CN114566628A - Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery - Google Patents
Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery Download PDFInfo
- Publication number
- CN114566628A CN114566628A CN202210207218.9A CN202210207218A CN114566628A CN 114566628 A CN114566628 A CN 114566628A CN 202210207218 A CN202210207218 A CN 202210207218A CN 114566628 A CN114566628 A CN 114566628A
- Authority
- CN
- China
- Prior art keywords
- vanadate
- phytic acid
- reaction
- solution
- ion battery
- 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.)
- Granted
Links
Images
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- 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
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a phytic acid doped polypyrrole @ vanadate water-based zinc ion battery anode material. According to the technical scheme, the phytic acid doped polypyrrole @ vanadate anode material obtained according to the technical scheme can effectively avoid the dissolution of vanadate in the electrolyte of the water-based zinc ion battery through the protection effect of the coating layer, and is beneficial to the structural stability of an electrode in the charging and discharging processes; meanwhile, the coating of the conductive polypyrrole can promote the electronic conduction process of the electrode material; in addition, the introduction of the hydrophilic phytic acid is beneficial to the desolvation process of zinc ions in the electrolyte, the migration rate of carriers between an electrode material and an electrolyte interface is promoted, and the rate capability is improved.
Description
Technical Field
The invention relates to a preparation method of a cathode material of a zinc ion battery doped with phytic acid and polypyrrole @ vanadate water system, belonging to the field of modification methods of cathode materials of zinc ion batteries.
Background
In order to meet the prospect of carbon neutralization, the development of advanced energy storage technology for storing energy for renewable energy sources is trending greatly. During the last two decades, lithium ion batteries have dominated energy storage batteries due to their higher energy density and wider voltage window. However, the sustainable development of lithium batteries is tested due to safety accidents, the shortage of lithium resources, the complex assembly process of lithium batteries and other problems which occur in the lithium batteries. Especially in recent years, with the rise of energy storage in the power grid scale, the energy storage market puts higher and higher requirements on the safety and low cost of the battery. Under the background, the development of novel lithium batteries to replace energy storage technology is urgent.
Zinc ion batteries based on near-neutral aqueous electrolytes have gained widespread attention in the last decade due to the relatively low price of zinc and the high safety of aqueous electrolytes. The zinc ion battery has the advantages of low cost and high safety, and also has convenient assembly and high volume energy density (5851 mAhmL)-1) And the electrolyte has high ion mobility (approximately equal to 1-10 mScm)-1) And the like. However, the development of zinc ion batteries is still limited by a number of challenges. From the perspective of the anode material, due to Zn in the charging and discharging process2+The strong interaction with the bulk structure of the positive electrode material makes the development of the positive electrode material of the high-performance zinc ion battery extremely challenging.
The positive electrode of the zinc ion battery reported at present comprises manganese-based oxide, Prussian blue analogue and vanadate (M)xVyOz·nH2O, M ═ Ni, Mg, Co, Zn, Ca, and the like). Among them, vanadates exhibit high capacity characteristics due to the multi-electron reaction of vanadium. And the crystal structure of the vanadate generally has larger pore channels which can supply Zn2+In vivoThe phase structure can be quickly embedded and removed. For example, CN105006561A reports a Zn2+Intercalated V10O24·12H2The O-layered vanadium oxide shows good zinc ion storage performance. CN113764661A reports a transition metal vanadate zinc ion battery anode material, which shows good rate capability. However, the problems of the vanadate zinc ion battery cathode material still exist in different degrees in actual operation and need to be solved urgently. For example, vanadium is easily dissolved in an aqueous electrolyte, and the structural stability of the material in the charge and discharge processes is reduced; vanadate materials generally have relatively low electrical conductivity, which hinders the high rate performance of such materials; in addition, as zinc ions are easy to solvate in aqueous electrolyte, the radius of a current carrier is greatly increased by a solvation shell layer, and the energy barrier of a phase structure of the embedded electrode material is increased, so that the ion conduction capability of the material is reduced. The problems greatly hinder the further improvement of the zinc storage performance of the vanadate material. In view of this, it is very important to further structure control of vanadate.
