CN116969841A - Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery - Google Patents
Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery Download PDFInfo
- Publication number
- CN116969841A CN116969841A CN202310846954.3A CN202310846954A CN116969841A CN 116969841 A CN116969841 A CN 116969841A CN 202310846954 A CN202310846954 A CN 202310846954A CN 116969841 A CN116969841 A CN 116969841A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- battery
- tetraketone
- active material
- solution
- 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
- 239000011701 zinc Substances 0.000 title claims abstract description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000013543 active substance Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 4
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004090 dissolution Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 6
- 239000002800 charge carrier Substances 0.000 abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000036647 reaction Effects 0.000 abstract 1
- 230000001568 sexual effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000011368 organic material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000008261 resistance mechanism Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode active material and a preparation method thereof, wherein the preparation method comprises the following steps: step S1, dissolving pyrene-4, 5,9,10 tetraketone in a dichloromethane/acetonitrile solvent, and uniformly mixing to form a solution A; step S2, adding sodium metaperiodate and ruthenium trichloride into deionized water, and uniformly mixing to form a solution B; and step S3, adding the solution B into the solution A under stirring, reacting at a preset temperature, filtering, washing and drying to obtain the positive active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone. The invention also provides a battery anode, which uses the anode active materialThe sexual substance is prepared. The invention also provides a water-based zinc battery prepared by using the battery anode. NH in electrolyte during electrochemical cell reaction 4 + The charge carrier and the redox active carbonyl and nitro of the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone undergo a coordination reaction to form a firm hydrogen bond network, so that the dissolution resistance effect in the electrolyte is realized, and the excellent cycle life is shown.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a positive electrode active material, a preparation method thereof, a battery positive electrode and a water-based zinc battery.
Background
To solve the increasingly serious problems of energy shortage and environmental deterioration, new energy and new energy technologies must be developed drastically. Batteries are being actively developed as an efficient electrochemical energy storage device driven by the demands of portable electronic products, wearable technologies, and the like. Among a plurality of energy storage devices, the water-based zinc battery is a novel green battery, consists of a zinc foil negative electrode, an organic material positive electrode and a zinc-based electrolyte, has the advantages of abundant zinc resources, various organic material structures and functions, simple battery assembly process, good safety and the like, and has wide application prospects in the fields of emerging electronic intelligent equipment and the like. In view of the inherent theoretical specific capacity of zinc cathodes (820 mAh g-1) and lower redox voltage (-0.76V vs. standard hydrogen electrode), the performance of zinc batteries is primarily determined by the organic cathode material.
Small organic molecules of light molecular weight are often used as zinc cell positive electrode materials because of their high density of redox active functional groups. However, there is a strong interaction between the polar functional groups of the organic small molecular material and the aqueous solvent, resulting in higher solubility in the electrolyte, causing problems of rapid decay of the small molecular electrode activity and insufficient battery cycle stability. To overcome this obstacle, researchers have developed various strategies such as expanding pi-conjugated planar organic structures, polymerizing soluble organic monomers, designing insoluble matrix encapsulation organics. The invention relates to an aza-aromatic ring organic material, a positive electrode, a battery and a preparation method thereof (Chinese patent application No. CN 202210988515.1), which can inhibit the dissolution of the organic material in water and enhance the electron conduction capability of the organic material by expanding the length of aza-aromatic ring molecules. The material can be used as a positive electrode material of a zinc battery, and the constructed zinc battery shows enhanced cycle stability (more than 2000 cycles can be circulated). The invention relates to a water system chargeable zinc ion battery based on aromatic organic matter anode material and application thereof (China patent application No. 202010655456.7), which is characterized in that a plurality of aromatic micromolecule monomers are electrochemically polymerized on nano porous carbon at the same time to prepare a carbon@polymer composite anode material, and the carbon@polymer composite anode material is assembled with a zinc anode to obtain the water system chargeable zinc ion battery, so that the problem of capacity attenuation caused by the fact that the organic micromolecule is easily dissolved in electrolyte is solved, and the capacity retention rate is more than 86% after 2000 charge and discharge cycles. However, these methods have presented new problems such as increased electrochemically inert sites, low utilization of electroactive functional groups, complex/inefficient material preparation processes, resulting in reduced capacity storage and rate capability of the battery, and greatly limiting the development of zinc batteries. Therefore, inhibiting the dissolution of small organic molecules by developing an efficient structural design strategy is a key for improving the cycling stability of the organic positive electrode material.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a positive electrode active material, a method for producing the same, a battery positive electrode, and an aqueous zinc battery.
