CN112635737A - Composite material, preparation method thereof, positive electrode material and water-based aluminum ion battery - Google Patents
Composite material, preparation method thereof, positive electrode material and water-based aluminum ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims abstract description 72
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 37
- -1 aluminum ion Chemical class 0.000 claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 54
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 40
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 5
- 230000003111 delayed effect Effects 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000002468 redox effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite material, a preparation method thereof, a positive electrode material and a water-based aluminum ion battery. The composite material comprises vanadium dioxide and a polypyrrole coating layer coated on the vanadium dioxide. Polypyrrole is a high molecular material, has excellent conductivity, reversible electrochemical redox characteristics and strong charge storage capacity, and has good stability in air and water. Meanwhile, the coated polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium removal, so that the pulverization and falling probability of active substances is delayed, and the cycle performance and the rate performance of the water-system aluminum ion battery are improved. The raw materials have wide sources and low cost.
Description
Technical Field
The invention relates to the technical field of water-system aluminum ion batteries, in particular to a composite material and a preparation method thereof, a positive electrode material and a water-system aluminum ion battery.
Background
With the development of national economy, the demand of China on green energy is more urgent. The development of renewable energy sources such as solar energy, wind energy and water energy is an important support for energy supply. Among various energy storage technologies, rechargeable batteries are considered as one of the most feasible methods. Lithium ion batteries have been widely used in the portable energy storage and electric vehicle fields due to their high energy density and good cycling stability. However, due to the problems of low safety and high cost, it is important to develop a secondary metal ion battery that can replace a lithium ion battery.
Among them, the aqueous aluminum ion battery has a higher safety factor, ionic conductivity, and a lower price, and is receiving wide attention. However, there are few electrode materials known to be used in aqueous aluminum ion batteries, and the cycle performance and rate capability of the electrode materials for aqueous aluminum ion batteries need to be improved.
Disclosure of Invention
The invention mainly aims to provide a composite material, a preparation method thereof, a positive electrode material and a water-based aluminum ion battery, and aims to solve the problem that the water-based aluminum ion battery in the prior art is low in cycle performance and rate capability.
In order to achieve the above object, according to one aspect of the present invention, there is provided a composite material including vanadium dioxide and a polypyrrole coating layer coated on the vanadium dioxide.
Further, the mass ratio of the vanadium dioxide to the polypyrrole coating layer is 1.0: 0.1-1.0, and preferably the mass ratio of the vanadium dioxide to the polypyrrole coating layer is 1.0: 0.5-1.0.
According to another aspect of the present invention, there is provided a method of preparing a composite material, the method comprising: step S1, mixing vanadium dioxide, pyrrole monomer and dispersant to obtain a mixture; and step S2, adding an oxidant into the mixture for polymerization reaction to obtain a composite material, wherein a polypyrrole coating layer in the composite material is coated on the surface of vanadium dioxide.
Further, the mass ratio of the pyrrole monomer to vanadium dioxide is 0.1 to 1.0:1.0, preferably 0.5 to 1.0:1.0, and further preferably the D50 particle size of vanadium dioxide is 20 to 100 nm.
Further, the oxidant is selected from ammonium persulfate, ferric chloride and H2O2Preferably, ammonium persulfate is added in the form of ammonium persulfate solution, and the mass ratio of the ammonium persulfate solution to the vanadium dioxide is preferably 1-5: 1.
Further, the adding speed of the ammonium persulfate solution is 0.04-2.4 mL/min.
Further, the temperature of the polymerization reaction is 0-5 ℃, and the time of the polymerization reaction is preferably 6-24 h.
Further, the solid content of the mixture is 0.5-5%, and the dispersing agent is preferably selected from one or more of water, ethanol and acetone.
According to another aspect of the present invention, there is provided a positive electrode material comprising a composite material as described above.
According to still another aspect of the present invention, there is provided an aqueous aluminum ion battery comprising a positive electrode and a negative electrode, wherein the positive electrode comprises a positive electrode material, and the positive electrode material is the positive electrode material.