Disclosure of Invention
Aiming at various problems of vanadate, the invention discloses a preparation method of a cathode material of a plant acid doped polypyrrole @ vanadate water-based zinc ion battery. The phytic acid doped polypyrrole @ vanadate is prepared by static chemical oxidative polymerization, due to the strong electron affinity of a phosphate group in phytic acid, the phytic acid doped polypyrrole @ vanadate can be uniformly coated on the surface of the vanadate through complexation, and pyrrole monomers are bridged through the action of hydrogen bonds, so that the phytic acid doped polypyrrole uniformly coated vanadate can be prepared by in-situ oxidative polymerization under the initiation of ammonium persulfate. Because the polypyrrole has a high pi-pi conjugated polymeric chain and belongs to a conductive polymer, the conductivity of the vanadium-based anode can be greatly improved; the hydrophilic property of the phytic acid can induce the desolvation process of zinc ions, which is beneficial to the rapid conduction of current carriers at the interface of an electrode/electrolyte; in addition, the uniform organic coating shell layer of the phytic acid doped with the polypyrrole can play a role in protection so as to prevent the vanadium from being dissolved in the water-based electrolyte. The phytic acid doped polypyrrole coated vanadate anode prepared by the invention can effectively improve the specific capacity, the cycling stability and the rate capability of an anode material.
The invention discloses a preparation method of a phytic acid doped polypyrrole @ vanadate water-based zinc ion battery anode material, which comprises the following steps of:
step 1: dissolving a metal ion (Ni, Mg, Co, Zn and Ca ions) precursor in deionized water to obtain a solution, adding vanadium pentoxide powder into the solution, uniformly stirring and mixing, then adding acetone, and continuously stirring to obtain a reaction solution; pouring the reaction liquid into a Teflon liner of a hydrothermal reaction kettle, transferring the reaction liquid to a drying oven, heating to a set temperature, continuously reacting for a certain time, naturally cooling to room temperature after the reaction is finished, carrying out suction filtration operation on the reaction product, washing the obtained filter cake for multiple times by using ultrapure water and isopropanol, and drying to obtain vanadate.
And 2, step: adding the vanadate powder obtained in the step 1 into a mixed solution of phytic acid and pyrrole monomers, and uniformly mixing to obtain a suspension; dissolving a certain amount of ammonium persulfate in deionized water to obtain a solution; rapidly adding an ammonium persulfate solution into a vanadate/phytic acid/pyrrole suspension, slightly shaking, uniformly mixing, and standing to enable a pyrrole monomer to be subjected to in-situ polymerization; and after the reaction is finished, carrying out suction filtration on the reaction product, washing the reaction product for multiple times by using deionized water and ethanol, and drying the reaction product to obtain the phytic acid doped polypyrrole coated vanadate zinc ion battery positive electrode material.
In the step 1, the metal ion precursor is one of nickel acetate, magnesium acetate, cobalt acetate, zinc acetate and calcium chloride.
In the step 1, the concentration range of the metal ion precursor solution is 0.01-0.1 mol/L, the molar ratio of the vanadium pentoxide to the metal ion precursor is 1-2: 1, and the volume ratio of the acetone to the deionized water is 0.01-0.1: 1.
In the step 1, the heating reaction temperature is 150-220 ℃, the reaction time is 24-72 hours, and the natural cooling refers to natural cooling in an oven.
In the step 2, the addition mass range of vanadate powder is 0.1-1 g.
In the step 2, the volume ratio of the phytic acid to the pyrrole monomer is 1: 1-1: 10.
In the step 2, the standing reaction time ranges from 1 min to 10 min.
In the step 2, the addition amount of the ammonium persulfate solution is 1mL, and the solution concentration is 100-200 mg/mL.
The phytic acid doped polypyrrole @ vanadate anode material prepared by the invention has a core-shell structure, a phytic acid doped polypyrrole layer is used as a coating shell layer, and a vanadate nanobelt is used as a coating inner core.
The application of the phytic acid doped polypyrrole @ vanadate as the anode material in the zinc ion battery comprises the following steps:
1) preparing a positive electrode plate: dissolving polyvinylidene fluoride in N-methyl pyrrolidone, uniformly grinding the phytic acid doped polypyrrole @ vanadate positive electrode material and acetylene black, adding the materials into the mixture, uniformly mixing to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, and drying to obtain the positive electrode plate. The mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is (6-8) to (1-3) to (0.5-1.5);
2) preparing a negative electrode plate: ultrasonically washing a zinc foil with the thickness of 80 mu m in absolute ethyl alcohol, drying and punching into a wafer to prepare a negative electrode slice;
3) preparing an electrolyte: dissolving zinc sulfate in deionized water to prepare an electrolyte, wherein the molar concentration of the zinc sulfate in the electrolyte is 1-3 mol/L, and the primary addition amount of the electrolyte is 100-200 mu L;
4) and (3) assembling the battery by using a commercial CR2032 type electrode shell and adopting a glass fiber diaphragm as the diaphragm according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and pressurizing and packaging after the assembly to obtain the water-based zinc ion battery.
