CN117038977A - Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof - Google Patents
Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117038977A CN117038977A CN202310602750.5A CN202310602750A CN117038977A CN 117038977 A CN117038977 A CN 117038977A CN 202310602750 A CN202310602750 A CN 202310602750A CN 117038977 A CN117038977 A CN 117038977A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- anthraquinone
- poly
- battery
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- LSOTZYUVGZKSHR-UHFFFAOYSA-N anthracene-1,4-dione Chemical compound C1=CC=C2C=C3C(=O)C=CC(=O)C3=CC2=C1 LSOTZYUVGZKSHR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 99
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 99
- 239000002041 carbon nanotube Substances 0.000 claims description 89
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 89
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 239000006258 conductive agent Substances 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 18
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- -1 super P Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- CAHGWVAXFJXDNI-UHFFFAOYSA-N 1,4-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2Cl CAHGWVAXFJXDNI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000447 polyanionic polymer Chemical class 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 7
- 239000011368 organic material Substances 0.000 abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 23
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 15
- 238000011056 performance test Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 10
- 238000010408 sweeping Methods 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000013543 active substance Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 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
- H01M4/36—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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of water-based battery materials, and particularly discloses a water-based battery poly-1, 4-anthraquinone negative electrode material, a preparation method and application thereof, wherein the adopted negative electrode is a poly-1, 4-anthraquinone organic material, compared with the existing water-based battery inorganic material negative electrode and small molecule organic negative electrode, the solution problem of the negative electrode material and the dissolution of discharge products in a water-based electrolyte is solved; the aqueous battery formed by the poly-1, 4 anthraquinone organic negative electrode and the commercial sintered nickel positive electrode has long cycle life, excellent multiplying power performance and high output voltage, and has wide raw material sources and low price, so that the problems of low energy density and short cycle life of the conventional aqueous battery can be effectively solved, and the application of the aqueous battery in the field of large-scale energy storage can be promoted.
Description
Technical Field
The invention belongs to the technical field of water-based battery materials, and particularly relates to a poly-1, 4-anthraquinone negative electrode material of a water-based battery, and a preparation method and application thereof.
Background
As one of the largest carbon emission sources, power generation needs to be free from dependence on fossil fuels, utilize sustainable energy sources such as solar energy and wind energy, however, their intermittence prevents integration with electric power systems. Rechargeable aqueous batteries are one of the effective ways to achieve power output due to factors such as high safety, cost effectiveness, and sustainability. The electrochemical performance of aqueous cells is largely dependent on the choice and matching of electrode materials. Compared with inorganic materials, the organic negative electrode has the advantages of wide sources, environmental friendliness, structural diversity, high controllability and the like.
The quinone organic compound with conjugated structure is mainly composed of C, H, O, is ubiquitous in natural plants, is easy to degrade, stores charge through coordination mechanism between metal ion and carbonyl when being used as electrode material, and shows high redox reversibility and quick kinetics, and has larger specific capacity. However, the research of quinone organic electronics has mainly focused on rechargeable organic batteries such as lithium/sodium/potassium ion batteries, which are generally faced with serious dissolution problems in organic electrolyte; the zinc metal side has the problem of dendrite growth when the zinc metal is applied to a water-based zinc ion battery; the low solubility of such organic materials in aqueous electrolytes results in a flow battery with limited energy density (j.am. Chem. Soc.2022,144, 8066-8072). In addition, the small molecular quinone organic material is generally poor in structural stability and easy to dissolve in aqueous solution in the circulating process, so that the problems of short circulating life and poor multiplying power performance of the water system battery are caused. Therefore, development of a quinone organic negative electrode material with stable structure and low cost is needed to construct a novel high-performance water-based battery.
Disclosure of Invention
The invention aims to develop a quinone organic negative electrode material with stable structure and low price to construct a novel high-performance water-based battery aiming at the problems of short cycle life and low capacity under high current when a small molecular quinone organic negative electrode for the water-based battery is applied to the water-based battery.
In order to achieve the above object, the invention provides a poly 1,4 anthraquinone negative electrode material of an aqueous battery, comprising poly 1,4 anthraquinone, wherein the poly 1,4 anthraquinone has the following structure:
；
wherein n is the degree of polymerization.
Further, in the poly-1, 4 anthraquinone negative electrode material of the water-based battery, n is the polymerization degree, and the value range of n is 3000-6000.