By applying the technical scheme of the invention, the polypyrrole is a high polymer material, has excellent conductivity, reversible electrochemical redox property and stronger charge storage capacity, and has better stability in air and water. Meanwhile, the coated polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium removal, so that the pulverization and falling probability of active substances is delayed, and the cycle performance and the rate performance of the water-system aluminum ion battery are improved. The raw materials have wide sources and low cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the charge-discharge curves of the composite materials obtained in example 1 and comparative example 1 according to the present invention at 2C;
FIG. 2 shows a graph of rate performance at 1C, 2C, 5C, 7C, 10C, 15C, 20C, 30C for composites obtained according to example 1 and comparative example 1 of the present invention, respectively; and
fig. 3 shows capacity retention rate graphs of the composite materials obtained in example 1 and comparative example 1 according to the present invention, respectively, after cycling at 5C for 200 weeks.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the problem of low cycle performance and rate capability of the water-based aluminum ion battery exists in the prior art, and in order to solve the problem, the invention provides a composite material, a preparation method thereof, a positive electrode material and the water-based aluminum ion battery.
In an exemplary embodiment of the present application, a composite material is provided that includes vanadium dioxide and a polypyrrole coating layer coated on the vanadium dioxide.
Polypyrrole is a high molecular material, has excellent conductivity, reversible electrochemical redox characteristics and strong charge storage capacity, and has good stability in air and water. Meanwhile, the coated polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium removal, so that the pulverization and falling probability of active substances is delayed, and the cycle performance and the rate performance of the water-system aluminum ion battery are improved. The raw materials have wide sources and low cost.
The polypyrrole is too little to sufficiently coat the vanadium dioxide, and too much polypyrrole easily causes too large weight of the composite material, so that the composite material is not beneficial to preparing a light battery, therefore, in order to balance the effects of the two aspects, the mass ratio of the vanadium dioxide to the polypyrrole coating layer is preferably 1.0: 0.1-1.0, and in order to further optimize the composite material, the mass ratio of the vanadium dioxide to the polypyrrole coating layer is preferably 1.0: 0.5-1.0.
In another exemplary embodiment of the present application, there is provided a method of preparing a composite material, the method comprising: step S1, mixing vanadium dioxide, pyrrole monomer and dispersant to obtain a mixture; and step S2, adding an oxidant into the mixture for polymerization reaction to obtain a composite material, wherein a polypyrrole coating layer in the composite material is coated on the surface of vanadium dioxide.
Firstly, uniformly dispersing vanadium dioxide and pyrrole monomers in a dispersing agent to obtain a mixture which is as uniform as possible, then adding an oxidant into the mixture to initiate the pyrrole monomers to carry out polymerization reaction, and coating the formed polypyrrole on the surface of the vanadium dioxide to obtain the polypyrrole-coated vanadium dioxide composite material. Because polypyrrole is a high molecular material, the polypyrrole has excellent conductivity, reversible electrochemical redox property and stronger charge storage capacity, and has better stability in air and water. Meanwhile, the coated polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium removal, so that the pulverization and falling probability of active substances is delayed, and the cycle performance and the rate performance of the water-system aluminum ion battery are improved. The preparation method is simple and low in cost.
In order to reasonably control the addition amount of the pyrrole monomer so as not to cause the overlarge weight of the composite material due to the excessive addition of the pyrrole monomer on the basis of achieving the effect of fully coating the vanadium dioxide, the mass ratio of the pyrrole monomer to the vanadium dioxide is preferably 0.1-1.0: 1.0, and the D50 particle size of the vanadium dioxide is preferably 20-100 nm. Thereby being beneficial to realizing the full coating of the vanadium dioxide.
In addition, the vanadium dioxide can be purchased or prepared, and the preparation method is preferably adopted by the applicant to improve the preparation efficiency of the vanadium dioxide:
adding vanadium pentoxide, citric acid and a surfactant into 50-70 mL of deionized water according to a certain proportion, and uniformly stirring; adding the solution into a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 130-220 ℃ for 6-24 h, and then naturally cooling to room temperature; and collecting the solid, washing the solid with absolute ethyl alcohol and distilled water for multiple times, and drying the solid in vacuum to obtain the vanadium dioxide nano material. Wherein the molar ratio of the citric acid to the vanadium pentoxide is 4: 1-1: 1, the surfactant is any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide, and the concentration of the surfactant is 0.001-0.01 mol/L. Of course, the synthesis of vanadium dioxide can be performed by those skilled in the art by referring to other methods in the prior art, and will not be described herein.
In one embodiment of the present application, the above-mentioned oxidizing agent is selected from ammonium persulfate, ferric chloride, H2O2Preferably, ammonium persulfate is added in the form of ammonium persulfate solution, and the mass ratio of the ammonium persulfate solution to the vanadium dioxide is preferably 1-5: 1.
The above-mentioned oxidant can initiate the polymerization reaction of pyrrole monomer, and in order to reduce the introduction of metal ions in the polymerization reaction system as much as possible, ammonium persulfate is preferably used as the oxidant. In order to further improve the efficiency of the polymerization reaction and avoid causing unnecessary waste of ammonium persulfate, the mass ratio of the ammonium persulfate solution to the vanadium dioxide is preferably 1-5: 1.
The method is to reasonably control the polymerization rate, thereby avoiding the problems of self polymerization of a large amount of pyrrole monomers, polypyrrole agglomeration and low coating efficiency. Preferably, the adding speed of the ammonium persulfate solution is 0.04-2.4 mL/min.
Besides controlling the polymerization speed through the adding speed of the ammonium persulfate solution, the temperature of the polymerization reaction can be controlled, the progress of the polymerization reaction can be controlled, so that the polypyrrole is coated on the surface of the vanadium dioxide as much as possible, meanwhile, in order to take the efficiency of the polymerization reaction into consideration, the temperature of the polymerization reaction is preferably 0-5 ℃, and the time of the polymerization reaction is preferably 6-24 hours.
The concentration of the pyrrole monomer and vanadium dioxide in the mixture can affect the rate of the polymerization reaction, in order to enable the pyrrole monomer in the mixture to be efficiently polymerized and to form a polypyrrole coating layer on the surface of the vanadium dioxide as much as possible, the solid content of the mixture is preferably 0.5-5%, and the dispersing agent is preferably selected from one or more of water, ethanol and acetone.
In yet another exemplary embodiment of the present application, a positive electrode material is provided, which includes a composite material, which is the aforementioned composite material.
The positive electrode material comprising the composite material has excellent conductivity, reversible electrochemical redox property and strong charge storage capacity, and has good stability in air and water.
In another exemplary embodiment of the present application, there is provided an aqueous aluminum ion battery including a positive electrode and a negative electrode, the positive electrode including a positive electrode material, the positive electrode material being the positive electrode material described above.
The aqueous aluminum ion battery with the positive electrode comprising the positive electrode material has excellent cycle performance and rate performance.
In addition, in order to facilitate the application of the technical personnel in the field, the application provides a preparation method of the positive pole piece of the water-based aluminum-ion battery, which comprises the following steps:
mixing the composite material with a conductive agent and a binder according to a certain proportion, dripping deionized water, stirring to obtain uniform slurry, coating the slurry on a current collector, drying, rolling, punching, and drying at 60-80 ℃ in a vacuum drying oven with the vacuum degree of-0.10 MPa to prepare the positive pole piece. Wherein the current collector is carbon paper, stainless steel, a titanium sheet or a tantalum sheet. The binder is Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) or Styrene Butadiene Rubber (SBR). The conductive agent is selected from any one or more of conductive graphite, conductive carbon black, conductive carbon fiber and carbon nano tube.
Of course, those skilled in the art may refer to the preparation methods of the positive electrode plates of other aqueous aluminum ion batteries in the prior art, and details are not described herein again.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Vanadium dioxide with the particle size of 50nm of D50, pyrrole monomer and water are mixed to obtain a mixture. The solid content of the mixture is 5 percent, and the ammonium persulfate solution is dropped into the mixture at the speed of 2.4mL/min and mixed at the temperature of 0 DEG CAnd carrying out polymerization reaction in the compound for 6h to obtain the polypyrrole-coated vanadium dioxide composite material. Wherein the mass ratio of the ammonium persulfate solution to the vanadium dioxide is 5:1, and the mass ratio of the pyrrole monomer to the vanadium dioxide is 1.0: 1.0. The mass ratio of the vanadium dioxide to the polypyrrole coating layer in the obtained composite material is 1.0: 1.0. The composite material (VO)2@ Ppy) at 2C, as shown in fig. 1, the rate performance of the composite material at 1C, 2C, 5C, 7C, 10C, 15C, 20C, and 30C, respectively, as shown in fig. 2, and the capacity retention rate of the composite material at 5C for 200 cycles, as shown in fig. 3.
Example 2
Example 2 differs from example 1 in that,
the dropping speed of the ammonium persulfate solution is 0.04mL/min, and the composite material is finally obtained.
Example 3
Example 3 differs from example 1 in that,
the dropping speed of the ammonium persulfate solution is 1.5mL/min, and the composite material is finally obtained.
Example 4
Example 4 differs from example 1 in that,
the dropping speed of the ammonium persulfate solution is 2.8mL/min, and the composite material is finally obtained.
Example 5
Example 5 differs from example 1 in that,
the mass ratio of the pyrrole monomer to the vanadium dioxide is 0.5:1.0, and the composite material is finally obtained, wherein the mass ratio of the vanadium dioxide to the polypyrrole coating layer in the composite material is 1.0: 0.5.
Example 6
Example 6 differs from example 1 in that,
the mass ratio of the pyrrole monomer to the vanadium dioxide is 0.1:1.0, and the composite material is finally obtained, wherein the mass ratio of the vanadium dioxide to the polypyrrole coating layer in the composite material is 1.0: 0.1.
Example 7
Example 7 differs from example 1 in that,
the mass ratio of the pyrrole monomer to the vanadium dioxide is 0.08:1.0, and the composite material is finally obtained, wherein the mass ratio of the vanadium dioxide to the polypyrrole coating layer in the composite material is 1.0: 0.08.
Example 8
Example 8 differs from example 1 in that,
the mass ratio of the ammonium persulfate solution to the vanadium dioxide is 1:1, and finally the composite material is obtained.
Example 9
Example 9 differs from example 1 in that,
the mass ratio of the ammonium persulfate solution to the vanadium dioxide is 3:1, and finally the composite material is obtained.
Example 10
Example 10 differs from example 1 in that,
the mass ratio of the ammonium persulfate solution to the vanadium dioxide is 0.05:1, and finally the composite material is obtained.
Example 11
Example 11 differs from example 1 in that,
the solid content of the mixture was 0.5%, and the composite material was finally obtained.
Example 12
Example 12 differs from example 1 in that,
the solid content of the mixture was 3%, and the composite material was finally obtained.
Example 13
Example 13 differs from example 1 in that,
the solid content of the mixture was 8%, and the composite material was finally obtained.
Example 14
Example 14 differs from example 1 in that,
and carrying out polymerization reaction at 5 ℃ to obtain the final composite material.
Example 15
Example 15 differs from example 1 in that,
and carrying out polymerization reaction at 2 ℃ to finally obtain the composite material.
Example 16
Example 16 differs from example 1 in that,
and carrying out polymerization reaction at 10 ℃ to obtain the final composite material.
Example 17
Example 17 differs from example 1 in that,
the D50 particle size of the vanadium dioxide is 20nm, and the composite material is finally obtained.
Example 18
Example 18 differs from example 1 in that,
the D50 particle size of the vanadium dioxide is 100nm, and the composite material is finally obtained.
Example 19
Example 19 differs from example 1 in that,
the D50 particle size of the vanadium dioxide is 120nm, and the composite material is finally obtained.
Example 20
Example 20 differs from example 1 in that,
mixing vanadium dioxide with the D50 particle size of 50nm, pyrrole monomer and ethanol to obtain a mixture, and finally obtaining the composite material.
Example 21
Example 21 differs from example 1 in that,
the time of the polymerization reaction is 24 hours, and the composite material is finally obtained.
Example 22
Example 22 differs from example 1 in that,
the time of the polymerization reaction is 15h, and the composite material is finally obtained.
Example 23
Example 23 differs from example 1 in that,
the time of the polymerization reaction is 4 hours, and the composite material is finally obtained.
Comparative example 1
Comparative example 1 differs from example 1 in that vanadium dioxide is not coated and is used directly as the final composite material. The charge-discharge curve of the vanadium dioxide composite material under 2C is shown in figure 1, the rate performance of the vanadium dioxide composite material under 1C, 2C, 5C, 7C, 10C, 15C, 20C and 30C is shown in figure 2, and the capacity retention rate of the vanadium dioxide composite material under 5C and 200 weeks of cycle is shown in figure 3.
And (2) respectively mixing the composite materials obtained in the embodiments 1 to 23 and the comparative example 1 with a conductive agent and polytetrafluoroethylene according to the mass ratio of 9:0.5:0.5, dripping deionized water, stirring to obtain uniform slurry, coating the uniform slurry on stainless steel, drying, rolling and punching, and drying at 80 ℃ in a vacuum drying oven with the vacuum degree of-0.10 MPa to prepare the positive pole pieces 1 to 24.
Electrochemical test method: silver-silver chloride is used as reference electrode and graphite rod electrode
For the counter electrode, the positive electrode pieces 1 to 24 are respectively positive electrodes, the aluminum chloride electrolyte is an aluminum ion aqueous electrolyte, corresponding aqueous aluminum ion batteries 1 to 24 are respectively obtained, the capacity retention rates of the aqueous aluminum ion batteries 1 to 24 from 1C to 5C are respectively tested, the capacity retention rates of the aqueous aluminum ion batteries 1 to 24 after 200 cycles are respectively tested at 5C, and the test results are listed in table 1.
TABLE 1
From the comparison of the above water-based aluminum ion batteries 1 to 24, it can be seen that the composite material obtained by coating vanadium dioxide with polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium deintercalation, thereby greatly improving the cycle performance and rate capability of the water-based aluminum ion battery.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
polypyrrole is a high molecular material, has excellent conductivity, reversible electrochemical redox characteristics and strong charge storage capacity, and has good stability in air and water. Meanwhile, the coated polypyrrole reduces the volume expansion effect of vanadium dioxide in the processes of lithium intercalation and lithium removal, so that the pulverization and falling probability of active substances is delayed, and the cycle performance and the rate performance of the water-system aluminum ion battery are improved. The raw materials have wide sources and low cost. The raw materials have wide sources and low cost.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite material is characterized by comprising vanadium dioxide and a polypyrrole coating layer coated on the vanadium dioxide.
2. The composite material according to claim 1, wherein the mass ratio of the vanadium dioxide to the polypyrrole coating layer is 1.0: 0.1-1.0, and preferably the mass ratio of the vanadium dioxide to the polypyrrole coating layer is 1.0: 0.5-1.0.
3. A method of making a composite material, the method comprising:
step S1, mixing vanadium dioxide, pyrrole monomer and dispersant to obtain a mixture;
and step S2, adding an oxidant into the mixture for polymerization reaction to obtain the composite material, wherein a polypyrrole coating layer in the composite material is coated on the surface of the vanadium dioxide.
4. The preparation method according to claim 3, wherein the mass ratio of the pyrrole monomer to the vanadium dioxide is 0.1-1.0: 1.0, preferably 0.5-1.0: 1.0, and further preferably the D50 particle size of the vanadium dioxide is 20-100 nm.
5. The method according to claim 3 or 4, wherein the oxidizing agent is selected from ammonium persulfate, ferric chloride, H2O2Preferably, the ammonium persulfate is added in the form of an ammonium persulfate solution, and the mass ratio of the ammonium persulfate solution to the vanadium dioxide is 1-5: 1.
6. The preparation method according to claim 5, wherein the ammonium persulfate solution is added at a rate of 0.04-2.4 mL/min.
7. The method according to any one of claims 3 to 6, wherein the temperature of the polymerization reaction is 0 to 5 ℃, and preferably the time of the polymerization reaction is 6 to 24 hours.
8. The preparation method according to any one of claims 3 to 6, wherein the solid content of the mixture is 0.5-5%, and preferably the dispersant is selected from any one or more of water, ethanol and acetone.
9. A positive electrode material comprising a composite material, characterized in that the composite material is the composite material according to claim 1 or 2.
10. An aqueous aluminum ion battery comprising a positive electrode and a negative electrode, wherein the positive electrode comprises a positive electrode material, and the positive electrode material is the positive electrode material according to claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050245A (en) * | 2021-11-16 | 2022-02-15 | 中科南京绿色制造产业创新研究院 | Composite cathode material with spring-shaped lamellar structure and preparation method and application thereof |
| CN114725391A (en) * | 2022-04-06 | 2022-07-08 | 华南理工大学 | Zinc-ion battery positive electrode material and preparation method and application thereof |
| CN114744197A (en) * | 2022-03-30 | 2022-07-12 | 五邑大学 | Vanadium oxide-polypyrrole composite material and preparation method and application thereof |
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2020
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050245A (en) * | 2021-11-16 | 2022-02-15 | 中科南京绿色制造产业创新研究院 | Composite cathode material with spring-shaped lamellar structure and preparation method and application thereof |
| CN114050245B (en) * | 2021-11-16 | 2023-12-15 | 中科南京绿色制造产业创新研究院 | Composite positive electrode material with spring-like lamellar structure, and preparation method and application thereof |
| CN114744197A (en) * | 2022-03-30 | 2022-07-12 | 五邑大学 | Vanadium oxide-polypyrrole composite material and preparation method and application thereof |
| CN114744197B (en) * | 2022-03-30 | 2024-05-28 | 五邑大学 | Vanadium oxide-polypyrrole composite material and preparation method and application thereof |
| CN114725391A (en) * | 2022-04-06 | 2022-07-08 | 华南理工大学 | Zinc-ion battery positive electrode material and preparation method and application thereof |
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