The invention has the following beneficial effects:
1. the phytic acid doped polypyrrole @ vanadate anode material prepared by the technical scheme of the invention can effectively block the dissolution of vanadium in aqueous electrolyte through the protection effect of the coating layer, promote the stability of the electrode material in the charging and discharging processes, and improve the cycle performance.
2. The phytic acid doped polypyrrole coated vanadate anode material prepared by the technical scheme of the invention can promote the desolvation process of zinc ions at the interface of an electrode/electrolyte based on the hydrophilicity of phytic acid, and effectively promote the conduction rate of current carriers.
3. The phytic acid doped polypyrrole coated vanadate anode material prepared by the technical scheme of the invention can promote the electron conduction capability of an electrode based on the conductive action of polypyrrole, and is beneficial to improving the rate capability of the material.
4. According to the method, based on the bridging effect of the phytic acid, the phytic acid-doped polypyrrole organic shell layer is uniformly coated on the surface of the vanadate through a static chemical oxidation polymerization method, so that the zinc ion storage performance of the vanadate can be obviously improved, the technical scheme is simple and effective, the operability is high, and the method has a high practical application value.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the phytic acid doped polypyrrole @ calcium vanadate cathode material prepared in example 1. As can be seen from the figure, the XRD peaks of calcium vanadate and phytic acid doped polypyrrole @ calcium vanadate are both equal to Ca0.24V2O5·nH2O (PDFNo.88-0579, space group C2/m) corresponds to the fact that the coating of the phytic acid doped polypyrrole has no influence on the crystal structure of the calcium vanadate.
Fig. 2 is a Transmission Electron Microscope (TEM) image and an element area scan (EDS) image of the phytic acid doped polypyrrole @ calcium vanadate prepared in example 1. As can be seen from figure 2, the phytic acid doped polypyrrole @ calcium vanadate has an obvious core-shell structure, the coating shell is a phytic acid doped polypyrrole organic matter layer, the core is a calcium vanadate nanobelt, the width of the nanobelt is about 100 nanometers, and the thickness of the coating layer is about 5-10 nm. As can be seen from the EDS results, the N and P elements are uniformly distributed on the nanobelt, indicating that the phytic acid and the polypyrrole are uniformly coated on the surface of the vanadate.
Fig. 3 is a graph of the cycle performance of the phytic acid doped polypyrrole @ calcium vanadate cathode material prepared in example 1. The phytic acid doped polypyrrole @ calcium vanadate prepared by the embodiment is used as the anode material of the water-based zinc ion battery, the discharge specific capacity of 1000 cycles of circulation is still up to 132.6mAh/g under the high current density of 5.0A/g, and compared with the initial capacity, the phytic acid doped polypyrrole @ calcium vanadate has almost no attenuation, and shows excellent circulation stability. In addition, the capacity of the original vanadate is only 52.7mAh/g after the original vanadate is circulated for 1000 circles under the same test condition, which shows that the coating layer greatly improves the zinc storage performance of the calcium vanadate.
