CN117567476A - Organic bipolar electrode material and preparation method and application thereof - Google Patents
Organic bipolar electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000003384 small molecules Chemical class 0.000 claims abstract description 42
- -1 cyclohexanecarboxylic acid octahydrate Chemical class 0.000 claims abstract description 9
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims abstract description 8
- WIHHVKUARKTSBU-UHFFFAOYSA-N 4-bromobenzene-1,2-diamine Chemical compound NC1=CC=C(Br)C=C1N WIHHVKUARKTSBU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 14
- 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 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical group 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 150000004689 octahydrates Chemical class 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 abstract 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 238000001816 cooling Methods 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, and discloses an organic bipolar electrode material, a preparation method and application thereof, wherein the structural formula of the organic bipolar small-molecule electrode material is as follows:named DQPZ-3PXZ; the preparation method comprises the following steps: obtaining an intermediate product through the reaction of 4-bromobenzene-1, 2-diamine and cyclohexanecarboxylic acid octahydrate,then the intermediate product reacts with phenoxazine to prepare the organic bipolar small molecular electrode material DQPZ-3PXZ. The invention obtains a high-performance organic bipolar small-molecule electrode material with a p-n structure through the design and synthesis of organic molecules and the control reaction, has insoluble characteristic, can be used as the only electrode material for constructing various double-ion symmetrical batteries, has high capacity, high potential and high stability, and can lead the batteries to have excellent energy density, cycle life and cycle stability; the application range of the organic electrode material is greatly improved, and the energy storage requirement of a large-scale and low-cost battery can be met.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an organic bipolar electrode material, a preparation method thereof and application thereof in an alkali metal ion battery.
Background
Most of the inorganic positive electrode materials used in the commercial lithium ion batteries at present contain oxides of transition metals (such as cobalt), so that the cost is high, the environment is polluted, and the energy storage requirements of the batteries with large scale and low cost are difficult to meet. Therefore, development of a novel lithium ion battery positive electrode material with low cost is urgent.
Organic electrode materials have many unique advantages over inorganic electrode materials, such as flexibility, low cost, eco-friendliness, designability of molecular structure, and better electrochemical performance. Meanwhile, due to the fact that the organic material has a loose solid lattice, compared with the inorganic material, the organic electrode material can store lithium ions and other metal cations more efficiently and stably.
Currently, organic positive electrode materials reported in lithium ion batteries are mostly n-type materials, and their redox potential is generally below 3V (vs. In contrast, organic p-type positive electrode materials with high redox potentials (> 3V) have been rarely reported in lithium ion batteries. In addition, the construction of symmetrical batteries using a single organic electrode material as both positive and negative electrode materials (referred to as bipolar materials) has been very rarely studied, and the cyclic stability of the constructed symmetrical batteries is extremely poor.
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide an organic bipolar electrode material, a preparation method and application thereof, and the organic bipolar electrode material can be used for preparing a high-performance organic bipolar small-molecule electrode material with a p-n structure by designing and synthesizing organic molecules and controlling reaction, wherein an n-type part can store alkali metal ions, a p-type part can store anions in electrolyte, the electrolyte has insoluble characteristic, and the organic bipolar electrode material can be used as a unique electrode material for various double-ion symmetrical batteries, so that the battery has excellent energy density, cycle life and cycle stability.
The invention is realized by the following technical scheme:
in one aspect, the invention provides an organic bipolar small-molecule electrode material with a p-n structure, wherein the structural formula of the organic bipolar small-molecule electrode material is as follows:
for convenience of description, it is named as DQPZ-3PXZ.
The invention designs and synthesizes organic molecules to obtain a high-performance organic bipolar small-molecule electrode material with a p-n structure, wherein an n-type part can store alkali metal ions, a p-type part can store anions in electrolyte, and the electrode material has insoluble characteristics, and the electrode material is used as a unique electrode material and is simultaneously applied to various double-ion symmetrical batteries, so that the battery has excellent energy density, cycle life and cycle stability.
The invention can be used as the only electrode material and applied to the lithium/sodium/potassium double-ion symmetrical battery, namely an organic double-electrode material can be used for constructing 3 alkali metal double-ion symmetrical batteries, so that the application range of the organic electrode material is greatly improved, and the energy storage requirement of the battery with large scale and low cost can be met.
In a second aspect, the invention also provides a preparation method of the organic bipolar small-molecule electrode material, which comprises the steps of obtaining an intermediate product through the reaction of 4-bromobenzene-1, 2-diamine and cyclohexaneketone octahydrate, and then reacting the intermediate product with phenoxazine to prepare the organic bipolar small-molecule electrode material DQPZ-3PXZ, wherein the reaction formula is shown as follows:
in a specific embodiment, the preparation method specifically includes the steps of:
(1) Mixing 4-bromobenzene-1, 2-diamine and cyclohexanecetone octahydrate in an organic solvent I, and reacting at 120-130 ℃ under inert atmosphere to obtain DQPZ-3Br;
(2) Phenoxazine, DQPZ-3Br, X-Phos, sodium t-butoxide and Pd 2 (dba) 3 After mixing, adding an organic solvent II in an inert atmosphere, and reacting at 100-120 ℃ to prepare the DQPZ-3PXZ.
In a specific embodiment, the first organic solvent comprises one or two of glacial acetic acid and ethanol; the organic solvent comprises toluene, xylene or 1, 4-dioxane.
In a third aspect, the invention also provides an application of the organic bipolar small molecular electrode material, or an application of the organic bipolar small molecular electrode material prepared by the preparation method of the organic bipolar small molecular electrode material in an alkali metal ion battery.
In a specific embodiment, the alkali metal ion comprises lithium ion, sodium ion, or potassium ion.
In a specific embodiment, the alkali metal ion battery is an alkali metal double ion symmetric battery.
In a fourth aspect, the present invention also provides an electrode sheet, which is used as a positive electrode sheet and a negative electrode sheet at the same time;
the positive plate comprises an organic positive electrode material, wherein the organic positive electrode material is the organic bipolar small-molecule electrode material or prepared by the preparation method of the organic bipolar small-molecule electrode material;
the negative plate comprises an organic negative electrode material, wherein the organic negative electrode material is the organic bipolar small-molecule electrode material or prepared by the preparation method of the organic bipolar small-molecule electrode material.
In a fifth aspect, the present invention further provides a method for preparing an electrode sheet, where the organic bipolar small molecular electrode material, or the organic bipolar small molecular electrode material prepared by the method for preparing an organic bipolar small molecular electrode material, is mixed with a conductive agent, a binder, and a solvent to prepare a slurry, and then the slurry is coated on an aluminum foil, and is dried to prepare the electrode sheet.
In a sixth aspect, the present invention further provides one or more alkali metal double-ion symmetrical batteries, where the battery positive electrode material includes the organic double-pole small-molecule electrode material, or the organic double-pole small-molecule electrode material prepared by the preparation method of the organic double-pole small-molecule electrode material; and/or the battery cathode material comprises the organic bipolar small-molecule electrode material or the organic bipolar small-molecule electrode material prepared by the preparation method of the organic bipolar small-molecule electrode material; or the positive electrode sheet and/or the negative electrode sheet of the battery include the electrode sheet described above. The alkali metal double-ion symmetrical batteries are lithium double-ion symmetrical batteries, sodium double-ion symmetrical batteries and potassium double-ion symmetrical batteries respectively.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the organic bipolar electrode material, the high-performance organic bipolar small-molecule electrode material with a p-n structure is obtained through the design and synthesis of organic molecules and the control reaction, the n-type part of the high-performance organic bipolar small-molecule electrode material can store alkali metal ions, the p-type part of the high-performance organic bipolar small-molecule electrode material can store anions in electrolyte and has the characteristic of insolubility, and the high-performance organic bipolar small-molecule electrode material is used as the only electrode material and is simultaneously applied to various double-ion symmetrical batteries, so that the high-capacity high-potential high-stability organic bipolar small-molecule electrode material has high capacity, high cycle life and high cycle stability;
2. the organic bipolar electrode material and the preparation method and application thereof provided by the embodiment of the invention can be used as the sole electrode material and simultaneously applied to lithium/sodium/potassium double-ion symmetrical batteries, namely the organic bipolar electrode material can be used for constructing 3 alkali metal double-ion symmetrical batteries, so that the application range of the organic electrode material is greatly improved, and the energy storage requirement of large-scale and low-cost batteries can be met.
Drawings
In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are needed in the examples will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and that other related drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an organic synthetic route for example DQPZ-3PXZ of the present invention;
FIG. 2 shows (a) a hydrogen nuclear magnetic resonance image and (b) a mass spectrum of DQPZ-3PXZ of the present invention;
FIG. 3 is a graph of electrochemical performance of an example DQPZ-3PXZ of the present invention in a lithium (Li) dual ion symmetric battery: (a) a low current charge-discharge graph; (b) a low current long cycle stability graph;
FIG. 4 is a graph of electrochemical performance of an example DQPZ-3PXZ of the invention in a sodium (Na) dual ion symmetric cell: (a) a low current charge-discharge graph; (b) a low current long cycle stability graph;
FIG. 5 is a graph of electrochemical performance of an example DQPZ-3PXZ of the invention in a potassium (K) dual ion symmetric cell: (a) a low current charge-discharge graph; (b) a low current long cycle stability graph.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: no such specific details are necessary to practice the invention. In other instances, well-known structures, circuits, materials, or methods have not been described in detail in order not to obscure the invention.
Throughout the specification, references to "one embodiment," "an embodiment," "one example," or "an example" mean: a particular feature, structure, or characteristic described in connection with the embodiment or example is included within at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment," "in an example," or "in an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Moreover, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and that the illustrations are not necessarily drawn to scale. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, the terms "front", "rear", "left", "right", "upper", "lower", "vertical", "horizontal", "high", "low", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the scope of the present invention.
Example 1
As shown in fig. 1, the preparation method of the organic bipolar electrode material DQPZ-3PXZ provided by the embodiment of the invention comprises the following steps:
4-bromobenzene-1, 2-diamine (1.41 g,7.53 mmol), cyclohexanecarboxylic acid octahydrate (0.783 g,2.51 mmol) was charged into a 250ml two-necked flask. While 50ml of glacial acetic acid was added. The mixture was stirred at 125℃for 24h. The mixture was then filtered and the precipitate was washed several times with water, ethanol and acetone, followed by drying overnight in an oven at 100 ℃. Finally, the DQPZ-3Br yellow-green solid with the yield of more than 90% is obtained.
Subsequently, phenoxazine (0.906 g,4.95 mmol), DQPZ-3Br (0.927 g,1.5 mmol), X-Phos (257.2 mg,54 mmol), sodium tert-butoxide (475.2 mg,4.95 mmol) and Pd were reacted 2 (dba) 3 (135 mg,13.5 mmol) then under N 2 45mL of toluene was added to the atmosphere. The mixture was reacted at 110℃for 3 days. After cooling to room temperature, the solid was directly washed three times with water and ethanol. Then dried at 100℃to give 1.11g of a bluish-black solid. The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum and mass spectrum detection, as shown in fig. 2, and the obtained product is DQPZ-3PXZ.
Example 2
As shown in fig. 1, the preparation method of the organic bipolar electrode material DQPZ-3PXZ provided by the embodiment of the invention comprises the following steps:
as shown in FIG. 1, 4-bromobenzene-1, 2-diamine (1.41 g,7.53 mmol), cyclohexanecarboxylic acid octahydrate (0.783 g,2.51 mmol) was charged into a 250ml two-necked flask. Simultaneously, 25ml of glacial acetic acid and 25ml of ethanol mixed solvent are added. The mixture was stirred at 125℃for 24h. The mixture was then filtered and the precipitate was washed several times with water, ethanol and acetone, followed by drying overnight in an oven at 100 ℃. Finally, the DQPZ-3Br yellow-green solid with the yield of more than 90% is obtained.
Subsequently, phenoxazine (0.906 g,4.95 mmol), DQPZ-3Br (0.927 g,1.5 mmol), X-Phos (257.2 mg,54 mmol), sodium tert-butoxide (475.2 mg,4.95 mmol) and Pd were reacted 2 (dba) 3 (135 mg,13.5 mmol) then under N 2 45mL of 1, 4-dioxane was added to the atmosphere. The mixture was reacted at 110℃for 3 days. After cooling to room temperature, the solid was directly washed three times with water and ethanol. Then dried at 100℃to give 1.11g of DQPZ-3-PXZ as a blue-black solid.
Example 3
As shown in fig. 1, the preparation method of the organic bipolar electrode material DQPZ-3PXZ provided by the embodiment of the invention comprises the following steps:
as shown in FIG. 1, 4-bromobenzene-1, 2-diamine (1.41 g,7.53 mmol), cyclohexanecarboxylic acid octahydrate (0.783 g,2.51 mmol) was charged into a 250ml two-necked flask. While 50ml of ethanol was added. The mixture was stirred at 125℃for 24h. The mixture was then filtered and the precipitate was washed several times with water, ethanol and acetone, followed by drying overnight in an oven at 100 ℃. Finally, the DQPZ-3Br yellow-green solid with the yield of more than 90% is obtained.
Subsequently, phenoxazine (0.906 g,4.95 mmol), DQPZ-3Br (0.927 g,1.5 mmol), X-Phos (257.2 mg,54 mmol), sodium tert-butoxide (475.2 mg,4.95 mmol) and Pd were reacted 2 (dba) 3 (135 mg,13.5 mmol) then under N 2 45mL of xylene was added to the atmosphere. The mixture was reacted at 110℃for 3 days. After cooling to room temperature, the solid was directly washed three times with water and ethanol. Then dried at 100℃to give 1.11g of DQPZ-3-PXZ as a blue-black solid.
Example 4
The preparation method of the DQPZ-3PXZ electrode sheet provided by the embodiment of the invention comprises the following steps:
the DQPZ-3PXZ (60 wt%), keqin black (30 wt%) and polyacrylonitrile copolymer (10 wt%) prepared in example 1 were mixed and then uniformly coated on an aluminum foil. Wherein the load mass of DQPZ-3PXZ on the electrode sheet is more than 2mg cm -2 Pressing into round aluminum electrode plate.
And then the single electrode plate is respectively used as an anode electrode plate and a cathode electrode plate to be applied to a lithium/sodium/potassium double-ion symmetrical battery, and the oxidation-reduction potential, the actual specific capacity and the cycling stability of the single electrode plate are tested.
Example 5
The preparation method of the lithium double-ion symmetrical battery provided by the embodiment of the invention comprises the following steps:
a lithium-ion-dual symmetric battery was assembled using the unactivated electrode sheet of DQPZ-3PXZ prepared in example 4 as the positive and negative electrodes and 3M LiFSI+TEGDME as the electrolyte, and its electrochemical performance was tested.
As can be seen from FIG. 3, the median voltage of the lithium-ion symmetrical battery is about 1.36V, and the stable specific capacity can reach 85mAh g -1 . Therefore, based on the calculation of the positive electrode material, the lithium double-ion symmetrical battery can reach 116Wh kg -1 Is a high energy density of (a). At 2Ag -1 Under large current, after long circulation of 15000 circles, the specific discharge capacity can be stabilized at 73mAh g -1 The capacity retention was about 100%.
Example 6
The preparation method of the sodium double-ion symmetrical battery provided by the embodiment of the invention comprises the following steps:
a sodium dual ion symmetric battery was assembled using the unactivated DQPZ-3PXZ electrode sheet prepared in example 4 as the positive and negative electrodes and 1.5M NaFSI+TEGDME as the electrolyte, and its electrochemical performance was tested.
As can be seen from FIG. 4, the median voltage of the sodium dual-ion symmetrical battery is about 1.34V, and the stable specific capacity can reach 66mAh g -1 . Therefore, based on the calculation of the positive electrode material, the sodium double-ion symmetrical battery can reach 88Wh kg -1 Is a high energy density of (a). At 2Ag -1 Under large current, the discharge specific capacity can be stabilized at 56mAh g after 40000 circles of long circulation -1 The capacity retention was about 98%.
Example 7
The preparation method of the potassium double-ion symmetrical battery provided by the embodiment of the invention comprises the following steps:
a potassium double ion symmetric battery was assembled using the unactivated DQPZ-3PXZ electrode sheet prepared in example 4 as the positive and negative electrode and 3M KFSI+TEGDME as the electrolyte, and its electrochemical performance was tested.
As can be seen from FIG. 5, the median voltage of the full electricity is about 1.43V, and the stable specific capacity can reach 72mAh g -1 . Therefore, based on the calculation of the positive electrode material, the symmetrical battery can reach 103Wh kg -1 Is a high energy density of (a). At 2Ag -1 Under large current, the discharge specific capacity can be stabilized at 60mAh g after 40000 circles of long circulation -1 The capacity retention was about 97%.
Through testing the performances of the lithium, sodium and potassium double-ion symmetrical batteries, the DQPZ-3PXZ is proved to be a novel organic bipolar small-molecule electrode material with high capacity, high potential and high stability in the lithium/sodium/potassium double-ion symmetrical battery, and the DQPZ-3PXZ is taken as the sole electrode material to be simultaneously applied to the lithium/sodium/potassium double-ion symmetrical battery, so that the DQPZ-3 double-ion symmetrical battery can obtain excellent energy density, cycle life and cycle stability.
The organic bipolar electrode material can be used for constructing 3 alkali metal double-ion symmetrical batteries, greatly improves the application range of the organic electrode material, and can meet the energy storage requirement of batteries with large scale and low cost.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. An organic bipolar small-molecule electrode material with a p-n structure is characterized in that the structural formula of the organic bipolar small-molecule electrode material is as follows:
named DQPZ-3PXZ.
2. The preparation method of the organic bipolar small molecular electrode material is characterized in that an intermediate product is obtained by reacting 4-bromobenzene-1, 2-diamine and cyclohexanecarboxylic acid octahydrate, and then the intermediate product is reacted with phenoxazine to prepare the organic bipolar small molecular electrode material DQPZ-3PXZ, wherein the reaction formula is shown as follows:
3. the method for preparing the organic bipolar small-molecule electrode material according to claim 2, which is characterized by comprising the following specific steps:
(1) Mixing 4-bromobenzene-1, 2-diamine and cyclohexanecetone octahydrate in an organic solvent I, and reacting at 120-130 ℃ under inert atmosphere to obtain DQPZ-3Br;
(2) Phenoxazine, DQPZ-3Br, X-Phos, sodium t-butoxide and Pd 2 (dba) 3 After mixing, adding an organic solvent II in an inert atmosphere, and reacting at 100-120 ℃ to prepare the DQPZ-3PXZ.
4. The method for preparing an organic bipolar small-molecule electrode material according to claim 3, wherein the organic solvent one comprises one or two of glacial acetic acid and ethanol; the organic solvent comprises toluene, xylene or 1, 4-dioxane.
5. The application of the organic bipolar type small molecular electrode material is characterized in that the organic bipolar type small molecular electrode material disclosed in claim 1 or the application of the organic bipolar type small molecular electrode material prepared by the preparation method of the organic bipolar type small molecular electrode material disclosed in any one of claims 2-4 in an alkali metal ion battery.
6. The use of an organic bipolar small molecule electrode material of claim 5, wherein said alkali metal ions comprise lithium, sodium or potassium ions.
7. The use of an organic bipolar small molecule electrode material according to claim 5 wherein said alkali metal ion battery is an alkali metal double ion symmetric battery.
8. An electrode sheet, characterized in that the electrode sheet is used as a positive electrode sheet and a negative electrode sheet at the same time;
the positive plate comprises an organic positive electrode material, wherein the organic positive electrode material is the organic bipolar small-molecule electrode material of claim 1 or prepared by the preparation method of the organic bipolar small-molecule electrode material of any one of claims 2-4;
the negative plate comprises an organic negative electrode material, wherein the organic negative electrode material is the organic bipolar small-molecule electrode material of claim 1 or prepared by the preparation method of the organic bipolar small-molecule electrode material of any one of claims 2-4.
9. The preparation method of the electrode slice is characterized in that the organic bipolar small-molecule electrode material of claim 1 or the organic bipolar small-molecule electrode material prepared by the preparation method of any one of claims 2-4 is mixed with a conductive agent, a binder and a solvent to prepare slurry, and then the slurry is coated on an aluminum foil, and the electrode slice is prepared after drying.
10. One or more alkali metal double-ion symmetrical batteries are characterized in that the battery anode material comprises the organic double-pole small-molecule electrode material of claim 1 or the organic double-pole small-molecule electrode material prepared by the preparation method of the organic double-pole small-molecule electrode material of any one of claims 2-4; and/or the battery cathode material comprises the organic bipolar small-molecule electrode material of claim 1 or the organic bipolar small-molecule electrode material prepared by the preparation method of the organic bipolar small-molecule electrode material of any one of claims 2-4; or the positive electrode sheet and/or the negative electrode sheet of the battery includes the electrode sheet of claim 7.
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