The present invention provides a method for preparing a positive electrode active material, having such characteristics that it comprises the steps of:
step S1, dissolving pyrene-4, 5,9,10 tetraketone in a dichloromethane/acetonitrile solvent, and uniformly mixing to form a solution A;
step S2, adding sodium metaperiodate and ruthenium trichloride into deionized water, and uniformly mixing to form a solution B;
step S3, adding the solution B into the solution A under stirring, reacting at a preset temperature, filtering, washing with deionized water, and vacuum drying to obtain the positive active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone,
wherein, the mass ratio of pyrene-4, 5,9,10 tetraketone, methylene dichloride/acetonitrile solvent, sodium metaperiodate, deionized water and ruthenium trichloride is 1: 20-40: 5-10: 10-20: 0.1 to 0.2.
The method for producing a positive electrode active material according to the present invention may further have the following feature: wherein in the step S3, the solution B is added into the solution A at the stirring speed of 300-800 rpm, and reacts for 12-24 hours at the preset temperature of 30-80 ℃,
in step S3, when vacuum drying is performed, vacuum drying is performed at 80℃for 12 hours.
The invention also provides a positive electrode active material, which has the characteristics that the positive electrode active material is prepared by the preparation method of the positive electrode active material, and the positive electrode active material is 2, 7-dinitropyridine-4, 5,9, 10-tetraketone.
The invention also provides a positive electrode active material, which has the characteristics that the positive electrode active material is prepared by the following steps:
weighing anode active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, graphite conductive agent and polytetrafluoroethylene adhesive, adding N-methyl pyrrolidine, uniformly grinding to obtain slurry, uniformly coating the slurry on a current collector, drying to obtain the anode of the battery,
wherein the current collector is one of titanium foil, nickel net, titanium net, stainless steel net or carbon paper.
The invention also provides a water-based zinc battery, which has the characteristics that the water-based zinc battery comprises an anode, a cathode, a diaphragm and electrolyte, wherein the diaphragm is arranged between the anode and the cathode, the finished water-based zinc battery is put into a battery shell, the electrolyte is added, and the water-based zinc battery is obtained through assembly,
wherein the positive electrode is the battery positive electrode,
the cathode is high-purity commercial zinc foil with the zinc content more than or equal to 99.99 percent,
the electrolyte is NH 4 Cl、NH 4 CF 3 SO 3 、(NH 4 ) 2 SO 4 、Zn(CF 3 SO 3 ) 2 One or more of the aqueous solutions, the concentration of the electrolyte is 1mol L -1 ～10mol L -1 ，
The membrane is filter paper or glass fiber.
Effects and effects of the invention
According to the positive electrode active material, the preparation method thereof, the battery positive electrode and the water-based zinc battery, the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone is prepared, the battery positive electrode is further prepared by using the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, and meanwhile, the prepared battery positive electrode is assembled to obtain the water-based zinc battery.
The 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecule prepared by the invention has carbonyl and nitro functional groups with double redox activities as hydrogen bond acceptors, and can be coupled with flexible tetrahedron NH as hydrogen bond donors 4 + Charge carrier, overcoming high-reaction energy barrier solvation of Zn 2+ The slow interfacial charge transfer caused by ions effectively reduces the charge transfer energy barrier and promotes high dynamics NH 4 + Coordination reaction, full utilization of electroactive carbonyl and nitro sites is realized, and remarkable improvement of battery capacity is facilitated.
And in the electrochemical reaction process of the battery, carbonyl/nitro functional groups and NH in 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules 4 + The ultra-stable interlocking hydrogen bond structure can be formed through the four-fold hydrogen bond topological coordination chemical reaction, and 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules are effectively stabilized, so that the anti-dissolution effect of the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules in an electrolyte is realized, and the problem that the battery cycle life is insufficient due to the fact that the existing organic micromolecule positive electrode material is easy to dissolve in the electrolyte is solved.
Thus, the invention is capable of combining with NH 4 + The hydrogen bond 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecule coordinated by the charge carrier is used as the positive electrode active material of the water-based zinc battery, and the assembled battery has excellent capacity storage and rate capability, and also has excellent cycling stability, so that the service life of the zinc battery is prolonged to a new level.