Fig. 4 shows different phytic acids prepared in example 1, example 2 and example 3: cycle performance diagram of calcium vanadate anode material coated with polypyrrole in proportion (1:8, 1:7, 3: 7). The results show that the capacity of the three materials after 1000 cycles at a high current density of 5.0A/g is 56.7mAh/g (1:8), 132.6mAh/g (1:7), 109.8mAh/g (3:7), respectively. Thus, phytic acid in the coating: the proportion of polypyrrole has a large influence on the material properties. Too high a phytic acid content can limit the conductive properties of the material; too low phytic acid content also reduces the chelating effect of phytic acid, thereby reducing the coating effect. Among the three materials mentioned above, phytic acid: the material with a polypyrrole ratio of 1:7 shows the best performance.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1: preparation of phytic acid doped polypyrrole @ calcium vanadate positive electrode material CVO @ PA/PPy (PA: PPy: 1:7)
Weighing 0.084g of anhydrous calcium chloride and dissolving in 26.9mL of deionized water to obtain a solution; 0.210g of vanadium pentoxide is weighed and added into the solution, and the solution is stirred and dispersed uniformly; under the condition of stirring, slowly dripping 1.7mL of acetone into the dispersion, stirring for 5min, pouring into a Teflon liner of a hydrothermal reaction kettle, moving into an oven, heating to 200 ℃, and keeping the reaction for 72 h. After natural cooling, carrying out suction filtration, washing (three times of deionized water and one time of isopropanol) and vacuum drying at 60 ℃ for 8-10 h on the reaction precipitate to obtain calcium vanadate. After 0.2g of the obtained calcium vanadate was slightly ground, a mixture of 184. mu.L of phytic acid and 1290. mu.L of pyrrole monomer was added thereto, and the mixture was gently shaken to prepare a suspension A. 184mg (NH)4)2S2O8Dissolve in 1mL deionized water to make solution B. And quickly pouring the solution B into the suspension A, slightly shaking and standing for 5min, carrying out suction filtration and washing for a plurality of times by using deionized water, and then carrying out vacuum drying to obtain the phytic acid doped polypyrrole @ calcium vanadate composite material.
The phytic acid doped polypyrrole @ calcium vanadate serving as the positive electrode material is applied to a water system zinc ion battery, and the method comprises the following steps:
(1) preparing a positive electrode plate: dissolving polyvinylidene fluoride in N-methyl pyrrolidone, uniformly grinding the phytic acid doped polypyrrole @ calcium vanadate positive electrode material and acetylene black, adding the materials into the mixture, uniformly mixing to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, and drying to obtain the positive electrode plate. The mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7:2: 1;
(2) preparing a negative plate: performing ultrasonic treatment on a zinc foil with the thickness of 80 mu m in absolute ethyl alcohol, washing, drying and then punching into a wafer as a negative electrode plate;
(3) preparing an electrolyte: 2mol/L zinc sulfate aqueous solution is used as electrolyte, and the addition amount of the electrolyte is 140 mu L each time;
(4) preparing a battery: and (3) assembling the battery by using a commercial CR2032 type electrode shell and adopting a glass fiber diaphragm as the diaphragm according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and pressurizing and packaging after the assembly to obtain the water-based zinc ion battery. The assembled battery is subjected to constant-current charge and discharge test at 25 ℃, and the test voltage window is set to be 0.4-1.6V (reference is made to Zn)2+/Zn)。
Example 2: preparation of phytic acid doped polypyrrole @ calcium vanadate positive electrode material CVO @ PA/PPy (PA: PPy: 1:8)
Weighing 0.084g of anhydrous calcium chloride and dissolving in 26.9mL of deionized water to obtain a solution; weighing 0.210g of vanadium pentoxide, adding into the solution, stirring, and uniformly dispersing; under the condition of stirring, slowly dripping 1.7mL of acetone into the dispersion, stirring for 5min, pouring into a Teflon liner of a hydrothermal reaction kettle, moving into an oven, heating to 200 ℃, and keeping the reaction for 72 h. After natural cooling, carrying out suction filtration, washing (three times of deionized water and one time of isopropanol) and vacuum drying at 60 ℃ for 8-10 h on the reaction precipitate to obtain calcium vanadate. After 0.2g of the obtained calcium vanadate was slightly ground, 184. mu.L of a mixture of phytic acid and 1472. mu.L of pyrrole monomer was added thereto, and the mixture was gently shaken to prepare a suspension A. 184mg (NH)4)2S2O8Dissolved in 1mL of deionized waterTo prepare a solution B. And pouring the solution B into the suspension A quickly, slightly shaking and standing for 5min, performing suction filtration and washing for several times by using deionized water, and then performing vacuum drying to obtain the phytic acid doped polypyrrole @ calcium vanadate composite material.
The phytic acid doped polypyrrole @ calcium vanadate serving as the positive electrode material is applied to a water system zinc ion battery, and the method comprises the following steps:
(1) preparing a positive electrode plate: dissolving polyvinylidene fluoride in N-methyl pyrrolidone, uniformly grinding the phytic acid doped polypyrrole @ calcium vanadate positive electrode material and acetylene black, adding the materials into the mixture, uniformly mixing to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, and drying to obtain the positive electrode plate. The mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7:2: 1;
(2) preparing a negative plate: performing ultrasonic treatment on a zinc foil with the thickness of 80 mu m in absolute ethyl alcohol, washing, drying and then punching into a wafer as a negative electrode plate;
(3) preparing an electrolyte: 2mol/L zinc sulfate aqueous solution is used as electrolyte, and the addition amount of the electrolyte is 140 mu L each time;
(4) preparing a battery: and (3) assembling the battery by using a commercial CR2032 type electrode shell and adopting a glass fiber diaphragm as the diaphragm according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and pressurizing and packaging after the assembly to obtain the water-based zinc ion battery. The assembled battery is subjected to constant-current charge and discharge test at 25 ℃, and the test voltage window is set to be 0.4-1.6V (reference is made to Zn)2+/Zn)。
Example 3: preparation of phytic acid doped polypyrrole @ calcium vanadate positive electrode material CVO @ PA/PPy (PA: PPy: 3:7)
Weighing 0.084g of anhydrous calcium chloride and dissolving in 26.9mL of deionized water to obtain a solution; weighing 0.210g of vanadium pentoxide, adding into the solution, stirring, and uniformly dispersing; under the condition of stirring, slowly dripping 1.7mL of acetone into the dispersion, stirring for 5min, pouring into a Teflon liner of a hydrothermal reaction kettle, moving into an oven, heating to 200 ℃, and keeping the reaction for 72 h. After natural cooling, the reaction precipitate is filtered, washed (three times of deionized water and once of isopropanol),And drying for 8-10 h at 60 ℃ in vacuum to obtain calcium vanadate. After 0.2g of the obtained calcium vanadate was slightly ground, a mixture of 550. mu.L of phytic acid and 1290. mu.L of pyrrole monomer was added thereto, and the mixture was gently shaken to prepare a suspension A. 184mg (NH)4)2S2O8Dissolve in 1mL of deionized water to obtain solution B. And quickly pouring the solution B into the suspension A, slightly shaking and standing for 5min, carrying out suction filtration and washing for a plurality of times by using deionized water, and then carrying out vacuum drying to obtain the phytic acid doped polypyrrole @ calcium vanadate composite material.
The phytic acid doped polypyrrole @ calcium vanadate serving as the positive electrode material is applied to a water system zinc ion battery, and the method comprises the following steps:
(1) preparing a positive electrode plate: dissolving polyvinylidene fluoride in N-methyl pyrrolidone, uniformly grinding the phytic acid doped polypyrrole @ calcium vanadate positive electrode material and acetylene black, adding the materials into the mixture, uniformly mixing to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, and drying to obtain the positive electrode plate. The mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7:2: 1;
(2) preparing a negative plate: performing ultrasonic treatment on a zinc foil with the thickness of 80 mu m in absolute ethyl alcohol, washing, drying and then punching into a wafer as a negative electrode plate;
(3) preparing an electrolyte: 2mol/L zinc sulfate aqueous solution is used as electrolyte, and the addition amount of the electrolyte is 140 mu L each time;
(4) preparing a battery: and (3) assembling the battery by using a commercial CR2032 type electrode shell and adopting a glass fiber diaphragm as the diaphragm according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and pressurizing and packaging after the assembly to obtain the water-based zinc ion battery. The assembled battery is subjected to constant-current charge and discharge test at 25 ℃, and the test voltage window is set to be 0.4-1.6V (reference is made to Zn)2+/Zn)。
Claims (9)
1. A preparation method of an anode material of a plant acid doped polypyrrole @ vanadate water-based zinc ion battery is characterized by comprising the following steps:
step 1: dissolving a metal ion precursor in deionized water to obtain a solution, adding vanadium pentoxide powder, stirring and mixing uniformly, then adding acetone, and continuously stirring to obtain a reaction solution; pouring the reaction liquid into a Teflon liner of a hydrothermal reaction kettle, transferring the reaction liquid to a drying oven, heating the reaction liquid to a set temperature, continuously reacting for a certain time, naturally cooling the reaction liquid to room temperature after the reaction is finished, carrying out suction filtration on the reaction product, washing the obtained filter cake for multiple times by using ultrapure water and isopropanol, and drying the filter cake to obtain vanadate;
step 2: adding the vanadate powder obtained in the step 1 into a mixed solution of phytic acid and pyrrole monomers, and uniformly mixing to obtain a suspension; dissolving a certain amount of ammonium persulfate in deionized water to obtain a solution; rapidly adding ammonium persulfate solution into vanadate/phytic acid/pyrrole suspension, slightly shaking, uniformly mixing, and standing to polymerize pyrrole monomers in situ; and after the reaction is finished, carrying out suction filtration on the reaction product, washing the reaction product for multiple times by using deionized water and ethanol, and drying the reaction product to obtain the phytic acid doped polypyrrole coated vanadate zinc ion battery positive electrode material.
