CN114566628B - Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material - Google Patents
Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material Download PDFInfo
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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 electron 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 becoming a great trend. 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, lack of lithium resources, complex assembly process of lithium batteries and the like during the lithium ion batteries. Especially in recent years, with the rise of the energy storage of 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 process 2+ 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 so far comprises manganese-based oxide, prussian blue analogue and vanadate (M) x V y O z ·nH 2 O, M = Ni, mg, co, zn, ca, etc.). Among them, vanadates allow such materials to 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 Zn 2+ Can be quickly inserted into and removed from the bulk phase structure. For example, CN105006561A reports a Zn 2+ Intercalated V 10 O 24 ·12H 2 The 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 positive electrode material of the vanadate zinc ion battery 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, since zinc ions are easily solvated in an aqueous electrolyte, the solventThe shell layer greatly increases the radius of a current carrier and increases the energy barrier of a phase structure of the current carrier embedded in the electrode material, thereby reducing the ion conduction capability of the material. 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, and is favorable for 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.
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.
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.
In the step 1, the heating reaction temperature is 150-220 ℃, the reaction time is 24-72 h, 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.
In the step 2, the standing reaction time range is 1-10 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 phytic acid doped polypyrrole @ vanadate provided by the invention is used as a positive electrode material and applied to a 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 @ 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 active 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 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) A commercial CR2032 type electrode shell is used, a glass fiber diaphragm is adopted as the diaphragm, the battery is assembled according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and the water system zinc ion battery is prepared by pressurizing and packaging after the assembly.
The invention has the beneficial effects that:
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. The phytic acid-doped polypyrrole organic matter shell layer is uniformly coated on the surface of the vanadate through a static chemical oxidation polymerization method based on the bridging effect of the phytic acid, so that the zinc ion storage performance of the vanadate can be obviously improved, and the technical scheme is simple and effective, has strong operability and has a strong 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 Ca 0.24 V 2 O 5 ·nH 2 O (PDFNo.88-0579, space group is C2/m) corresponds to the content, and shows 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 as high as 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 shows 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 profile of polypyrrole ratio (1. The results show that after 1000 cycles at a high current density of 5.0A/g, the capacities of the three materials are 56.7mAh/g (1:8), 132.6mAh/g (1:7) and 109.8mAh/g (3:7). Thus, phytic acid in the coating: the ratio 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 polypyrrole ratio of 1:7 showed 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; 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 liquid, 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 72h. After natural cooling, the reaction precipitate is subjected to suction filtration, washing (three times of deionized water and one time of isopropanol) and vacuum drying at 60 ℃ for 8-10 h to obtain the 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 suspension A. 184mg (NH) 4 ) 2 S 2 O 8 Dissolve in 1mL of deionized water to obtain 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) 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: a commercial CR2032 type electrode shell is used, a glass fiber diaphragm is adopted as the diaphragm, the battery is assembled according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and the water system zinc ion battery is prepared by pressurizing and packaging after the assembly. 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 anode 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 72h. After natural cooling, the reaction precipitate is subjected to suction filtration, washing (three times of deionized water and one time of isopropanol) and vacuum drying at 60 ℃ for 8-10 hours 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 1472. Mu.L of pyrrole monomer was added thereto, and the mixture was gently shaken to prepare suspension A. 184mg (NH) 4 ) 2 S 2 O 8 Dissolve 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) 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 anode 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 72h. After natural cooling, the reaction precipitate is subjected to suction filtration, washing (three times of deionized water and one time of isopropanol) and vacuum drying at 60 ℃ for 8-10 h to obtain the calcium vanadate. After 0.2g of the obtained calcium vanadate was lightly 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 suspension A. 184mg (NH) 4 ) 2 S 2 O 8 Dissolve in 1mL of deionized water to obtain 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 ground materials into the N-methyl pyrrolidone, 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) 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: a commercial CR2032 type electrode shell is used, a glass fiber diaphragm is adopted as the diaphragm, the battery is assembled according to the sequence of negative electrode shell-shrapnel-gasket-negative electrode sheet-diaphragm + electrolyte-positive electrode sheet-positive electrode shell, and the water system zinc ion battery is prepared by pressurizing and packaging after the assembly. 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 (8)
1. A preparation method of a cathode material of a phytic acid doped polypyrrole @ vanadate water-based zinc ion battery is characterized by comprising the following steps of:
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; after the reaction is finished, carrying out suction filtration on a 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.
2. The method of claim 1, wherein:
in the step 1, the concentration range of the metal ion precursor solution is 0.01 to 0.1mol/L, and the molar ratio of the vanadium pentoxide to the metal ion precursor is 1 to 2.
3. The production method according to claim 1, characterized in that:
in the step 1, the volume ratio of acetone to deionized water is within the range of 0.01 to 0.1.
4. The method of claim 1, wherein:
in the step 1, heating the reaction temperature to be 150 to 220 ℃, and the reaction time to be 24 to 72 hours, wherein the natural cooling refers to natural cooling in an oven.
5. The method of claim 1, wherein:
in the step 2, the mass range of vanadate powder is 0.1 to 1g.
6. The method of claim 1, wherein:
in the step 2, the volume ratio of the phytic acid to the pyrrole monomer is 1 to 1.
7. The method of claim 1, wherein:
in the step 2, standing and reacting for 1 to 10min.
8. The method of claim 5, wherein:
in the step 2, the addition amount of the ammonium persulfate solution is 1mL, and the solution concentration is 100 to 200mg/mL.
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