In addition, the main raw materials used in the invention have wide sources, low cost and environmental protection, the whole system electrode and electrolyte preparation process is carried out at normal temperature and normal pressure, and the operation is simple, safe and pollution-free.
Drawings
FIG. 1 is a scanning electron microscope image of 2, 7-dinitropyridine-4, 5,9, 10-tetraketone as a positive electrode active material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone prepared in example 2 of the present invention;
FIG. 3 is a schematic representation of the invention in example 3 with 2, 7-dinitropyridine-4, 5,9, 10-tetraketone positive electrode, zinc foil negative electrode and NH 4 CF 3 SO 3 Assembling the electrolyte to obtain a cycle stability diagram of the zinc battery at a current density of 10A/g;
FIG. 4 shows a comparative example of the present invention with 2, 7-dinitropyridine-4, 5,9, 10-tetraketone positive electrode, zinc foil negative electrode and Zn (CF) 3 SO 3 ) 2 Assembling the electrolyte to obtain a cycle stability diagram of the zinc battery at a current density of 10A/g;
FIG. 5 is a schematic representation of the NH of the 2, 7-dinitropyridine-4, 5,9, 10-tetratone positive electrode active material of example 3 of the present invention 4 CF 3 SO 3 Dissolution resistance mechanism diagram in electrolyte.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the present invention easy to understand, the following examples specifically describe a positive electrode active material, a preparation method thereof, a battery positive electrode and a water-based zinc battery according to the present invention with reference to the accompanying drawings.
Example 1 ]
The preparation method of the positive electrode active material of the embodiment comprises the following steps:
step S1, pyrene-4, 5,9,10 tetraketone is dissolved in a dichloromethane/acetonitrile solvent and uniformly mixed to form a solution A.
And S2, adding sodium metaperiodate and ruthenium trichloride into deionized water, and uniformly mixing to form a solution B.
Step S3, adding the solution B into the solution A under stirring, reacting at a preset temperature, filtering, washing with deionized water, and vacuum drying to obtain the positive active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, wherein the specific process is as follows:
adding the solution B into the solution A at a stirring speed of 500 r/min, reacting at 50 ℃ for 12h, filtering and washing with deionized water, and vacuum drying at 80 ℃ for 12h to obtain pyrene-4, 5,9,10 tetraketone.
In the embodiment, the mass ratio of pyrene-4, 5,9,10 tetraketone, methylene dichloride/acetonitrile solvent, sodium metaperiodate, deionized water and ruthenium trichloride is 1:30:5:10:0.1.
the starting materials used in this example were all commercial reagent grade products.
FIG. 1 is a scanning electron microscope image of 2, 7-dinitropyridine-4, 5,9, 10-tetraketone as a positive electrode active material prepared in example 1 of the present invention.
As shown in fig. 1, it can be seen from scanning by an electron microscope that the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone prepared in this example is formed by stacking nanoparticle structures.
Example 2 ]
The preparation method of the positive electrode active material of the embodiment comprises the following steps:
step S1, pyrene-4, 5,9,10 tetraketone is dissolved in a dichloromethane/acetonitrile solvent and uniformly mixed to form a solution A.
And S2, adding sodium metaperiodate and ruthenium trichloride into deionized water, and uniformly mixing to form a solution B.
Step S3, adding the solution B into the solution A under stirring, reacting at a preset temperature, filtering, washing with deionized water, and vacuum drying to obtain the positive active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, wherein the specific process is as follows:
adding the solution B into the solution A at the stirring speed of 600 r/min, reacting for 12h at 40 ℃, filtering and washing with deionized water, and vacuum drying for 12h at 80 ℃ to obtain pyrene-4, 5,9,10 tetraketone.
In the embodiment, the mass ratio of pyrene-4, 5,9,10 tetraketone, methylene dichloride/acetonitrile solvent, sodium metaperiodate, deionized water and ruthenium trichloride is 1:20:8:10:0.15.
the starting materials used in this example were all commercial reagent grade products.
FIG. 2 is a scanning electron microscope image of 2, 7-dinitropyridine-4, 5,9, 10-tetraketone as a positive electrode active material prepared in example 2 of the present invention.
As shown in fig. 2, it can be seen from electron microscope scanning that the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone prepared in this example is formed by stacking nanoparticle structures.