2. The method of claim 1, wherein:
in the step 1, the metal ion precursor is one of nickel acetate, magnesium acetate, cobalt acetate, zinc acetate and calcium chloride.
3. The method of claim 1, wherein:
in the step 1, the concentration range of the metal ion precursor solution is 0.01-0.1 mol/L, and the molar ratio of the vanadium pentoxide to the metal ion precursor is 1-2: 1.
4. The production method according to claim 1, characterized in that:
in the step 1, the volume ratio of the acetone to the deionized water is 0.01-0.1: 1.
5. The method of claim 1, wherein:
in the step 1, the heating reaction temperature is 150-220 ℃, the reaction time is 24-72 hours, and the natural cooling refers to natural cooling in an oven.
6. The method of claim 1, wherein:
in the step 2, the addition mass range of vanadate powder is 0.1-1 g.
7. The method of claim 1, wherein:
in the step 2, the volume ratio of the phytic acid to the pyrrole monomer is 1: 1-1: 10.
8. The method of claim 1, wherein:
in the step 2, the standing reaction time is 1-10 min.
9. The method of claim 6, wherein:
in the step 2, the addition amount of the ammonium persulfate solution is 1mL, and the solution concentration is 100-200 mg/mL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210207218.9A CN114566628B (en) | 2022-03-04 | 2022-03-04 | Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210207218.9A CN114566628B (en) | 2022-03-04 | 2022-03-04 | Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114566628A true CN114566628A (en) | 2022-05-31 |
CN114566628B CN114566628B (en) | 2023-02-24 |
Family
ID=81717508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210207218.9A Active CN114566628B (en) | 2022-03-04 | 2022-03-04 | Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114566628B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115799586A (en) * | 2022-12-12 | 2023-03-14 | 南阳汉鼎高新材料有限公司 | Sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte and preparation method thereof |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106340401A (en) * | 2016-11-28 | 2017-01-18 | 中物院成都科学技术发展中心 | Preparing method of composite electrode material and application thereof |
CN109809485A (en) * | 2018-12-13 | 2019-05-28 | 南京林业大学 | A kind of height ratio capacity hydration vanadic acid magnesium and the preparation method and application thereof |
CN110350186A (en) * | 2019-07-09 | 2019-10-18 | 齐鲁工业大学 | A kind of preparation method of novel water system Zinc ion battery positive electrode |
KR20200013933A (en) * | 2018-07-31 | 2020-02-10 | 한국과학기술연구원 | A method of uniformly forming a conductive polymer coating layer on the surface of an electrode active material of a secondary battery |
CN111573731A (en) * | 2020-04-26 | 2020-08-25 | 上海大学 | Vanadium-based positive electrode material of water-based zinc ion battery and preparation method and application thereof |
CN111785942A (en) * | 2020-07-17 | 2020-10-16 | 北京大学深圳研究生院 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
CN112349909A (en) * | 2020-11-06 | 2021-02-09 | 常州大学 | Zinc-ion battery positive electrode composite material and preparation method and application thereof |
CN112421028A (en) * | 2020-12-02 | 2021-02-26 | 齐鲁工业大学 | Preparation method of novel water-based zinc ion battery positive electrode material |
CN113921796A (en) * | 2021-10-11 | 2022-01-11 | 河南科技大学 | Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery |
CN113991096A (en) * | 2021-10-09 | 2022-01-28 | 武汉理工大学 | Vanadium pentoxide nanobelt with hydrogen bond network and preparation and application thereof |
-
2022
- 2022-03-04 CN CN202210207218.9A patent/CN114566628B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106340401A (en) * | 2016-11-28 | 2017-01-18 | 中物院成都科学技术发展中心 | Preparing method of composite electrode material and application thereof |
KR20200013933A (en) * | 2018-07-31 | 2020-02-10 | 한국과학기술연구원 | A method of uniformly forming a conductive polymer coating layer on the surface of an electrode active material of a secondary battery |
CN109809485A (en) * | 2018-12-13 | 2019-05-28 | 南京林业大学 | A kind of height ratio capacity hydration vanadic acid magnesium and the preparation method and application thereof |
CN110350186A (en) * | 2019-07-09 | 2019-10-18 | 齐鲁工业大学 | A kind of preparation method of novel water system Zinc ion battery positive electrode |
CN111573731A (en) * | 2020-04-26 | 2020-08-25 | 上海大学 | Vanadium-based positive electrode material of water-based zinc ion battery and preparation method and application thereof |