The invention also provides a preparation method of the poly 1,4 anthraquinone negative electrode material of the water-based battery, which comprises the following steps:
(1) Dissolving bis 1, 5-cyclooctadiene, 2-bipyridine and 1, 5-cyclooctadiene into dimethylformamide to obtain a first mixed solution;
(2) Dissolving 1, 4-dichloro anthraquinone into dimethylformamide to obtain a second mixed solution;
(3) Adding the second mixed solution in the step (2) into the first mixed solution in the step (1), fully reacting at the temperature of 45-55 ℃ under the protection of nitrogen, and cooling to room temperature to obtain a reaction solution;
(4) Settling the reaction solution in the step (3) in a dilute hydrochloric acid solution to generate yellow precipitate, and filtering to obtain the yellow precipitate;
(5) Washing the yellow precipitate with dimethylformamide, dilute hydrochloric acid, deionized water and methanol in sequence, and vacuum drying to obtain the poly-1, 4-anthraquinone.
Further, the reaction is carried out in three sections in the step (3) to obtain a reaction solution; the first-stage reaction: the temperature is 50-55 ℃, the pressure is normal pressure, and the reaction time is 6-8 hours; two-stage reaction: the temperature is 45-50 ℃, the pressure is 1.2-1.5 megapascals, and the reaction time is 7-9 hours; three-stage reaction: the temperature is 50-55 ℃, the pressure is 0.6-0.8 megapascal, and the reaction time is 4-6 hours.
Further, the concentration of the dilute hydrochloric acid solution in the step (4) is 0.45-0.55 mol/L.
Further, in the step (5), the temperature of vacuum drying is 70-80 ℃ and the time is 9-12 hours.
The invention also provides application of the poly-1, 4-anthraquinone negative electrode material of the water-based battery, wherein the poly-1, 4-anthraquinone is used as a negative electrode of the water-based battery.
The invention also provides a water-based battery, which comprises a positive electrode, a negative electrode, a diaphragm, a current collector and electrolyte, wherein the poly-1, 4 anthraquinone is used as the negative electrode of the water-based battery; the preparation method of the negative electrode comprises the following steps:
1) The negative electrode comprises the following components in parts by weight: 58-62 parts of poly 1,4 anthraquinone, 28-32 parts of conductive agent and 8-12 parts of binder; weighing all components composing the negative electrode according to the weight proportion, and uniformly mixing to obtain a mixture;
2) And (3) grinding the mixture uniformly, adding deionized water and ethanol to prepare slurry, grinding into sheets, fixing on a foam nickel current collector, and vacuum drying to obtain the P14AQ organic negative electrode.
Further, the conductive agent is one or more of ketjen black, carbon black, super P, carbon nano tubes and graphene; the binder is one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose, polyacrylic acid and polytetrafluoroethylene; the diaphragm is filter paper or glass fiber; the electrolyte is one or more of lithium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution, and the concentration of the electrolyte is 5-10 mol/L; the positive electrode is made of any one of nickel-based compounds, prussian blue analogues or polyanion compounds; the current collector is made of nickel screen, titanium foil, stainless steel foil, carbon paper or graphite felt.
Further, the conductive agent comprises the following components in parts by weight: 20-25 parts of carbon nanotubes and 30-35 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.7-0.9 mol/L, and acidizing for 4-6 hours to obtain an acidized carbon nano tube; 2) Placing the acidified carbon nanotubes in absolute ethyl alcohol, and performing ultrasonic vibration for 15-20 min to obtain ultrasonic vibration carbon nanotubes; 3) And placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, carrying out ultrasonic vibration for 25-30 min, taking out and drying.
The invention relates to a poly 1,4 anthraquinone negative electrode material of a water system battery, a preparation method and application thereof, wherein the reaction formula of the poly 1,4 anthraquinone is as follows:
。
compared with the prior art, the invention has the following beneficial effects: compared with the existing inorganic material negative electrode and micromolecular organic negative electrode of the water-based battery, the adopted negative electrode is a poly-1, 4-anthraquinone organic material, and solves the problem of dissolution of the negative electrode material and a discharge product thereof in the water-based electrolyte; the aqueous battery formed by the poly-1, 4 anthraquinone organic negative electrode and the commercial sintered nickel positive electrode has long cycle life, excellent multiplying power performance and high output voltage, and has wide raw material sources and low price, so that the problems of low energy density and short cycle life of the conventional aqueous battery can be effectively solved, and the application of the aqueous battery in the field of large-scale energy storage can be promoted.
According to the poly 1,4 anthraquinone negative electrode material of the water-based battery, and the preparation method and application thereof, the preparation method of the poly 1,4 anthraquinone is optimized, the polymerization degree of the poly 1,4 anthraquinone is distributed more uniformly in three sections in the step (3), and the polymerization degree of more than 90wt% of the polymer is concentrated in 5000-5500, so that the performance of the water-based battery is more stable, the energy density of the water-based battery is effectively increased, and the cycle life of the water-based battery is prolonged; the conductive agent consists of carbon nanotubes and Super P, and the carbon nanotubes are modified, and acid treatment is carried out on the carbon nanotubes, so that the affinity between the carbon nanotubes and a solute can be increased, and the dispersibility of the carbon nanotubes in the solute is improved; and then sequentially placing the carbon nano tube in absolute ethyl alcohol and isopropanol for ultrasonic vibration treatment, so that lattice defects or lattice distortion can be formed on the surface of the carbon nano tube, the carbon nano tube is tightly combined with Super P, poly 1,4 anthraquinone and other components, the dissolution process of the poly 1,4 anthraquinone in the water-based electrolyte is effectively delayed, the performance stability of the water-based battery is further improved, and the service life of the water-based battery is prolonged.
The invention relates to a poly-1, 4 anthraquinone negative electrode material of a water-based battery, a preparation method and application thereof, and an assembly method of the water-based battery comprises the following steps: and (3) adopting commercial sintered nickel (or other available materials) as a positive electrode, matching the positive electrode with the P14AQ organic negative electrode and electrolyte, and assembling the aqueous potassium ion battery.
Drawings
FIG. 1 is a MALDI-TOF spectrum of example 1 of the present invention; the polymerization degree of the P14AQ is between 3000 and 6000 as shown by the graph;
FIG. 2 is a cyclic voltammogram of the aqueous cell of example 1 of the present invention at 1m V/s and 2 mV/s; at 1mV/s, the water system battery has 1 peak position corresponding to oxidation reaction in the charging process: 1.31 V, 1 peak position corresponding to reduction reaction appears in the discharge process: 1.04 V is provided. When the sweeping speed is increased to 2 mV/s, the sweeping speed is respectively moved to 1.37V and 0.99V;
FIG. 3 is a graph showing the cycle performance of the aqueous battery of example 1 of the present invention at 0.3A/g; 0.3 The first circle coulomb efficiency of the A/g water system battery reaches 32.11 percent, and the reversible capacity reaches 82.88 mAh/g; after 100 circles of circulation, the coulomb efficiency is 97.22%, and the reversible capacity reaches 78.33 mAh/g, which shows that the water system battery has better circulation performance;
FIG. 4 is a graph showing the rate performance of the aqueous battery of example 1 of the present invention; the initial circulation is that the capacity of the water system battery is attenuated to some extent at 0.1A/g, the coulombic efficiency is low, but the reversible capacities at 0.3, 0.5, 0.8 and 1.0A/g are 97.59, 90.03, 84.22 and 80.57 mAh/g respectively, which shows that the water system battery has excellent multiplying power performance and considerable research prospect;
FIG. 5 is a graph showing the charge and discharge curves of the aqueous battery of example 1 according to the present invention at different current densities; the average working voltage of the water-based battery is maintained at 1.05-1.07V, so that the energy density of the water-based battery is improved.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments.
A poly 1,4 anthraquinone negative electrode material for an aqueous battery comprising poly 1,4 anthraquinone, said poly 1,4 anthraquinone having the following structure:
；
wherein n is the polymerization degree, and the value range of n is 3000-6000; the quinone organic electrode is applied to a water-based zinc ion battery, and dendrite growth is caused on the zinc metal side; the solubility of the organic materials in the aqueous electrolyte is low, so that the energy density of the flow battery is limited; in addition, the small molecular quinone organic material is generally poor in structural stability and easy to dissolve in aqueous solution in the circulating process, so that the problems of short circulating life and poor multiplying power performance of the water system battery are caused; the poly 1,4 anthraquinone cathode material is synthesized, and compared with 1,4 anthraquinone monomer, the poly 1,4 anthraquinone in polymerization state has higher structural stability, is less easy to be dissolved in aqueous solution, and has longer cycle life and better multiplying power performance.
A preparation method of a poly-1, 4 anthraquinone negative electrode material of a water-based battery comprises the following steps:
(1) Dissolving bis 1, 5-cyclooctadiene, 2-bipyridine and 1, 5-cyclooctadiene into dimethylformamide to obtain a first mixed solution;
(2) Dissolving 1, 4-dichloro anthraquinone into dimethylformamide to obtain a second mixed solution;
(3) Adding the second mixed solution in the step (2) into the first mixed solution in the step (1), fully reacting at the temperature of 45-55 ℃ under the protection of nitrogen, and cooling to room temperature to obtain a reaction solution;
(4) Settling the reaction solution in the step (3) in a dilute hydrochloric acid solution to generate yellow precipitate, and filtering to obtain the yellow precipitate;
(5) Washing the yellow precipitate with dimethylformamide, dilute hydrochloric acid, deionized water and methanol in sequence, and vacuum drying to obtain the poly-1, 4-anthraquinone;
the reaction formula of the poly-1, 4 anthraquinone is as follows:
。
the invention relates to a poly-1, 4 anthraquinone negative electrode material of a water-based battery, a preparation method and application thereof, and the process of the step (3) is optimized; the reaction is carried out in three sections in the step (3) to obtain a reaction liquid; the first-stage reaction: the temperature is 50-55 ℃, the pressure is normal pressure, and the reaction time is 6-8 hours; two-stage reaction: the temperature is 45-50 ℃, the pressure is 1.2-1.5 megapascals, and the reaction time is 7-9 hours; three-stage reaction: the temperature is 50-55 ℃, the pressure is 0.6-0.8 megapascal, and the reaction time is 4-6 hours; the polymerization degree of the poly-1, 4 anthraquinone obtained by the reaction is more uniformly distributed through the first-stage reaction, the second-stage reaction and the third-stage reaction in sequence, and the polymerization degree of more than 90wt% of the polymer is concentrated at 5000-5500, so that the performance of the water system battery is more stable, the energy density of the water system battery is effectively increased, and the cycle life of the water system battery is prolonged.
An aqueous battery comprising a positive electrode, a negative electrode, a separator, a current collector and an electrolyte, wherein the poly-1, 4 anthraquinone is used as the negative electrode of the aqueous battery; the preparation method of the negative electrode comprises the following steps:
1) The negative electrode comprises the following components in parts by weight: 58-62 parts of poly 1,4 anthraquinone, 28-32 parts of conductive agent and 8-12 parts of binder; weighing all components composing the negative electrode according to the weight proportion, and uniformly mixing to obtain a mixture; the conductive agent is one or more of ketjen black, carbon black, super P, carbon nano tube and graphene; the binder is one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose, polyacrylic acid and polytetrafluoroethylene; the diaphragm is filter paper or glass fiber; the electrolyte is one or more of lithium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution, and the concentration of the electrolyte is 5-10 mol/L; the positive electrode is made of any one of nickel-based compounds, prussian blue analogues or polyanion compounds; the current collector is made of nickel screen, titanium foil, stainless steel foil, carbon paper or graphite felt;
2) And (3) grinding the mixture uniformly, adding deionized water and ethanol to prepare slurry, grinding into sheets, fixing on a foam nickel current collector, and vacuum drying to obtain the P14AQ organic negative electrode.
According to the poly-1, 4-anthraquinone negative electrode material of the water-based battery and the preparation method and application thereof, the composition ratio of the conductive agent and the modification method of the carbon nano tube are optimized, so that the carbon nano tube can be tightly combined with the Super P, the poly-1, 4-anthraquinone and other components, the dissolution process of the poly-1, 4-anthraquinone in the water-based electrolyte is effectively delayed, the performance stability of the water-based battery is further improved, and the service life of the water-based battery is prolonged; the conductive agent comprises the following components in parts by weight: 20-25 parts of carbon nanotubes and 30-35 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.7-0.9 mol/L, and acidizing for 4-6 hours to obtain an acidized carbon nano tube; 2) Placing the acidified carbon nanotubes in absolute ethyl alcohol, and performing ultrasonic vibration for 15-20 min to obtain ultrasonic vibration carbon nanotubes; 3) And placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, carrying out ultrasonic vibration for 25-30 min, taking out and drying.
Example 1: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) At the reaction temperature of 50 ℃, under the protection of nitrogen, reacting for 20 hours, cooling to room temperature, and then settling the reaction liquid into 100 ml and 0.5M dilute hydrochloric acid to generate yellow precipitate;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 75deg.C for 10h to obtain the product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 90mg of P14AQ, 45mg of Carbon Nano Tube (CNT) and 15 mg of Polytetrafluoroethylene (PTFE) are mixed according to the mass ratio of 6:3:1, deionized water and absolute ethyl alcohol are added, mixed and ground for 30min, rolled into thin slices, cut into small electrode materials by scissors, the electrode materials are pressed onto foamed nickel at the pressure of 0.3T, and placed in a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 6M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 6M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Example 2: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) At the reaction temperature of 45 ℃, under the protection of nitrogen, reacting and cooling to room temperature, and then settling the reaction liquid into 100 ml and 0.45M dilute hydrochloric acid to generate yellow precipitate; carrying out reaction in three sections to obtain a reaction solution; the first-stage reaction: the temperature is 50 ℃, the pressure is normal pressure, and the reaction time is 6 hours; two-stage reaction: the temperature is 45 ℃, the pressure is 1.2 megapascals, and the reaction time is 7 hours; three-stage reaction: the temperature is 50 ℃, the pressure is 0.6 megapascal, and the reaction time is 4 hours;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 70deg.C for 9h to obtain the product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 58mg of P14AQ, 28mg of a conductive agent, 8mg of Polytetrafluoroethylene (PTFE) were mixed as follows: 28:8, adding deionized water and absolute ethyl alcohol, mixing, grinding for 30min, rolling into thin slices, cutting into small electrode materials by scissors, pressing the electrode materials onto foam nickel at a pressure of 0.3T, and placing into a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ; the conductive agent comprises the following components in parts by weight: 20 parts of carbon nano tube and 30 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.7mol/L for acidizing treatment for 4 hours to obtain an acidized carbon nano tube; 2) Placing the acidified carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic oscillation for 15min to obtain an ultrasonic oscillating carbon nano tube; 3) Placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, carrying out ultrasonic vibration for 25min, taking out and drying;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 5M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 5M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Example 3: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) The reaction temperature is 55 ℃, the reaction is carried out under the protection of nitrogen and cooled to room temperature, and then the reaction liquid is settled into 100 ml and 0.55M dilute hydrochloric acid to generate yellow precipitate; carrying out reaction in three sections to obtain a reaction solution; the first-stage reaction: the temperature is 55 ℃, the pressure is normal pressure, and the reaction time is 8 hours; two-stage reaction: the temperature is 50 ℃, the pressure is 1.5 megapascals, and the reaction time is 9 hours; three-stage reaction: the temperature is 55 ℃, the pressure is 0.8 megapascal, and the reaction time is 6 hours;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 80deg.C for 12 hr to obtain product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 62mg of P14AQ, 32mg of a conductive agent, 12mg of Polytetrafluoroethylene (PTFE) were mixed according to a ratio of 62:32:12, adding deionized water and absolute ethyl alcohol, mixing, grinding for 30min, rolling into thin slices, cutting into small electrode materials by scissors, pressing the electrode materials onto foam nickel at a pressure of 0.3T, and placing into a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ; the conductive agent comprises the following components in parts by weight: 25 parts of carbon nano tube and 35 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.9mol/L for acidizing for 6 hours to obtain an acidized carbon nano tube; 2) Placing the acidified carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic oscillation for 20min to obtain an ultrasonic oscillating carbon nano tube; 3) Placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, carrying out ultrasonic vibration for 30min, taking out and drying;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 10M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 10M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Example 4: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) At the reaction temperature of 50 ℃, under the protection of nitrogen, reacting and cooling to room temperature, and then settling the reaction liquid into 100 ml and 0.5M dilute hydrochloric acid to generate yellow precipitate; carrying out reaction in three sections to obtain a reaction solution; the first-stage reaction: the temperature is 52 ℃, the pressure is normal pressure, and the reaction time is 7 hours; two-stage reaction: the temperature is 48 ℃, the pressure is 1.3 megapascals, and the reaction time is 8 hours; three-stage reaction: the temperature is 53 ℃, the pressure is 0.7 megapascal, and the reaction time is 5 hours;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 75deg.C for 10h to obtain the product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 90mg of P14AQ, 45mg of conductive agent and 15 mg Polytetrafluoroethylene (PTFE) are mixed according to the mass ratio of 6:3:1, deionized water and absolute ethyl alcohol are added, mixed and ground for 30min, rolled into a sheet, cut into small pieces of electrode material by scissors, the electrode material is pressed onto foam nickel by 0.3T pressure, and placed in a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ; the conductive agent comprises the following components in parts by weight: 23 parts of carbon nano tube and 32 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.8mol/L for acidification treatment for 5 hours to obtain an acidified carbon nano tube; 2) Placing the acidified carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic oscillation for 17min to obtain an ultrasonic oscillation carbon nano tube; 3) Placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, performing ultrasonic vibration for 28min, taking out and drying;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 6M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 6M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Example 5: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) At the reaction temperature of 50 ℃, under the protection of nitrogen, reacting for 20 hours, cooling to room temperature, and then settling the reaction liquid into 100 ml and 0.5M dilute hydrochloric acid to generate yellow precipitate;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 75deg.C for 10h to obtain the product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 90mg of P14AQ, 45mg of conductive agent and 15 mg Polytetrafluoroethylene (PTFE) are mixed according to the mass ratio of 6:3:1, deionized water and absolute ethyl alcohol are added, mixed and ground for 30min, rolled into a sheet, cut into small pieces of electrode material by scissors, the electrode material is pressed onto foam nickel by 0.3T pressure, and placed in a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ; the conductive agent comprises the following components in parts by weight: 23 parts of carbon nano tube and 32 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.8mol/L for acidification treatment for 5 hours to obtain an acidified carbon nano tube; 2) Placing the acidified carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic oscillation for 17min to obtain an ultrasonic oscillation carbon nano tube; 3) Placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, performing ultrasonic vibration for 28min, taking out and drying;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 6M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 6M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Example 6: poly 1,4 anthraquinone negative electrode material of water-based battery and preparation method thereof
(1) The synthesis method of the P14AQ anode material comprises the following steps:
1) 2.2g of bis 1, 5-cyclooctadiene, 1.25g of 2, 2-bipyridine and 0.65g of 1, 5-cyclooctadiene were dissolved in 60ml of Dimethylformamide (DMF);
2) 1.662g of 1, 4-dichloroanthraquinone dissolved in 40 ml of DMF is added to the above solution;
3) At the reaction temperature of 50 ℃, under the protection of nitrogen, reacting and cooling to room temperature, and then settling the reaction liquid into 100 ml and 0.5M dilute hydrochloric acid to generate yellow precipitate; carrying out reaction in three sections to obtain a reaction solution; the first-stage reaction: the temperature is 52 ℃, the pressure is normal pressure, and the reaction time is 7 hours; two-stage reaction: the temperature is 48 ℃, the pressure is 1.3 megapascals, and the reaction time is 8 hours; three-stage reaction: the temperature is 53 ℃, the pressure is 0.7 megapascal, and the reaction time is 5 hours;
4) Filtering and washing with DMF, dilute hydrochloric acid, deionized water and methanol for 2 times in sequence, and vacuum drying at 75deg.C for 10h to obtain the product; the structural formula of the product is as follows:
；
(2) Preparing an organic negative electrode: 90mg of P14AQ, 45mg of Carbon Nano Tube (CNT) and 15 mg of Polytetrafluoroethylene (PTFE) are mixed according to the mass ratio of 6:3:1, deionized water and absolute ethyl alcohol are added, mixed and ground for 30min, rolled into thin slices, cut into small electrode materials by scissors, the electrode materials are pressed onto foamed nickel at the pressure of 0.3T, and placed in a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ;
(3) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 6M KOH electrolyte;
(4) And (3) designing a water system battery: the anode is a P14AQ organic electrode, the electrolyte is 6M KOH, the PP/PE diaphragm, and the cathode is sintered nickel with the diameter of 10 mm, so as to assemble a CR2032 button battery;
(5) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
Comparative example 1: negative electrode material of water-based battery and preparation method thereof
(1) Preparing an organic negative electrode: mixing 90mg of 1, 4-dichloroanthraquinone, 45mg of conductive agent and 15 mg Polytetrafluoroethylene (PTFE) according to the mass ratio of 6:3:1, adding deionized water and absolute ethyl alcohol, mixing, grinding for 30min, rolling into thin slices, cutting into small electrode materials by scissors, pressing the electrode materials onto foamed nickel at the pressure of 0.3T, and placing the foamed nickel in a vacuum drying oven at 60 ℃ for 24 h; weighing after drying, and calculating to obtain the mass of the electrode material and the mass of the active substance P14 AQ; the conductive agent comprises the following components in parts by weight: 23 parts of carbon nano tube and 32 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.8mol/L for acidification treatment for 5 hours to obtain an acidified carbon nano tube; 2) Placing the acidified carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic oscillation for 17min to obtain an ultrasonic oscillation carbon nano tube; 3) Placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, performing ultrasonic vibration for 28min, taking out and drying;
(2) Preparing an electrolyte: mixing KOH and deionized water, stirring and dissolving uniformly to prepare 6M KOH electrolyte;
(3) And (3) designing a water system battery: the anode is an organic electrode prepared in the step (1), the electrolyte is 6M KOH, the PP/PE diaphragm, and the anode is sintered nickel with the diameter of 10 mm, so that a CR2032 button cell is assembled;
(4) Electrochemical performance test of aqueous cell: the cyclic voltammetry test adopts a blue electrochemical workstation, the battery is placed at 12h after being assembled, and is charged and discharged firstly, the voltage ranges from 1.45 to 0.5V, and the sweeping speed is 1mV/s and 2 mV/s; the cycle performance test uses a new Weibull battery tester, the battery is charged and discharged after standing for 12h, the voltage range is 1.45 to 0.5V, the current density is 0.3A/g, and the current size is set according to the quality of P14AQ in the cathode; the new Weibull battery tester is used for testing the multiplying power performance, the battery is charged and discharged after standing for 12h, the voltage ranges from 1.45 to 0.5V, the current densities are respectively 0.1, 0.3, 0.5, 0.8, 1.0, 0.8, 0.5, 0.3 and 0.1A/g, 7 circles are circulated under each current, and the current is set according to the quality of P14AQ in the cathode; the specific capacity of the aqueous battery was calculated from the mass of P14AQ in the negative electrode.
The results of the above-described examples 1 to 6 and comparative example 1 are shown in Table 1 below:
TABLE 1
Therefore, compared with the existing inorganic material negative electrode and small molecular organic negative electrode of the water-based battery, the poly-1, 4 anthraquinone negative electrode material of the water-based battery and the preparation method and application thereof solve the problem of dissolution of the negative electrode material and the discharge product in the water-based electrolyte; the water-based battery formed by the poly-1, 4 anthraquinone organic negative electrode and the commercial sintered nickel positive electrode has long cycle life, excellent multiplying power performance and high output voltage, and the raw materials are wide in source and low in price, so that the problems of low energy density and short cycle life of the conventional water-based battery can be effectively solved, and the application of the water-based battery in the field of large-scale energy storage can be promoted; the preparation method of the poly-1, 4 anthraquinone is optimized, the reaction is carried out in three sections in the step (3), the polymerization degree of the poly-1, 4 anthraquinone is more uniformly distributed, and the polymerization degree of more than 90wt% of the polymer is concentrated in 5000-5500, so that the performance of the water system battery is more stable, the energy density of the water system battery is effectively increased, and the cycle life of the water system battery is prolonged; the conductive agent consists of carbon nanotubes and Super P, and the carbon nanotubes are modified, and acid treatment is carried out on the carbon nanotubes, so that the affinity between the carbon nanotubes and a solute can be increased, and the dispersibility of the carbon nanotubes in the solute is improved; and then sequentially placing the carbon nano tube in absolute ethyl alcohol and isopropanol for ultrasonic vibration treatment, so that lattice defects or lattice distortion can be formed on the surface of the carbon nano tube, the carbon nano tube is tightly combined with Super P, poly 1,4 anthraquinone and other components, the dissolution process of the poly 1,4 anthraquinone in the water-based electrolyte is effectively delayed, the performance stability of the water-based battery is further improved, and the service life of the water-based battery is prolonged.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A poly 1,4 anthraquinone negative electrode material of an aqueous battery, comprising poly 1,4 anthraquinone, said poly 1,4 anthraquinone having the following structure:
；
wherein n is the degree of polymerization.
2. The aqueous battery poly-1, 4-anthraquinone negative electrode material according to claim 1, wherein n is a polymerization degree and the value range of n is 3000-6000.
3. The preparation method of the poly 1,4 anthraquinone negative electrode material of the water-based battery according to any one of claims 1 to 2, which is characterized by comprising the following steps:
(1) Dissolving bis 1, 5-cyclooctadiene, 2-bipyridine and 1, 5-cyclooctadiene into dimethylformamide to obtain a first mixed solution;
(2) Dissolving 1, 4-dichloro anthraquinone into dimethylformamide to obtain a second mixed solution;
(3) Adding the second mixed solution in the step (2) into the first mixed solution in the step (1), fully reacting at the temperature of 45-55 ℃ under the protection of nitrogen, and cooling to room temperature to obtain a reaction solution;
(4) Settling the reaction solution in the step (3) in a dilute hydrochloric acid solution to generate yellow precipitate, and filtering to obtain the yellow precipitate;
(5) Washing the yellow precipitate with dimethylformamide, dilute hydrochloric acid, deionized water and methanol in sequence, and vacuum drying to obtain the poly-1, 4-anthraquinone.
4. The method for producing a poly-1, 4-anthraquinone negative electrode material for an aqueous battery according to claim 3, wherein the reaction in the step (3) is performed in three steps to obtain a reaction solution; the first-stage reaction: the temperature is 50-55 ℃, the pressure is normal pressure, and the reaction time is 6-8 hours; two-stage reaction: the temperature is 45-50 ℃, the pressure is 1.2-1.5 megapascals, and the reaction time is 7-9 hours; three-stage reaction: the temperature is 50-55 ℃, the pressure is 0.6-0.8 megapascal, and the reaction time is 4-6 hours.
5. The method for preparing a poly-1, 4-anthraquinone negative electrode material of an aqueous battery according to claim 3, wherein the concentration of the dilute hydrochloric acid solution in the step (4) is 0.45-0.55 mol/L.
6. The method for preparing a poly-1, 4-anthraquinone negative electrode material for an aqueous battery according to claim 3, wherein in the step (5), the temperature of vacuum drying is 70-80 ℃ and the time is 9-12 hours.
7. The use of a poly-1, 4-anthraquinone negative electrode material for an aqueous battery according to any one of claims 1 to 2, wherein the poly-1, 4-anthraquinone is used as a negative electrode of the aqueous battery.
8. An aqueous battery comprising a positive electrode, a negative electrode, a separator, a current collector and an electrolyte, wherein the poly-1, 4 anthraquinone is used as the negative electrode of the aqueous battery; the preparation method of the negative electrode comprises the following steps:
1) The negative electrode comprises the following components in parts by weight: 58-62 parts of poly 1,4 anthraquinone, 28-32 parts of conductive agent and 8-12 parts of binder; weighing all components composing the negative electrode according to the weight proportion, and uniformly mixing to obtain a mixture;
2) And (3) grinding the mixture uniformly, adding deionized water and ethanol to prepare slurry, grinding into sheets, fixing on a foam nickel current collector, and vacuum drying to obtain the P14AQ organic negative electrode.
9. The aqueous battery of claim 8, wherein the conductive agent is one or more of ketjen black, carbon black, super P, carbon nanotubes, and graphene; the binder is one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose, polyacrylic acid and polytetrafluoroethylene; the diaphragm is filter paper or glass fiber; the electrolyte is one or more of lithium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution, and the concentration of the electrolyte is 5-10 mol/L; the positive electrode is made of any one of nickel-based compounds, prussian blue analogues or polyanion compounds; the current collector is made of nickel screen, titanium foil, stainless steel foil, carbon paper or graphite felt.
10. The aqueous battery of claim 8, wherein the conductive agent comprises, in parts by weight: 20-25 parts of carbon nanotubes and 30-35 parts of Super P; before the carbon nano tube is used, the carbon nano tube is modified by the following steps: 1) Placing the carbon nano tube into a saline solution with the concentration of 0.7-0.9 mol/L, and acidizing for 4-6 hours to obtain an acidized carbon nano tube; 2) Placing the acidified carbon nanotubes in absolute ethyl alcohol, and performing ultrasonic vibration for 15-20 min to obtain ultrasonic vibration carbon nanotubes; 3) And placing the carbon nano tube subjected to ultrasonic vibration in isopropanol, carrying out ultrasonic vibration for 25-30 min, taking out and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310602750.5A CN117038977A (en) | 2023-05-25 | 2023-05-25 | Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310602750.5A CN117038977A (en) | 2023-05-25 | 2023-05-25 | Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117038977A true CN117038977A (en) | 2023-11-10 |
Family
ID=88626871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310602750.5A Pending CN117038977A (en) | 2023-05-25 | 2023-05-25 | Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117038977A (en) |
-
2023
- 2023-05-25 CN CN202310602750.5A patent/CN117038977A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113809325B (en) | Alkaline aqueous secondary battery based on electroactive covalent organic framework polymer and application thereof | |
| CN108183039B (en) | Preparation method of carbon-modified titanium niobate material, lithium ion capacitor and negative electrode slurry thereof | |
| CN107895779B (en) | High-capacity potassium ion battery negative electrode material and preparation method and application thereof | |
| CN113113605B (en) | Network structure ion conductive adhesive and preparation method and application thereof | |
| CN111244561B (en) | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte | |
| CN109786742B (en) | Se-doped MXene battery negative electrode material and preparation method and application thereof | |
| CN112652757B (en) | Modified silicon-carbon negative electrode material and preparation method and application thereof | |
| CN111785942A (en) | Water-based zinc ion battery positive electrode material and preparation method and application thereof | |
| CN111640921A (en) | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery | |
| CN113594453A (en) | Sodium-ion battery negative electrode material and preparation method thereof | |
| CN112038637A (en) | Composite conductive agent, preparation method thereof and lithium ion battery | |
| CN113644269A (en) | Preparation method of nitrogen-doped hard carbon material, product and application thereof | |
| CN110556537B (en) | Method for improving electrochemical performance of anion-embedded electrode material | |
| CN116621143A (en) | Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate preparation method and application thereof in sodium ion battery | |
| CN114520321B (en) | Graphite@manganese dioxide/polymer composite positive electrode material and preparation method and application thereof | |
| CN114122394B (en) | Polyoxazine material and preparation method and application thereof | |
| CN117038977A (en) | Poly 1,4 anthraquinone negative electrode material of water-based battery, and preparation method and application thereof | |
| CN114843459A (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN113078295A (en) | All-solid-state zinc-sulfur battery and manufacturing method thereof | |
| CN111430715A (en) | Two-dimensional Ti3C2TxPreparation method and application of modified carbon fluoride composite positive electrode material | |
| CN114497539B (en) | Aqueous rechargeable battery based on copper ferrocyanide anode and phenazine organic matter cathode | |
| CN115745972B (en) | Nitrogen-containing organic positive electrode material, and preparation method and application thereof | |
| CN113594443B (en) | Phosphorus-metal poly phthalocyanine/carbon composite material and preparation method and application thereof | |
| CN114975994B (en) | Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof | |
| CN114349936B (en) | Synthesis method of quinone-nitrogen heterocyclic polymer and application of quinone-nitrogen heterocyclic polymer in secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |