vacuumized after being added into the reaction bottle, then nitrogen is introduced, and the gas is pumped and ventilated for 3 times repeatedly; finally, under the protection of nitrogen, the mixture is slowly heatedHeating to 110 deg.C for 2h, and heating to 140 deg.C for at least 2 d. After the reaction is finished, 100ml of deionized water is added into the reaction bottle after the temperature is returned to room temperature, and the mixture is filtered after being fully stirred. The crude product was dried and then solvent extracted with Tetrahydrofuran (THF) at elevated temperature for at least 1 week to remove the two soluble starting materials. The remaining product was PTCDI-DAQ with a yield of 95% (975mg,1.22mmol) and structural characterization as shown in FIG. 1.
The reaction formula is shown as follows:
Figure BDA0002341294420000032
example 2
The embodiment provides a potassium ion half cell, and the preparation process of the potassium ion half cell is as follows: mixing PTCDI-DAQ, conductive carbon additive and binder; then evenly coating the aluminum foil; pressing into a circular aluminum electrode plate; applying the electrode plate to a potassium ion half cell; and testing the oxidation-reduction potential, the actual specific capacity, the cycling stability and the rate capability of the material. The half-cell performance proves that PTCDI-DAQ is an organic small-molecule cathode material with high capacity, high rate performance and high stability in a potassium ion cell.
As can be seen from the attached figures 3 to 5, the PTCDI-DAQ organic positive electrode shows 200mAh g in the potassium ion half-cell-1～220mAh·g-1The actual specific capacity of (a); at 10 A.g-1(50C) Under the condition of large current, the PTCDI-DAQ still keeps 150mAh g-1～170mAh·g-1The actual specific capacity of (a); at 3 A.g-1Under the condition of large current, PTCDI-DAQ stably circulates for 900 weeks, and the specific capacity is still kept at 147mAh g-1. These properties are the best performance of the organic small molecule material in the potassium ion half cell at present.
Example 3
The embodiment provides a potassium ion full cell, and the preparation process of the full organic potassium ion full cell comprises the following steps:
(1) firstly preparing potassium terephthalate (K)2TP) negative electrode sheet: firstly, K is2TP, conductive carbon additive and binder are mixed; then theUniformly coating on a copper foil; pressing into a circular copper electrode slice; the electrode slice is firstly applied to a potassium ion half cell, and the reduction state-K is generated through the first reduction process4TP; will be based on K4Taking out the electrode slice of the TP;
(2) assembly of PTCDI-DAQ-based positive electrode and K4A full organic potassium ion battery with a TP cathode; and testing the working voltage, the actual specific capacity, the cycling stability and the rate capability of the material.
As can be seen from FIGS. 6 to 9, PTCDI-DAQ II K2The working voltage of the TP full cell is 0.2V-3.2V, and the average working voltage is about 1.2V. At 100mA · g-1Under the condition of small current, the full battery is circulated for 300 weeks, and the specific capacity of the positive electrode is still maintained to be 132mAh g-1And (4) a positive electrode. At 10 A.g-1Under the condition of large current, the full battery still keeps 87 mAh.g-1Actual specific capacity of the positive electrode. The full cell exhibited superior stability at 3A g-1The specific capacity of the positive electrode is maintained at 62mAh g after 10000 cycles under the condition of large current-1And (4) a positive electrode. These performance indicators are currently the best organic potassium ion full cell performance worldwide.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The high-performance organic cathode material is named as PTCDI-DAQ, and the structural formula is as follows:
Figure FDA0002341294410000011
2. the preparation method of the high-performance organic cathode material is characterized in that the high-performance organic cathode material PTCDI-DAQ is obtained by reacting 3,4,9, 10-perylenetetracarboxylic dianhydride and 2-aminoanthraquinone as raw materials:
Figure FDA0002341294410000012
3. the preparation method of the high-performance organic cathode material as claimed in claim 2, wherein the high-performance organic cathode material PTCDI-DAQ is prepared by using zinc acetate as a catalyst and catalyzing 3,4,9, 10-perylenetetracarboxylic dianhydride and 2-aminoanthraquinone to react in an inert atmosphere.
4. The method for preparing a high-performance organic cathode material according to claim 2 or 3, wherein imidazole is used as a solvent.
5. The preparation method of the high-performance organic cathode material according to claim 4, characterized in that 3,4,9, 10-perylenetetracarboxylic dianhydride, 2-aminoanthraquinone and a catalyst are added into a solvent under inert atmosphere; firstly heating to 100-120 ℃, and keeping for 1-2 h; continuously heating to 130-150 ℃ for continuous reaction.
6. Use of the high performance organic positive electrode material according to any one of claims 1 to 5 in a potassium ion battery.
7. A positive electrode sheet is characterized in that PTCDI-DAQ is used as a positive electrode material.
8. A potassium-ion half cell, characterized in that PTCDI-DAQ is used as a positive electrode material or a positive electrode sheet according to claim 7 is used.
9. A potassium ion full cell, wherein PTCDI-DAQ is used as a positive electrode material or the positive electrode sheet according to claim 7 is used.
10. The potassium ion full cell according to claim 9, wherein the potassium ion full cell comprises a positive electrode sheet and a negative electrode sheet, and the raw material of the positive electrode sheet comprises PTCDI-DAQ; the active organic negative electrode material of the negative electrode plate comprises K4TP; the negative plate is K2TP is taken as a raw material to be prepared into K through electrochemical in-situ reduction after being prepared into an electrode slice4And (3) preparing TP.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939760A (en) * 2021-02-05 2021-06-11 青岛科技大学 Application of oxidized perylene in organic anode material of lithium ion battery
CN114456356A (en) * 2022-01-24 2022-05-10 郑州大学 Poly (perylene) tetracarboxydiimide, preparation method thereof and application thereof in lithium/sodium battery
CN114744163A (en) * 2022-04-21 2022-07-12 电子科技大学 Organic positive electrode material, preparation method and application in alkali metal ion battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085864A (en) * 2019-06-04 2019-08-02 欧格尼材料科技江苏有限公司 The preparation method and application of potassium or based lithium-ion battery positive plate
CN110112414A (en) * 2019-06-11 2019-08-09 欧格尼材料科技江苏有限公司 A kind of novel anode material, preparation method and applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085864A (en) * 2019-06-04 2019-08-02 欧格尼材料科技江苏有限公司 The preparation method and application of potassium or based lithium-ion battery positive plate
CN110112414A (en) * 2019-06-11 2019-08-09 欧格尼材料科技江苏有限公司 A kind of novel anode material, preparation method and applications

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939760A (en) * 2021-02-05 2021-06-11 青岛科技大学 Application of oxidized perylene in organic anode material of lithium ion battery
CN114456356A (en) * 2022-01-24 2022-05-10 郑州大学 Poly (perylene) tetracarboxydiimide, preparation method thereof and application thereof in lithium/sodium battery
CN114744163A (en) * 2022-04-21 2022-07-12 电子科技大学 Organic positive electrode material, preparation method and application in alkali metal ion battery
CN114744163B (en) * 2022-04-21 2023-04-25 电子科技大学 Organic positive electrode material, preparation method and application thereof in alkali metal ion battery

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