CN111785942A (en) * | 2020-07-17 | 2020-10-16 | 北京大学深圳研究生院 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
CN112349909A (en) * | 2020-11-06 | 2021-02-09 | 常州大学 | Zinc-ion battery positive electrode composite material and preparation method and application thereof |
CN112421028A (en) * | 2020-12-02 | 2021-02-26 | 齐鲁工业大学 | Preparation method of novel water-based zinc ion battery positive electrode material |
CN113991096A (en) * | 2021-10-09 | 2022-01-28 | 武汉理工大学 | Vanadium pentoxide nanobelt with hydrogen bond network and preparation and application thereof |
CN113921796A (en) * | 2021-10-11 | 2022-01-11 | 河南科技大学 | Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery |
Non-Patent Citations (1)
Title |
---|
XUN ZHAO等: ""Dual-cation preintercalated and amorphous carbon confined vanadium oxides as a superior cathode for aqueous zinc-ion batteries"", 《CARBON》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115799586A (en) * | 2022-12-12 | 2023-03-14 | 南阳汉鼎高新材料有限公司 | Sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte and preparation method thereof |
CN115799586B (en) * | 2022-12-12 | 2023-09-01 | 南阳汉鼎高新材料有限公司 | High-performance vanadium battery electrolyte of sulfuric acid/hydrochloric acid mixed acid system and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114566628B (en) | 2023-02-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
He et al. | Solvent-free mechanochemical synthesis of Na-rich Prussian white cathodes for high-performance Na-ion batteries | |
CN108461719A (en) | It is a kind of richness lithium material/conductive organic polymer composite positive pole and electrode preparation method | |
CN108711613B (en) | Polyaniline/polyethylene glycol co-coated composite ternary cathode material and preparation and application thereof | |
CN104716317B (en) | A kind of sodium-ion battery NaxMnO2The synthetic method of positive electrode | |
CN108539190A (en) | The molybdenum trioxide of a kind of oxygen-containing vacancy and using it as the water system aluminium ion battery of negative electrode active material and their preparation method | |
CN101944588B (en) | Preparation method of capacitor carbon/lithium iron phosphate composite material | |
CN112133897B (en) | Method for reducing surface alkali amount of positive electrode material and improving electrochemical performance through wet coating | |
CN104681795A (en) | Preparation method for lithium ferric manganese phosphate/carbon composite material | |
CN112952047B (en) | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery | |
CN112331830A (en) | Preparation method of graphene-coated nickel-cobalt-manganese ternary positive electrode material | |
CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
CN112053860A (en) | Two-dimensional Ni-MOF/Ti applied to super capacitor3C2Preparation method of (1) | |
CN105406071B (en) | A kind of high magnification vanadium phosphate cathode material and its preparation method and application | |
CN113629242A (en) | Preparation method of polyanionic vanadium iron sodium phosphate positive electrode material | |
CN114566628B (en) | Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material | |
CN103746117A (en) | Preparation method of magnesium-ion-doped lithium ion battery positive pole lithium vanadium phosphate/carbon material | |
CN108217725B (en) | Hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2Preparation method and application of O) material | |
CN107204424B (en) | Preparation method of lithium-rich manganese-based layered lithium battery positive electrode material | |
CN114122394B (en) | Polyoxazine material and preparation method and application thereof | |
CN114530584B (en) | Polyaniline micron-rod structured lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
CN115020660B (en) | PQ-MnO 2 Composite electrode material, preparation method and application thereof | |
CN114335552B (en) | Positive electrode material, modification process thereof and solid-state battery | |
CN114455609B (en) | Preparation method and application of low-cost sodium ion battery positive electrode material with stable circulation | |
CN115703633B (en) | Micron-sized embroidered ball-shaped porous carbon material and preparation method and application thereof | |
CN115295781B (en) | Manganese-based positive electrode material and application thereof in lithium 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |