Preparation method of OrgVO material and application of OrgVO material as positive electrode material of secondary battery

Abstract

The invention provides a preparation method of an OrgVO material and application of the OrgVO material as a positive electrode material of a secondary battery. The OrgVO material is prepared by the following steps: adding V2O5 into deionized water, stirring, adding a hydrogen peroxide solution, and continuously stirring until the mixture is uniform; adding Org into absolute ethyl alcohol or water, and uniformly stirring; uniformly mixing the two solutions, and carrying out solvothermal reaction in a hydrothermal kettle; and after the reaction is finished, cooling and centrifuging to obtain a precipitate, washing and drying to obtain solid powder, and carrying out vacuum drying to obtain the OrgVO material. The OrgVO material is used as an aqueous zinc ion secondary battery positive electrode material for the first time, and compared with an existing positive electrode material, the OrgVO material shows excellent reversible capacity, rate capability and cycling stability. The material can be used as an electrode material in other secondary batteries, such as lithium, sodium, magnesium, calcium and aluminum ion batteries. In addition, the preparation process of the OrgVO material is simple and easy to control, the controllability and efficiency of the preparation process are greatly improved, the cost is low, and industrialization is easy to achieve.

Description

Technical Field

[0001] The invention belongs to the field of electrochemical power sources, and in particular relates to a preparation method of an OrgVO material and an application of the OrgVO material as a positive electrode material for a secondary battery. Background Art

[0002] Currently, lithium-ion batteries (LIBs) dominate the electrochemical energy storage market for electronic devices and electric vehicles, providing satisfactory energy density, excellent specific capacity and cycle stability. However, due to limited lithium resources, relatively expensive cathode materials and electrolytes, and frequent safety accidents, lithium-ion batteries are still unable to meet the low-cost and high-safety requirements of large-scale energy storage systems. Large-scale energy storage systems are an important part of the utilization of renewable energy such as solar energy and wind energy, which has prompted people to seek safer, more economical and efficient electrochemical energy storage technologies.

[0003] Compared with the high cost of lithium resources in LIBs and the safety hazards of organic electrolytes, aqueous zinc ion batteries (AZIBs) have attracted widespread attention due to their safety, environmental friendliness, low cost and simple manufacturing process. The advantages of metallic zinc are high theoretical specific capacity, up to 820mAh / g; low reversible potential, as low as -0.76V relative to the standard hydrogen electrode; high element abundance and lower cost compared to alkali metals. In addition, the price of the cathode material of AZIBs is much cheaper than the commonly used cathode materials of LIBs, and the aqueous electrolyte commonly used in AZIBs has a lower price, higher safety and better ionic conductivity than the organic electrolyte of LIBs, making AZIBs a potential electrochemical energy storage system.

[0004] Among the many positive electrode materials of AZIBs, vanadium-based materials with high capacity, layered structure and multiple valence states are a class of materials with great development prospects. Studies have explored the application of organic molecules and polymers as intercalants, such as ethylene glycol (EG) molecules and polyaniline (PANI). The flexibility of organic matter helps to relieve interlayer lattice strain and inhibit structural degradation. In addition, organic matter with conjugated structure can shield Zn 2+ The electrostatic interaction between Zn and [VO] framework promotes 2+ Rapid diffusion. Recent studies have also explored the application of organic cations. The introduced organic cations combine the properties of inorganic ions and organic matter, and have the advantages of expanding interlayer spacing, shielding Zn 2+The pre-intercalation of organic cations is considered to be an effective way to solve the bottleneck problem of the further development of hydrated vanadium pentoxide. By pre-embedding organic / inorganic cations or organic molecules into the interlayers of hydrated vanadium pentoxide (V2O5·nH2O, referred to as VOH) to expand the interlayer spacing and increase the stability of the layered structure, the specific capacity, rate performance, cycle stability and other electrochemical properties of VOH are improved.

[0005] Therefore, how to explore vanadium-based positive electrodes with high stability in aqueous electrolytes has gradually become the focus of research in this field. Summary of the invention

[0006] Based on the defects and problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a method for preparing an OrgVO material and its application as a positive electrode material for a secondary battery. In order to prepare a vanadium-based aqueous zinc ion battery positive electrode material with high capacity, layered structure and multiple valence states, a method for preparing an OrgVO material is provided, which is simple and easy to control, the process is simple, and it is easy to realize industrial mass production. Another object of the present invention is to use the prepared OrgVO material to provide an aqueous zinc ion secondary battery positive electrode material with high specific capacity at a large rate and no capacity decay after multiple cycles. This application uses OrgVO as a positive electrode material for an aqueous zinc ion secondary battery for the first time, and its electrochemical performance is good. At the same time, the method proposed by the present invention is used to prepare the OrgVO material, the preparation method is simple, the process is easy to control, and the obtained phase is free of impurities. It is a very promising industrial preparation method.

[0007] To achieve the above objectives, the present invention provides the following technical solutions:

[0008] The technical solution of the present application provides a method for preparing an OrgVO material, comprising the following steps:

[0009] (1) dissolving vanadium pentoxide (V2O5) in deionized water, stirring, then adding hydrogen peroxide solution and stirring until uniform; finally adding Org solution and stirring evenly to obtain a mixed solution;

[0010] (2) subjecting the mixed solution obtained in step (1) to a solvothermal reaction;

[0011] (3) After the solvothermal reaction is completed, the solid precipitate is centrifuged and washed to obtain a solid precipitate, and the solid precipitate is freeze-dried to obtain a solid powder. The solid powder is then dried and cooled to obtain the OrgVO material.

[0012] Furthermore, the above operations are preferably performed in a fume hood.

[0013] Furthermore, the concentration of vanadium pentoxide (V2O5) in water in step (1) is 1 to 10 mg / mL.

[0014] Furthermore, the solvent of the Org solution in step (1) is preferably anhydrous ethanol or deionized water, and the molar mass of the added Org is 0.1% to 100% of the vanadium pentoxide.

[0015] Furthermore, the Org in step (1) is at least one of an organic halide, an organic molecule, an organic molecule hydrochloride, an inorganic ion halide or a sulfate.

[0016] Furthermore, the Org is selected from 1-oxa-2-oxo-3-thia-indolizine chloride, trifluoromethanesulfonic acid diphenylamine salt, 1-ethylpyridin-1-ium bis(trifluoromethanesulfonyl)imide salt, diclofenac pyrrolidine ethanol salt, methylamine lead chloride bromide, 1-hexyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, trifluoromethanesulfonic acid diphenylamine salt, dimethylamine lead iodide, dimethylamine lead iodide, 1-methylpyridine iodide, benzylamine chloride, butylamine chloride, propylamine chloride, benzylamine bromide, butylamine bromide, 1-ethyl-3-methylimidazolium bromide, 1-vinyl-3-ethylimidazolium bromide, 1-ethyl-2,3-dimethylimidazolium bromide, formamidine lead bromide iodide, formamidine lead chloride iodide, methylamine lead bromide iodide, pyridine hydrofluoride, triethylamine trihydrofluoride, pyrrolidone tribromide, benzyltrimethylammonium chloride, 1-vinyl-3-butylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-carboxymethyl-3-methylimidazolium chloride, 1,3-diaminopropane dihydroiodide, 1-allyl-3-vinylimidazolium chloride, 1-methylpyridine-2-aldehyde oxime chloride, 1-butyl-3-methylimidazolium bromide, 1,3-propylenediamine dihydrobromide, 1,3-diaminopropane dihydrobromide or 1,4-phenylenediamine dihydroiodide, toluene, p-xylene, 1,3,5-trimethylbenzene, trichlorotoluene, trifluorotoluene, dibromotoluene, 1,2,4- trimethylbenzene, p-chlorotoluene, o-bromotoluene, 2-ethyltoluene, 3,4-dichlorotoluene, 1,2,4,5-tetramethylbenzene, 3,4-dibromotoluene, 4-ethyltoluene, 4-propyltoluene, 3,5-dibromotoluene, 2-fluorotoluene, 4-fluorotoluene, 3-bromotoluene, p-bromotoluene, o-chlorotoluene, m-chlorotoluene, p-tert-butyltoluene, 3-bromo-5-chlorotoluene, α,α-dibromotoluene, 4-bromo-2-fluorotoluene, 4-chloro-2-fluorotoluene, 2-bromo-6-fluorotoluene, 5-chloro-2-fluorotoluene, fluorobenzene, 3-fluorothiophenol, 2-fluorothiophenol, 3-fluoroaniline, 4-fluorothiophenol, 2-fluoroanisole, o-fluoroaniline, 4-fluoroaniline, m-fluorophenylethylamine, 4-fluoroanisole, m-bromofluorobenzene, 1,3-difluorobenzene, p- difluorobenzene, 3-fluorobenzamide, 1,2-difluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 2,3-difluorophenol, 4-fluorophenyl isonitrile, 2,6-difluorophenol, chlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, o-chloroanisole, 4-chlorobenzamide, 3-chlorobenzonitrile, p-bromochlorobenzene, 2-bromochlorobenzene, 2-chlorophenethyl ether, 1,2,4-trichlorobenzene, 3-chlorobenzamide, 1,2,3,4-tetrachlorobenzene, 1-bromo-3-chlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,3-dibromo-2-chlorobenzene, 2,3-difluorochlorobenzene, 4-amino-3-chlorobenzonitrile, 2,4,6-Trimethylchlorobenzene, bromobenzene, 3-bromothiophenol, 4-bromothiophenol, o-bromoanisole, m-bromoanisole, 4-bromophenol, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 1,2-dibromobenzene, 2-bromobenzonitrile, 2,5-dimethylbromobenzene, 1,3,5-tribromobenzene, 2,4-dimethylbromobenzene, m-dibromobenzene, p-dibromobenzene, 3,4-dimethylbromobenzene, 1,2,3-tribromobenzene, 2,5-dibromoaniline, 2, 4-Dibromoaniline, 3,5-Dibromoaniline, 2,6-Dibromoaniline, 2,4,6-Tribromoaniline, 3,4-Dichlorobromobenzene, 1,4-Dibromobenzene, benzylamine, n-propylamine, furfuralamine, isopropanolamine, tert-amylamine, monocyanamide, 5-thiazole, cyclobutylamine, isobutylamine, tert-butylamine, n-propylamine, mono-n-butylamine, N-ethylpropylamine, (±)-tetrahydrofurfurylamine, sec-butylamine, N-methylpropylamine, 1,2-propylenediamine, diethylene glycol, diethylene glycol Alcoholamine, dicyandiamide, diethanolamine, 4,5-dibromo-1,2-phenylenediamine or 1,4-dibromo-2,5-difluorobenzene, 1,3-diaminoguanidine hydrochloride, guanidine hydrochloride, aminoguanidine hydrochloride, o-xylylenediamine dihydrochloride, cysteamine hydrochloride, glycine hydrochloride, ethanolamine hydrochloride, N,N-dimethyl-p-phenylenediamine dihydrochloride, acridine orange hydrochloride, L-NIL hydrochloride, AMT hydrochloride, A-3 hydrochloride, di Metformin hydrochloride, N,N-diethyl-1,2-ethylenediamine dihydrochloride, Xylemin dihydrochloride, phenanthene hydrochloride, triethylamine hydrochloride, imidazole hydrochloride, 4,4-piperidinediol, 3,3-difluorohydrochloride, chloramine hydrochloride, isonicotinoyl chloride hydrochloride, dimethylaminoacetyl chloride hydrochloride, L-2,4-diaminobutyric acid dihydrochloride, 4-pyridylpyridinium chloride hydrochloride, 6-chloronicotinoyl chloride hydrochloride, cyclobutane-1,3-Diamine dihydrochloride, β-glutamic acid hydrochloride, triethanolamine hydrochloride, cystamine dihydrochloride, L-β-homoisoleucine hydrochloride, chitosan hydrochloride, cysteamine-d4 hydrochloride, creatinine hydrochloride, betaine hydrochloride, H-Sar-NH2 hydrochloride, butylamine hydrochloride, aminoacetone hydrochloride, 4-fluoroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromophenylhydrazine hydrochloride, trimethylamine hydrochloride, propylamine hydrochloride, methylamine hydrochloride, allylamine hydrochloride, cyclohexylamine hydrochloride, isopentylamine hydrochloride, piperidine hydrochloride, pyrrolidine hydrochloride, thiosemicarbazide hydrochloride, hexylamine hydrochloride, glycine ethyl ester hydrochloride, diethanolamine hydrochloride, methylguanidine hydrochloride, 2-chloroethylamine hydrochloride, m-toluidine hydrochloride, methylguanidine hydrochloride, DL-α-amino-ε-caprolactam hydrochloride, ethylamine hydrochloride, 3-butenylamine hydrochloride, guanidine hydrochloride Hydrochloride, serinol hydrochloride, ethylenediamine hydrochloride, 2-hydroxypyrimidine hydrochloride, benzamidine hydrochloride, 2-fluoroethylamine hydrochloride, benzylamine hydrochloride, m-anisidine hydrochloride, ethylhydrazine hydrochloride, 1-methylimidazole hydrochloride, β-alanine methyl ester hydrochloride, ethylacetimidate hydrochloride, pentamidine hydrochloride, semicarbazide hydrochloride, 4-hydroxypiperidine hydrochloride, sarcosine ethyl ester hydrochloride, formamidine hydrochloride, propionamidine hydrochloride, chloroformamidine salt Hydrochloride, 3-pyrrolidone hydrochloride, hydrazine monohydrochloride, isobutylamine hydrochloride, 3-hydroxypiperidine hydrochloride, 4-chloroaniline hydrochloride, glycinamide hydrochloride, aminoacetonitrile hydrochloride, propargylamine hydrochloride, 3-amino-1-propanol hydrochloride, acetamidine hydrochloride, pyridine-2-carbonyl chloride hydrochloride, 2-(dimethylamino)acetyl chloride hydrochloride, D-(-)-phenylglycine chloride hydrochloride, N,N-diethyl-1,3-Propylenediamine dihydrochloride, methylenediamine dihydrochloride, (R)-(+)-diaminopropane dihydrochloride or methylenediamine dihydrochloride, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium phosphate, sodium bromide, sodium iodide, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium chloride, rubidium bromide, cesium iodide, sodium nitrate, potassium nitrate, potassium sulfate, potassium hydrogen sulfate, potassium carbonate, Potassium bicarbonate, potassium phosphate, lithium carbonate, lithium bicarbonate, lithium sulfate, lithium bisulfate, lithium chloride, lithium bromide, lithium iodide, potassium chlorate, potassium perchlorate, sodium perchlorate, sodium sulfide, potassium sulfide, sodium cyanide, potassium cyanide, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, beryllium sulfate, magnesium sulfate, calcium sulfate, beryllium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, beryllium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, beryllium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, barium phosphate, aluminum sulfate, aluminum chloride, aluminum sulfide, Aluminum phosphate, sodium aluminate, scandium chloride, scandium sulfate, scandium nitrate, scandium carbonate, scandium acetate, titanium tetrachloride, titanium sulfate, titanium trichloride, titanium tetraiodide, titanium tetrabromide, chromium chloride, chromium sulfate, chromium nitrate, potassium chromate, sodium chromate, potassium dichromate, sodium dichromate, manganese chloride, manganese sulfate, manganese nitrate, potassium manganate, potassium permanganate, ferrous chloride, ferrous sulfate, ferrous nitrate, ferric chloride, ferrous sulfate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, nickel chloride, nickel sulfate, nickel nitrate, nickel carbonate, cuprous chloride, cuprous sulfide, cupric sulfate, cupric chloride, cupric nitrate, carbon At least one of copper oxide, zinc chloride, zinc sulfate, zinc nitrate, zinc carbonate, yttrium chloride, yttrium sulfate, yttrium nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, niobium chloride, sodium niobate, sodium molybdate, ammonium molybdate, molybdenum chloride, sodium technetate, ruthenium chloride, ruthenium sulfate, rhodium chloride, rhodium nitrate, gadolinium chloride, gadolinium sulfate, gadolinium nitrate, samarium chloride, samarium sulfate, samarium nitrate, hafnium tetrachloride, hafnium tetrafluoride, hafnium sulfate, sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate, zinc tungstate, tungsten hexachloride, tungsten fluoride, potassium perrhenate, ammonium perrhenate, rhenium hexachloride, and rhenium pentachloride.

[0017] Furthermore, the stirring time in step (1) is 0.5 to 1 h, and the suitable temperature range during the stirring process is 5 to 30° C., and it is not suitable to use a heater for heating.

[0018] Furthermore, the solvent thermal reaction in step (2) is carried out in a hydrothermal kettle;

[0019] Furthermore, the temperature of the solvent thermal reaction in step (2) is 100 to 200° C., and the reaction time is 0.5 to 48 hours.

[0020] Furthermore, the washing in step (3) is washing three times with ethanol and deionized water;

[0021] Furthermore, the drying in step (3) is preferably carried out in a vacuum drying oven, the drying temperature is 60 to 150° C., and the drying time is 0.5 to 6 hours.

[0022] The technical solution of the present application also provides an OrgVO material prepared by the above preparation method.

[0023] The technical solution of the present application also provides an application of the OrgVO material prepared by the above technical solution, in which OrgVO, acetylene black and PVDF are mixed in a ratio of 70:20:10, coated on a carbon sheet or titanium foil to form an electrode film, and then dried for use as a positive electrode material for a secondary battery.

[0024] Furthermore, the secondary battery is any one of a zinc ion battery, a lithium ion battery, a sodium ion battery, a magnesium ion battery, a calcium ion battery or an aluminum ion battery.

[0025] The technical solution of the present application also provides an aqueous zinc ion secondary battery, which uses OrgVO material as the positive electrode material, 3M Zn(CF3SO3)2 or 2M ZnSO4 dissolved in deionized water as the electrolyte, and zinc sheet as the negative electrode.

[0026] Furthermore, the performance of the aqueous zinc-ion secondary battery was tested. When charged and discharged at a current density of 8 A / g, the discharge specific capacity could reach 308 mAh / g.

[0027] Compared with the prior art, the present invention has the following significant improvements:

[0028] 1. The present invention provides a method for preparing OrgVO material with low production cost, simple and easy controllable method, simple process, and easy industrial mass production. The preparation process is simple and easy to operate, and there are no by-products.

[0029] 2. The OrgVO material described in the present invention is used for the first time as a positive electrode material for aqueous zinc ion secondary batteries, and has high specific capacity and excellent cycle stability.

[0030] 3. The selection range of the Org material of this application is very wide. Whether ions or molecules can be placed into the crystal structure simultaneously or separately to form the same physical phase. The advantage is that the interplanar spacing of the layered structure can be controlled, the local coordination environment can be changed, the ion diffusion channel and the electron orbital energy level can be improved, and the working voltage or fast charge and discharge function of the material can be improved. At the same time, the selectivity of the molecular or ionic polarity can regulate the electrostatic shielding effect of the lattice ions, reduce the ion migration barrier, and realize a variety of valence cations, such as Li + ,Na + ,K + ,Ca2+ Mg 2+ ,Al 3+ In addition, the microscopic morphology that can be designed and regulated is conducive to improving the surface capacitance effect and can expand its application in the capacitor field. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0032] Figure 1 is the phase structure diffraction spectrum of OrgVO in Example 1;

[0033] Figure 2 The battery performance measured when the OrgVO material prepared in Example 1 is used as the positive electrode material of aqueous zinc ion secondary battery and the positive electrode material of lithium ion secondary battery, Figure 2 (a) is the rate characteristics of the aqueous zinc ion secondary battery with OrgVO material as the positive electrode under different current densities in Example 1 of the present invention, Figure 2 (b) is the cycle characteristics of aqueous zinc ion secondary battery at 8A / g. Figure 2 (c) is the complete charge and discharge curve of the aqueous zinc ion secondary battery when cycled at 0.5A / g. Figure 2 (d) is the complete charge and discharge curve of the lithium-ion secondary battery when cycled at 0.01 A / g;

[0034] Figure 3 The CV curve of the aqueous zinc ion secondary battery with the OrgVO material as the positive electrode collected at a scan rate of 0.1 mV / s in Example 1 of the present invention;

[0035] Figure 4 (a) is the phase structure diffraction spectrum of OrgVO in Example 2 of the present invention, Figure 4 (b) is a complete charge-discharge curve of the lithium-ion secondary battery with OrgVO as the positive electrode material when cycled at 0.01 A / g in Example 2;

[0036] Figure 5 is the phase structure diffraction spectrum of OrgVO in Example 3 of the present invention;

[0037] Figure 6 The figure shows the rate characteristics at different current densities in the aqueous zinc ion secondary battery with the OrgVO material as the positive electrode in Example 3 of the present invention. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, several variations and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0039] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0040] Embodiment 1:

[0041] (1) Weigh 1.4550 g of vanadium pentoxide and dissolve it in 220 mL of deionized water. Stir it in a fume hood for half an hour, then add 8 mL of 30% hydrogen peroxide solution and stir it for half an hour until it is uniform. Add 3 mL of trifluorotoluene solution to 115 mL of anhydrous ethanol in a fume hood and stir it to obtain a uniform solution, thereby obtaining a colorless uniform solution. The temperature in the fume hood is 25° C., and the above two solutions are mixed and stirred until they are uniform.

[0042] (2) Take 80 mL of the above solution, put it into a 100 mL reactor, and place it in an oven for hydrothermal reaction at an oven temperature of 120°C for 6 hours. After the reaction is completed, cool it naturally and centrifuge to obtain a green precipitate. Wash the green precipitate twice with ethanol and once with deionized water, freeze it in liquid nitrogen, and then dry it in a cold dryer to obtain a dark green powder. Dry the dark green powder in a vacuum drying oven at a drying temperature of 80°C for 2 hours. Finally, the OrgVO material is obtained.

[0043] The obtained OrgVO material was characterized by XRD. Figure 1 The diffraction pattern of the physical structure of OrgVO was measured by X-ray diffractometer. Figure 1 As shown in the figure, the diffraction pattern of the obtained OrgVO material is similar to that of (Na,Ca)(V,Fe)8O 20 The standard PDF card of nH2O (PDF#45-1363) is very consistent after comparison, indicating that OrgVO and (Na,Ca)(V,Fe)8O 20 nH2O has a similar layered structure.

[0044] The prepared OrgVO material is made into an aqueous zinc ion secondary battery: it is mixed evenly with acetylene black as an active material, and then a polyvinylidene fluoride (PVDF) solution dissolved in N-methylpyrrolidone (NMP) is added, and then ultrasonically mixed evenly, wherein the mass ratio of OrgVO to acetylene black and PVDF is 7:2:1, and then coated on a carbon sheet or titanium foil to form an electrode film, and dried as a positive electrode material; 3MZn(CF3SO3)2 dissolved in deionized water is used as an electrolyte, and a metal zinc sheet is used as a negative electrode to assemble a battery.

[0045] Figure 2 (a) The rate characteristics of the aqueous zinc ion secondary battery with OrgVO material as the positive electrode at different current densities measured by the Xinwei battery test system. When the current density is 0.5A / g, the specific capacity reaches 395mAh / g. As the charge and discharge current density increases to 1A / g, 2A / g, 4A / g and 8A / g, the corresponding specific capacities are 392mAh / g, 376mAh / g, 356mAh / g and 296mAh / g respectively; when the charge and discharge current density decreases again, the corresponding specific capacity increases slightly. This shows that this type of material has very excellent reaction reversibility and charge and discharge capabilities at different currents. (b) The cycle stability of the aqueous zinc ion secondary battery at 8A / g measured by the Xinwei battery test system. After 3000 cycles of charge and discharge, the battery specific capacity has almost no attenuation compared with the first cycle, and the coulombic efficiency is ~100%, indicating excellent rapid charge and discharge stability. (c) is the complete charge and discharge curve of the aqueous zinc ion secondary battery measured by the Xinwei battery test system when it is cycled at 0.5A / g, with a specific capacity of more than 390mAh / g, indicating that the battery can provide high energy density at low current. (d) is the complete charge and discharge curve of the lithium ion secondary battery measured by the Xinwei battery test system when it is cycled at 0.01A / g, with a specific capacity of more than 240mAh / g. This shows that the material can also be used as a positive electrode material for lithium ion batteries. Figure 3 The CV curve of an aqueous zinc-ion secondary battery with OrgVO as the positive electrode was collected at a scan rate of 0.1 mV / s. The two pairs of redox peaks indicate that the energy storage process is accompanied by changes in the valence state of vanadium ions.

[0046] The results show that for aqueous zinc-ion secondary batteries, where OrgVO material is used as the positive electrode material for the first time, it exhibits excellent reversible capacity, rate performance and cycle stability. At the same time, it also shows application potential in lithium-ion batteries.

[0047] Embodiment 2:

[0048] (1) Weigh 1.4550 g of vanadium pentoxide and dissolve it in 220 mL of deionized water. Stir it in a fume hood for half an hour, then add 8 mL of 30% hydrogen peroxide solution and stir it for half an hour until it is uniform. Add 3 mL of trichlorotoluene solution to 115 mL of anhydrous ethanol in a fume hood and stir it to obtain a uniform solution, thereby obtaining a colorless uniform solution. The temperature in the fume hood is 25° C., and the above two solutions are mixed and stirred until they are uniform.

[0049] (2) Take 80 mL of the above solution, put it into a 100 mL reactor, and place it in an oven for hydrothermal reaction at an oven temperature of 120°C for 6 hours. After the reaction is completed, cool it naturally and centrifuge to obtain a green precipitate. Wash the green precipitate twice with ethanol and once with deionized water, freeze it in liquid nitrogen, and then dry it in a cold dryer to obtain a dark green powder. Dry the dark green powder in a vacuum drying oven at a drying temperature of 80°C for 2 hours. Finally, the OrgVO material is obtained.

[0050] The obtained OrgVO material was characterized by XRD. Figure 4 (a) is the diffraction pattern of the physical structure of OrgVO measured by X-ray diffractometer. Figure 4 (a) The diffraction pattern of the obtained OrgVO material is similar to that of (Na,Ca)(V,Fe)8O 20 The standard PDF card of nH2O (PDF#45-1363) is very consistent after comparison, indicating that OrgVO and (Na,Ca)(V,Fe)8O 20 nH2O has a similar layered structure.

[0051] A lithium-ion secondary battery is prepared by using the above-prepared OrgVO material as a positive electrode material (the preparation method is the same as that provided in Example 1), Figure 4 (b) is a complete charge-discharge curve of a lithium-ion secondary battery measured by the Xinwei system at 0.01A / g. The charge-discharge specific capacity is 245mAh / g, indicating that the material has lithium-ion storage capacity.

[0052] Embodiment 3:

[0053] (1) Weigh 0.3638 g of vanadium pentoxide and dissolve it in 50 mL of deionized water. Stir it in a fume hood for half an hour, then add 2 mL of 30% hydrogen peroxide solution and stir it for half an hour until it is uniform; dissolve 1 mmol of benzyltrimethylammonium chloride in 30 mL of deionized water to obtain a colorless transparent solution. The temperature in the fume hood is 25°C, and the above two solutions are mixed and stirred until they are uniform.

[0054] (2) Take 80 mL of the above solution, put it into a 100 mL reactor, and place it in an oven for hydrothermal reaction at a temperature of 120°C for 6 hours. After the reaction is completed, cool it naturally, centrifuge it to obtain a solid precipitate, continue to wash the solid precipitate with ethanol and deionized water for 3 times, dry the precipitate at 70°C for 15 hours, and then dry it in a vacuum drying oven at a drying temperature of 120°C for 2 hours. Finally, the OrgVO material is obtained.

[0055] The obtained OrgVO material was characterized by XRD. Figure 5 The diffraction pattern of the phase structure of OrgVO was measured by X-ray diffractometer. Figure 6 The rate characteristics of aqueous zinc-ion secondary batteries with OrgVO material as the positive electrode at different current densities. Rate performance refers to the discharge capacity of the battery or positive electrode material at different currents (i.e., different rates). When the current density is 0.5A / g, the specific capacity reaches 400mAh / g. As the charge and discharge current density increases to 1A / g, 2A / g, 4A / g and 8A / g, the corresponding specific capacities are 380mAh / g, 353mAh / g, 323mAh / g and 290mAh / g respectively; when the charge and discharge current density decreases again, the corresponding specific capacity can also be restored. The corresponding coulomb efficiency is ~100%, indicating that this type of material has very excellent reaction reversibility and charge and discharge capabilities at different currents.

[0056] The results show that the aqueous zinc-ion secondary battery with OrgVO material as the positive electrode exhibits excellent reversible capacity, rate performance and cycle stability.

[0057] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing an OrgVO material, characterized in that: The steps include: (1) dissolving vanadium pentoxide in deionized water, stirring, then adding hydrogen peroxide solution and stirring until uniform; finally adding Org solution and stirring evenly to obtain a mixed solution; (2) subjecting the mixed solution obtained in step (1) to a solvothermal reaction; (3) After the solvothermal reaction is completed, the solid precipitate is centrifuged and washed to obtain a solid precipitate, and the solid precipitate is freeze-dried to obtain a solid powder. The solid powder is then dried and cooled to obtain the OrgVO material.

2. The method for preparing the OrgVO material according to claim 1, characterized in that: The Org in step (1) is at least one of an organic halide, an organic molecule, an organic molecule hydrochloride, or an inorganic ion sulfate or halide.

3. The method for preparing the OrgVO material according to claim 2, characterized in that: The Org is 1-oxa-2-oxo-3-thia-indolizine chloride, trifluoromethanesulfonic acid diphenylamine salt, 1-ethylpyridin-1-ium bis(trifluoromethanesulfonyl)imide salt, diclofenac pyrrolidine ethanol salt, methylamine lead chloride bromide, 1-hexyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, trifluoromethanesulfonic acid diphenylamine salt, dimethylamine lead iodide, dimethylamine lead iodide, 1-methylpyridine iodide, benzylamine chloride, butylamine chloride, propylamine chloride, benzylamine bromide, butylamine bromide, 1-ethyl-3-methylimidazolium bromide, 1-vinyl-3-ethylimidazolium bromide, 1-ethyl-2,3-dimethylimidazolium bromide, formamidine lead bromide iodide, formamidine lead chloride iodide, methylamine lead bromide iodide, pyridine hydrofluoride, benzylamine chloride, butylamine chloride, propylamine chloride, benzylamine bromide, butylamine bromide, 1-ethyl-3-methylimidazolium bromide, 1-vinyl-3-ethylimidazolium bromide, 1-ethyl-2,3-dimethylimidazolium bromide, formamidine lead bromide iodide, formamidine lead chloride iodide, methylamine lead bromide iodide, pyridine hydrofluoride, trimethylammonium chloride, triethylamine trihydrofluoride, pyrrolidone tribromide, 1-vinyl-3-butylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-carboxymethyl-3-methylimidazolium chloride, 1,3-diaminopropane dihydroiodide, 1-allyl-3-vinylimidazolium chloride, 1-methylpyridine-2-aldehyde oxime chloride, 1-butyl-3-methylimidazolium bromide, 1,3-propylenediamine dihydrobromide, 1,3-diaminopropane dihydrobromide or 1,4-phenylenediamine dihydroiodide, toluene, p-xylene, 1,3,5-trimethylbenzene, trichlorotoluene, trifluorotoluene, dibromotoluene, 1,2,4-trimethylbenzene, p-Chlorotoluene, o-bromotoluene, 2-ethyltoluene, 3,4-dichlorotoluene, 1,2,4,5-tetramethylbenzene, 3,4-dibromotoluene, 4-ethyltoluene, 4-propyltoluene, 3,5-dibromotoluene, 2-fluorotoluene, 4-fluorotoluene, 3-bromotoluene, p-bromotoluene, o-chlorotoluene, m-chlorotoluene, p-tert-butyltoluene, 3-bromo-5-chlorotoluene, α,α-dibromotoluene, 4-bromo-2-fluorotoluene, 4-chloro-2-fluorotoluene, 2-bromo-6-fluorotoluene, 5-chloro-2-fluorotoluene, fluorobenzene, 3-fluorothiophenol, 2-fluorothiophenol, 3-fluoroaniline, 4-fluorothiophenol, 2-fluoroanisole, o-fluoroaniline, 4-fluoroanisole, m-fluorophenylethylamine, 4-fluoroanisole, m-bromofluorobenzene, 1,3-difluorobenzene, p-difluoro Benzene, 3-fluorobenzamide, 1,2-difluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 2,3-difluorophenol, 4-fluorophenyl isonitrile, 2,6-difluorophenol, chlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, o-chloroanisole, 4-chlorobenzamide, 3-chlorobenzonitrile, p-bromochlorobenzene, 2-bromochlorobenzene, 2-chlorophenethyl ether, 1,2,4-trichlorobenzene, 3-chlorobenzamide, 1,2,3,4-tetrachlorobenzene, 1-bromo-3-chlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,3-dibromo-2-chlorobenzene, 2,3-difluorochlorobenzene, 4-amino-3-chlorobenzonitrile, 2,4,6-Trimethylchlorobenzene, bromobenzene, 3-bromothiophenol, 4-bromothiophenol, o-bromoanisole, m-bromoanisole, 4-bromophenol, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 1,2-dibromobenzene, 2-bromobenzonitrile, 2,5-dimethylbromobenzene, 1,3,5-tribromobenzene, 2,4-dimethylbromobenzene, m-dibromobenzene, p-dibromobenzene, 3,4-dimethylbromobenzene, 1,2,3-tribromobenzene, 2,5-dibromoaniline, 2, 4-Dibromoaniline, 3,5-Dibromoaniline, 2,6-Dibromoaniline, 2,4,6-Tribromoaniline, 3,4-Dichlorobromobenzene, 1,4-Dibromobenzene, benzylamine, n-propylamine, furfuralamine, isopropanolamine, tert-amylamine, monocyanamide, 5-thiazole, cyclobutylamine, isobutylamine, tert-butylamine, n-propylamine, mono-n-butylamine, N-ethylpropylamine, (±)-tetrahydrofurfurylamine, sec-butylamine, N-methylpropylamine, 1,2-propylenediamine, diethylene glycol, diethylene glycol Alcoholamine, dicyandiamide, diethanolamine, 4,5-dibromo-1,2-phenylenediamine or 1,4-dibromo-2,5-difluorobenzene, 1,3-diaminoguanidine hydrochloride, guanidine hydrochloride, aminoguanidine hydrochloride, o-xylylenediamine dihydrochloride, cysteamine hydrochloride, glycine hydrochloride, ethanolamine hydrochloride, N,N-dimethyl-p-phenylenediamine dihydrochloride, acridine orange hydrochloride, L-NIL hydrochloride, AMT hydrochloride, A-3 hydrochloride, di Metformin hydrochloride, N,N-diethyl-1,2-ethylenediamine dihydrochloride, Xylemin dihydrochloride, phenanthene hydrochloride, triethylamine hydrochloride, imidazole hydrochloride, 4,4-piperidinediol, 3,3-difluorohydrochloride, chloramine hydrochloride, isonicotinoyl chloride hydrochloride, dimethylaminoacetyl chloride hydrochloride, L-2,4-diaminobutyric acid dihydrochloride, 4-pyridylpyridinium chloride hydrochloride, 6-chloronicotinoyl chloride hydrochloride, cyclobutane-1,3-Diamine dihydrochloride, β-glutamic acid hydrochloride, triethanolamine hydrochloride, cystamine dihydrochloride, L-β-homoisoleucine hydrochloride, chitosan hydrochloride, cysteamine-d4 hydrochloride, creatinine hydrochloride, betaine hydrochloride, H-Sar-NH2 hydrochloride, butylamine hydrochloride, aminoacetone hydrochloride, 4-fluoroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromophenylhydrazine hydrochloride, trimethylamine hydrochloride, propylamine hydrochloride, methylamine hydrochloride, allylamine hydrochloride, cyclohexylamine hydrochloride, isopentylamine hydrochloride, piperidine hydrochloride, pyrrolidine hydrochloride, thiosemicarbazide hydrochloride, hexylamine hydrochloride, glycine ethyl ester hydrochloride, diethanolamine hydrochloride, methylguanidine hydrochloride, 2-chloroethylamine hydrochloride, m-toluidine hydrochloride, methylguanidine hydrochloride, DL-α-amino-ε-caprolactam hydrochloride, ethylamine hydrochloride, 3-butenylamine hydrochloride, guanidine hydrochloride Hydrochloride, serinol hydrochloride, ethylenediamine hydrochloride, 2-hydroxypyrimidine hydrochloride, benzamidine hydrochloride, 2-fluoroethylamine hydrochloride, benzylamine hydrochloride, m-anisidine hydrochloride, ethylhydrazine hydrochloride, 1-methylimidazole hydrochloride, β-alanine methyl ester hydrochloride, ethylacetimidate hydrochloride, pentamidine hydrochloride, semicarbazide hydrochloride, 4-hydroxypiperidine hydrochloride, sarcosine ethyl ester hydrochloride, formamidine hydrochloride, propionamidine hydrochloride, chloroformamidine salt Hydrochloride, 3-pyrrolidone hydrochloride, hydrazine monohydrochloride, isobutylamine hydrochloride, 3-hydroxypiperidine hydrochloride, 4-chloroaniline hydrochloride, glycinamide hydrochloride, aminoacetonitrile hydrochloride, propargylamine hydrochloride, 3-amino-1-propanol hydrochloride, acetamidine hydrochloride, pyridine-2-carbonyl chloride hydrochloride, 2-(dimethylamino)acetyl chloride hydrochloride, D-(-)-phenylglycine chloride hydrochloride, N,N-diethyl-1,3-Propylenediamine dihydrochloride, methylenediamine dihydrochloride, (R)-(+)-diaminopropane dihydrochloride or methylenediamine dihydrochloride, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium phosphate, sodium bromide, sodium iodide, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium chloride, rubidium bromide, cesium iodide, sodium nitrate, potassium nitrate, potassium sulfate, potassium hydrogen sulfate, potassium carbonate, Potassium bicarbonate, potassium phosphate, lithium carbonate, lithium bicarbonate, lithium sulfate, lithium bisulfate, lithium chloride, lithium bromide, lithium iodide, potassium chlorate, potassium perchlorate, sodium perchlorate, sodium sulfide, potassium sulfide, sodium cyanide, potassium cyanide, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, beryllium sulfate, magnesium sulfate, calcium sulfate, beryllium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, beryllium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, beryllium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, barium phosphate, aluminum sulfate, aluminum chloride, aluminum sulfide, Aluminum phosphate, sodium aluminate, scandium chloride, scandium sulfate, scandium nitrate, scandium carbonate, scandium acetate, titanium tetrachloride, titanium sulfate, titanium trichloride, titanium tetraiodide, titanium tetrabromide, chromium chloride, chromium sulfate, chromium nitrate, potassium chromate, sodium chromate, potassium dichromate, sodium dichromate, manganese chloride, manganese sulfate, manganese nitrate, potassium manganate, potassium permanganate, ferrous chloride, ferrous sulfate, ferrous nitrate, ferric chloride, ferrous sulfate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, nickel chloride, nickel sulfate, nickel nitrate, nickel carbonate, cuprous chloride, cuprous sulfide, cupric sulfate, cupric chloride, cupric nitrate, carbon At least one of copper oxide, zinc chloride, zinc sulfate, zinc nitrate, zinc carbonate, yttrium chloride, yttrium sulfate, yttrium nitrate, zirconium chloride, zirconium sulfate, zirconium nitrate, niobium chloride, sodium niobate, sodium molybdate, ammonium molybdate, molybdenum chloride, sodium technetate, ruthenium chloride, ruthenium sulfate, rhodium chloride, rhodium nitrate, gadolinium chloride, gadolinium sulfate, gadolinium nitrate, samarium chloride, samarium sulfate, samarium nitrate, hafnium tetrachloride, hafnium tetrafluoride, hafnium sulfate, sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate, zinc tungstate, tungsten hexachloride, tungsten fluoride, potassium perrhenate, ammonium perrhenate, rhenium hexachloride, and rhenium pentachloride.

4. The method for preparing the OrgVO material according to claim 1, characterized in that: The concentration of vanadium pentoxide in step (1) is 1-10 mg / mL; the molar mass of the added Org is 0.1%-100% of the vanadium pentoxide.

5. The method for preparing the OrgVO material according to claim 1, characterized in that: The stirring time in step (1) is 0.5 to 1 h, and the temperature range is 5 to 30° C.

6. The method for preparing the OrgVO material according to claim 1, characterized in that: The temperature of the solvent thermal reaction in step (2) is 100-200° C., and the reaction time is 0.5-48 h.

7. The method for preparing the OrgVO material according to claim 1, characterized in that: The drying temperature in step (3) is 60-150° C. and the drying time is 0.5-6 h.

8. An OrgVO material, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 7.

9. A use of the OrgVO material as claimed in claim 8, characterized in that: In the application, OrgVO, acetylene black and PVDF are mixed in a ratio of 70:20:10, coated on a carbon sheet or titanium foil to form an electrode film, and then dried to be used as a positive electrode material of a secondary battery; the secondary battery is any one of a zinc ion battery, a lithium ion battery, a sodium ion battery, a magnesium ion battery, a calcium ion battery or an aluminum ion battery.

10. An aqueous zinc ion secondary battery, characterized in that: The aqueous zinc ion secondary battery uses the OrgVO material as claimed in claim 8 as the positive electrode material, Zn(CF3SO3)2 or ZnSO4 dissolved in deionized water as the electrolyte, and a zinc sheet as the negative electrode.

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