Example 3 ]
In this example, the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone prepared in example 1 was used to prepare a positive electrode of a battery, and the preparation method was as follows:
according to the mass ratio of 7:2:1 weighing the positive active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, graphite conductive agent and polytetrafluoroethylene adhesive prepared in the example 1, adding N-methylpyrrolidine into a mortar, uniformly grinding for 30min to obtain slurry, uniformly coating the slurry on a stainless steel mesh current collector with the diameter of 1.2cm by a blade, and drying in a vacuum oven at 80 ℃ for 12h to obtain an electrode plate to be assembled as a positive electrode of a battery.
In this example, the prepared battery positive electrode was further used to assemble a water-based zinc battery, specifically as follows:
taking the prepared battery anode as the anode, taking high-purity commercial zinc foil (zinc content is more than or equal to 99.99%) as the cathode, placing a GE-Whatman glass fiber diaphragm between the anode and the cathode, putting the finished battery anode into a CR2032 button battery shell, and adding 3M NH 4 CF 3 SO 3 And (3) assembling the electrolyte to obtain the water-based zinc battery.
The starting materials used in this example were all commercial reagent grade products.
In this embodiment, electrochemical performance test is also performed on the prepared aqueous zinc battery, including: the device energy storage performance was tested by the CHI660E electrochemical workstation. Cycling and rate performance tests were performed on the LAND CT2001A battery test system. The voltage window is 0.1-1.8V.
Analysis and test show that the specific capacity of the zinc battery prepared by the embodiment reaches 300mAh g when the zinc battery is charged and discharged at 0.2A/g -1 The multiplying power capacity reaches 100mAh g when the battery is charged and discharged at 50A/g -1 The above shows high specific capacity storage performance.
FIG. 3 is an implementation of the present inventionIn example 3, 2, 7-dinitropyridine-4, 5,9, 10-tetraketone positive electrode, zinc foil negative electrode and NH 4 CF 3 SO 3 The electrolyte was assembled to give a cycle stability profile for zinc cells at a current density of 10A/g.
As shown in fig. 3, the capacity retention rate of the zinc battery assembled in this example after 60,000 times of cyclic charge and discharge is 81.2%, and the zinc battery has excellent cyclic stability, and the service life of the zinc battery is pushed to a new level.
Comparative example
In this comparative example, the positive electrode of a battery was first prepared using the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone prepared in example 1, as follows:
according to the mass ratio of 7:2:1 weighing the positive active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, graphite conductive agent and polytetrafluoroethylene adhesive prepared in the example 1, adding N-methylpyrrolidine into a mortar, uniformly grinding for 30min to obtain slurry, uniformly coating the slurry on a stainless steel mesh current collector with the diameter of 1.2cm by a blade, and drying in a vacuum oven at 80 ℃ for 12h to obtain an electrode plate to be assembled as a positive electrode of a battery.
In this example, the prepared battery positive electrode was further used to assemble a water-based zinc battery, specifically as follows:
taking the prepared battery anode as the anode, taking high-purity commercial zinc foil (zinc content is more than or equal to 99.99%) as the cathode, placing a GE-Whatman glass fiber diaphragm between the anode and the cathode, putting the finished battery anode into a CR2032 button battery shell, and adding 3M Zn (CF) 3 SO 3 ) 2 And (3) assembling the electrolyte to obtain the water-based zinc battery.
In this comparative example, electrochemical performance test was also performed on the prepared aqueous zinc cell, including: the device energy storage performance was tested by the CHI660E electrochemical workstation. Cycling and rate performance tests were performed on the LAND CT2001A battery test system. The voltage window is 0.1-1.8V.
FIG. 4 shows a comparative example of the present invention with 2, 7-dinitropyridine-4, 5,9, 10-tetraketone positive electrode, zinc foil negative electrode and Zn (CF) 3 SO 3 ) 2 The electrolyte was assembled to give a cycle stability profile for zinc cells at a current density of 10A/g.
As shown in fig. 4, the capacity retention rate of the zinc cell assembled in this example after 60,000 cycles of charge and discharge was 17.7%, and the cycle stability was poor.
As can be seen from comparison of the results of the performance tests of the zinc cell prepared by using different electrolytes in example 3 and the comparison of the comparison documents, the positive electrode of 2, 7-dinitropyridine-4, 5,9, 10-tetraketone is NH 4 CF 3 SO 3 The cycle stability in the electrolyte (81.2%) is significantly better than that in Zn (CF) 3 SO 3 ) 2 Cycling stability in electrolyte (17.7%).
FIG. 5 is a schematic representation of the NH of the 2, 7-dinitropyridine-4, 5,9, 10-tetratone positive electrode active material of example 3 of the present invention 4 CF 3 SO 3 Dissolution resistance mechanism diagram in electrolyte.
As shown in fig. 5, the double redox active carbonyl and nitro functional groups in the 2, 7-dinitropyridine-4, 5,9, 10-tetralone positive electrode can act as hydrogen bond acceptors, flexible tetrahedral NH during battery discharge 4 + The charge carrier can be used as a hydrogen bond donor, and the charge carrier and the hydrogen bond donor are subjected to topological coordination chemical reaction under the action of a quadruple hydrogen bond (N-H … O) to form an ultra-stable interlocking hydrogen bond structure. The interlocking hydrogen bond structure can effectively stabilize 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules, thereby realizing the anti-dissolution effect in electrolyte and solving the problem of insufficient cycle life of a battery caused by easy dissolution of the current organic micromolecular positive electrode material in the electrolyte.
In contrast, 2, 7-dinitropyridine-4, 5,9, 10-tetraketone positive electrode stores Zn 2+ The ions form a rigid chemical bond structure and cannot inhibit the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone from being in Zn (CF) 3 SO 3 ) 2 Dissolution in the electrolyte, while resulting in solvated Zn 2+ The ion reaction energy barrier is too high and the interfacial charge transfer kinetics are retarded, resulting in zinc cells exhibiting poor cycling stability.
Effects and effects of the examples
According to examples 1 and 2, the positive electrode active material 2, 7-dinitropyridine-4, 5,9, 10-tetraketone and the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone nanoparticle structure can be successfully prepared and stacked by the preparation method of the positive electrode active material.
According to example 3, the invention is achieved by 4 + The hydrogen bond 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecule coordinated by charge carrier is used as the positive electrode active material of the water-based zinc battery, and the specific capacity of the assembled battery reaches 300mAh g when the assembled battery is charged and discharged at 0.2A/g -1 The multiplying power capacity reaches 100mAh g when the battery is charged and discharged at 50A/g -1 The zinc battery has high specific capacity storage performance, and capacity retention rate after 60,000 times of cyclic charge and discharge is more than 80%, so that the service life of the zinc battery is prolonged to a new level.
According to the comparative example, the carbonyl/nitro functional group and NH in the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecule prepared by the invention are in the electrochemical reaction process of the battery 4 + The ultra-stable interlocking hydrogen bond structure can be formed through the four-fold hydrogen bond topological coordination chemical reaction, and 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules are effectively stabilized, so that the anti-dissolution effect of the 2, 7-dinitropyridine-4, 5,9, 10-tetraketone molecules in an electrolyte is realized, and the problem that the battery cycle life is insufficient due to the fact that the existing organic micromolecule positive electrode material is easy to dissolve in the electrolyte is solved.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (5)
1. A method for preparing a positive electrode active material, comprising the steps of:
step S1, dissolving pyrene-4, 5,9,10 tetraketone in a dichloromethane/acetonitrile solvent, and uniformly mixing to form a solution A;
step S2, adding sodium metaperiodate and ruthenium trichloride into deionized water, and uniformly mixing to form a solution B;
step S3, adding the solution B into the solution A under stirring, reacting at a preset temperature, filtering, washing with deionized water, and vacuum drying to obtain the positive active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone,
wherein the mass ratio of the pyrene-4, 5,9,10 tetraketone, the dichloromethane/acetonitrile solvent, the sodium metaperiodate, the deionized water and the ruthenium trichloride is 1: 20-40: 5-10: 10-20: 0.1 to 0.2.
2. The method for producing a positive electrode active material according to claim 1, characterized in that:
wherein in the step S3, the solution B is added into the solution A at the stirring speed of 300-800 rpm, and reacts for 12-24 hours at the preset temperature of 30-80 ℃,
in step S3, when vacuum drying is performed, vacuum drying is performed at 80℃for 12 hours.
3. A positive electrode active material prepared by the method for preparing a positive electrode active material according to any one of claims 1 to 2, wherein the positive electrode active material is 2, 7-dinitropyridine-4, 5,9, 10-tetraketone.
4. A battery positive electrode prepared by using the positive electrode active material according to claim 3, wherein the preparation method of the battery positive electrode comprises the following steps:
weighing anode active substance 2, 7-dinitropyridine-4, 5,9, 10-tetraketone, graphite conductive agent and polytetrafluoroethylene adhesive, adding N-methyl pyrrolidine, uniformly grinding to obtain slurry, uniformly coating the slurry on a current collector, drying to obtain the anode of the battery,
wherein the current collector is one of titanium foil, nickel mesh, titanium mesh, stainless steel mesh or carbon paper.
5. A water-based zinc battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm is placed between the negative electrode and the positive electrode, the battery is placed in a battery shell after finishing, the electrolyte is added, the water-based zinc battery is obtained through assembly,
wherein the positive electrode is a battery positive electrode according to claim 4,
the negative electrode is a high-purity commercial zinc foil with the zinc content more than or equal to 99.99 percent,
the electrolyte is NH 4 Cl、NH 4 CF 3 SO 3 、(NH 4 ) 2 SO 4 、Zn(CF 3 SO 3 ) 2 One or more of the aqueous solutions, wherein the concentration of the electrolyte is 1mol L -1 ～10molL -1 ，
The membrane is filter paper or glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310846954.3A CN116969841A (en) | 2023-07-11 | 2023-07-11 | Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310846954.3A CN116969841A (en) | 2023-07-11 | 2023-07-11 | Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116969841A true CN116969841A (en) | 2023-10-31 |
Family
ID=88484226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310846954.3A Pending CN116969841A (en) | 2023-07-11 | 2023-07-11 | Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116969841A (en) |
-
2023
- 2023-07-11 CN CN202310846954.3A patent/CN116969841A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111769278B (en) | Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof | |
| CN101740754B (en) | Preparation method of composite anode material for lithium element sulphur secondary battery | |
| CN111916640B (en) | WS2/CNTs modified diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN111081971B (en) | Preparation method of electrode of water-based zinc ion battery, electrode and battery | |
| CN112349893A (en) | Method for inhibiting growth of zinc dendrite by polydopamine film | |
| CN111640921A (en) | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery | |
| CN111261872A (en) | Organic electrode material and preparation method and application thereof | |
| CN112952077A (en) | Flexible zinc ion battery and preparation method thereof | |
| CN113725414B (en) | Cathode material of aqueous zinc-iodine secondary battery, cathode of aqueous zinc-iodine secondary battery and aqueous zinc-iodine secondary battery | |
| CN114361611A (en) | Zinc ion battery based on manganese dioxide-based positive electrode and polyimide-based negative electrode and preparation method thereof | |
| CN114122394B (en) | Polyoxazine material and preparation method and application thereof | |
| CN113422053A (en) | Battery negative electrode material based on tricyclic quinazoline and derivative thereof and application of battery negative electrode material in alkali metal ion battery | |
| CN116874775A (en) | Conjugated organic material BQBQ-COF, preparation method, positive electrode material, preparation method and application | |
| CN112952214A (en) | Aqueous zinc ion battery and preparation method thereof | |
| CN116969841A (en) | Positive electrode active material, preparation method thereof, battery positive electrode and water-based zinc battery | |
| CN113437360A (en) | Novel gel electrolyte for zinc battery and preparation method thereof | |
| CN113066992A (en) | Alkaline aqueous single flow battery based on double-metal MOF positive electrode and organic matter negative electrode | |
| CN117624517A (en) | Organic super-structure material, preparation method, battery anode and water-based zinc battery | |
| CN110148752A (en) | A kind of negative current collector surface electropolymerization pyrroles's method of modifying | |
| CN114497539B (en) | Aqueous rechargeable battery based on copper ferrocyanide anode and phenazine organic matter cathode | |
| CN116217952A (en) | Supermolecule organic superstructure material, and preparation method and application thereof | |
| CN115873242B (en) | Preparation method of organic polymer based on hexaazanaphthalene and application of organic polymer as positive electrode material of water-based aluminum ion battery | |
| CN117865972A (en) | Multi-electron tetranitroporphyrin active material, organic positive electrode material and water-based zinc battery | |
| CN116454278A (en) | Organic positive electrode material, preparation method, positive electrode plate, lithium ion capacitor and lithium metal battery | |
| CN118039831A (en) | Preparation method of co-doped polyaniline water-based zinc ion battery positive electrode material |
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 |