CN110467170B - High-potential positive electrode material of potassium ion battery and preparation method thereof - Google Patents
High-potential positive electrode material of potassium ion battery and preparation method thereof Download PDFInfo
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- CN110467170B CN110467170B CN201910797563.0A CN201910797563A CN110467170B CN 110467170 B CN110467170 B CN 110467170B CN 201910797563 A CN201910797563 A CN 201910797563A CN 110467170 B CN110467170 B CN 110467170B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
Potassium ion batteryThe high-potential anode material and the preparation method thereof comprise the following steps: s1, mixing vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (2-8): (10-20) mixing and dissolving in deionized water, and stirring to obtain a precipitate; s2, drying the precipitate to obtain a final product K0.5VOPO4·1.5H2And O. The polyanion material is easy to prepare and has good performance, and the synthesized hydrated potassium vanadyl phosphate anode material has good crystal form and layer structure and excellent electrochemical performance. The conductivity and electrochemical performance of the material are improved by further compounding with graphene oxide.
Description
Technical Field
The invention relates to the field of batteries, in particular to a high-potential positive electrode material of a potassium ion battery and a preparation method thereof.
Background
Over the past 20 years, Lithium Ion Batteries (LIBs) have dominated the consumer electronics market due to the high energy density, high efficiency and long cycle life of advanced electrical energy storage systems that have become the first choice. However, to meet the increasing demand of human beings for smaller and lighter electronic devices as well as large-scale grid storage and electric vehicles, lithium ion battery technology needs to be further improved in terms of energy, power density, efficiency, and the like. The increasing demand for lithium resources by mankind and the limited distribution thereof in the earth's crust also inevitably lead to a continuous increase in the price of lithium ion batteries.
These concerns over lithium resources have prompted the development of Sodium Ion Batteries (SIBs) and Potassium Ion Batteries (PIBs) because sodium and potassium are not only available in large quantities, but are also uniformly distributed throughout the world. Furthermore, Na and K are cognate to Li, have similar chemical properties to Li, so empirical knowledge from LIB can be extended to both SIB and PIB. Due to the standard electrochemical potential K/K of potassium+SHE is lower than Na/Na (-2.93V vs. SHE)+(-2.71V vs. SHE), closer to Li/Li+She, even lower than lithium in some carbonate solvents, may have a higher energy density for PIB compared to SIB and LIB. Further, unlike sodium ions, graphiteCan reversibly intercalate and deintercalate K ions, so that graphite can be used as a negative electrode material of a potassium ion battery. In summary, PIB is a more suitable alternative to LIB based on its material abundance, standard electrode potential and potassium intercalation chemistry.
However, due to K+Compared with Na+And Li+With a larger radius
One of the major challenges in PIB is to develop a suitable cathode material to accommodate the large size of K ions for greater capacity and more stable cycling performance. The first potassium cell prototype was introduced by Eftekhari in 2004, using a Prussian Blue (PB) positive electrode. At present, besides PB and the like, a layered oxide, a polyanion compound, and an organic material are widely studied and reported as a positive electrode material for a potassium ion battery. KVPO4F、KVOPO4、K3V2(PO4)3、KVP2O7The modified poly anion lithium ion battery is a novel polyanion material, can effectively store potassium, has higher working voltage, and has good prospect as a PIB anode. How to further improve the electrochemical performance of the polyanionic material and prepare the polyanionic material by a simple and easy method is a problem faced by the prior art.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provides a high-potential positive electrode material of a potassium ion battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-potential positive electrode material of a potassium ion battery comprises the following steps:
s1, mixing vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (2-8): (10-20) mixing and dissolving in deionized water, and stirring to obtain a precipitate;
s2, drying the precipitate to obtain a final product K0.5VOPO4·1.5H2O。
Further:
in step S1, the vanadium pentoxide is 4mmol, and the amount of deionized water is controlled to 10-50 ml, preferably 20-40 ml.
In step S1, the mixed solution is stirred at room temperature for 12-24 h to obtain the precipitate.
In step S2, the drying temperature is not higher than 80 ℃, and the drying time is more than 24 h.
The high-potential positive electrode material of the potassium ion battery is K prepared by the preparation method0.5VOPO4·1.5H2O。
A preparation method of a high-potential positive electrode material of a potassium ion battery comprises the following steps:
s1, mixing vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (4-8) mixing and dissolving in deionized water and uniformly stirring;
s2, adding a Graphene Oxide (GO) aqueous solution in a matching amount, stirring, adding phosphoric acid with a molar ratio of 10-20, and continuously stirring to obtain a precipitate;
s3, drying the obtained precipitate to obtain a final product K0.5VOPO4·1.5H2O/GO。
Further:
in step S1, vanadium pentoxide is 4mmol, and the amount of deionized water is controlled to 10-50 ml, preferably 20-40 ml; in step S2, the 2.5 wt% Graphene Oxide (GO) aqueous solution is controlled to be 10-50 ml, preferably 20-40 ml.
In step S1, the mixed solution is stirred at room temperature; in the step S2, adding a Graphene Oxide (GO) aqueous solution, stirring at room temperature for 2-4 hours, adding phosphoric acid, and continuing stirring for 12-24 hours to obtain a precipitate.
In step S3, the drying temperature is not higher than 80 ℃, and the drying time is more than 24 h.
The high-potential positive electrode material of the potassium ion battery is K prepared by the preparation method0.5VOPO4·1.5H2O/GO。
The invention has the following beneficial effects:
the present invention providesA novel polyanion high-potential anode material-K0.5VOPO4·1.5H2O、K0.5VOPO4·1.5H2Experiments show that the prepared material has a good crystal form, can effectively intercalate potassium ions, and shows a higher electrochemical window and excellent electrochemical performance.
Compared with the existing KIB anode material, the polyanion material provided by the invention is simple to prepare and has good performance, and the synthesized hydrated potassium vanadyl phosphate anode material has good crystal form and layered structure and excellent electrochemical performance. The conductivity and electrochemical performance of the material are improved by further compounding with graphene oxide.
Drawings
Fig. 1 is an XRD image of a high potential positive electrode material of a potassium ion battery of an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of the high-potential positive electrode material of the potassium ion battery of the embodiment of the invention (wherein a) and b) are K0.5VOPO4·1.5H2O in a scanning electron microscope image, c) d) is K0.5VOPO4·1.5H2Scanning electron microscope images of O/GO composites);
fig. 3 is a graph a) of charge and discharge curves and a graph b) of cycle performance for examples of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
In some embodiments, a high potential positive electrode material (K) for a potassium ion battery0.5VOPO4·1.5H2O) synthesis method, comprising the following steps:
step 1, mixing raw materials of vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (2-8): (10-20) mixing and dissolving in a certain amount of deionized water, and stirring at room temperature for 12-24 hours.
And 2, washing the obtained dark green precipitate with deionized water, carrying out suction filtration, and drying in a drying oven to obtain a final product.
Since the amount of added water can affect the final product and yield, in a preferred embodiment, in the step 1, the amount of vanadium pentoxide is 4mmol, the amount of deionized water is controlled to 10-50 ml, and the amount of deionized water better matches the mass of the added raw materials.
Since insufficient drying has certain influence on the structure of the product, in a preferred embodiment, the drying temperature of the step 2 is not higher than 80 ℃, and the drying time is more than 24 hours.
In order to achieve better electrochemical performance, the invention also provides a preparation method of the composite material based on the material.
In other embodiments, a potassium ion battery high potential positive electrode composite (K)0.5VOPO4·1.5H2O/GO), comprising the following steps:
step 1, mixing raw materials of vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (2-8) mixing and dissolving in a certain amount of deionized water, and stirring uniformly at room temperature.
And 2, adding a certain amount of GO aqueous solution (2.5 wt%), stirring at room temperature for 2-4 hours, adding 10-20 mol% phosphoric acid, and continuing stirring for 12-24 hours.
And 3, washing the obtained dark green precipitate with deionized water, carrying out suction filtration, and drying in a drying oven to obtain a final product.
Since the amount of water can affect the final product and yield, in a preferred embodiment, in step 1, the amount of vanadium pentoxide is 4mmol, the amount of deionized water is controlled to 10-50 ml, and in step 2, the GO solution is controlled to 10-50 ml. The amount of deionized water in step 1 and the amount of GO solution in step 2 better match the quality of the added feedstock.
Since insufficient drying has certain influence on the structure of the product, in a preferred embodiment, the drying temperature of the step 3 is not higher than 80 ℃, and the drying time is more than 24 hours.
The technical scheme of the invention has simple operation and good reproducibility, and the synthesized anode material of the potassium vanadyl phosphate hydrate has a layered structure and shows a good crystal form.
Embodiments of the present invention will be specifically explained below with reference to the drawings.
The synthesis method of the high-potential positive electrode material of the potassium ion battery provided by the embodiment of the invention comprises the following specific steps:
step 1, mixing raw materials of vanadium pentoxide (4mmol), oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: 2: (2-8): 20 are mixed and dissolved in 20-40 ml of deionized water and stirred at room temperature for 18 hours.
And 2, washing the obtained green precipitate with deionized water, carrying out suction filtration, and drying in a drying oven at the temperature of 80 ℃ for more than 24 hours to obtain a final product.
In order to improve the conductivity of the material and achieve better electrochemical performance, the material and GO are compounded in situ, and the synthesis steps are as follows:
step 1, mixing raw materials of vanadium pentoxide (4mmol), oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: 2: (2-8) mixing and dissolving in 20-40 ml of deionized water, and stirring uniformly at room temperature.
And 2, adding 20-40 ml of GO aqueous solution (2.5 wt%), stirring at room temperature for 2 hours, adding 20 mol% of phosphoric acid, and continuing stirring for 18 hours.
And 3, washing the obtained dark green precipitate with deionized water, carrying out suction filtration, and drying in a drying oven at the temperature of 80 ℃ for 48 hours to obtain a final product.
The electrochemical performance test process and the test result of the embodiment of the invention are as follows:
firstly, K is firstly0.5VOPO4·1.5H2O material (or K)0.5VOPO4·1.5H2O/GO composite) was thoroughly ground in a mortar, then the material, conductive agent (Super P) and binder (PVDF) were mixed and dissolved in NMP in a ratio of 7:1.5:1.5 to form a slurry, and finally coated on an aluminum foil current collector, wherein the mass of active material was about 1 mg. At 0.1mol/L KClO4a/PC as electrolyte, a K as negative electrode, a coated electrodeThe sheet is the positive electrode, the Glass Fiber (GFA) is the diaphragm, and the button cell is assembled in a glove box filled with argon. Constant current charge and discharge test and cycle life test are carried out on the button cell by a LAND cell test system produced by blue electronic corporation of Wuhan city, and the current density is 10 mA/g.
Shown in FIG. 1 as K0.5VOPO4·1.5H2XRD images before and after O compounding show that the synthesized hydrated potassium vanadyl phosphate has good crystal forms before and after compounding and no obvious change in structure, which indicates that the content of GO is low and the crystal structure of the material is not changed. FIG. 2 shows K0.5VOPO4·1.5H2O (a, b) and K0.5VOPO4·1.5H2SEM images of O/GO compounds (c, d) show that the synthesized material has a good layered structure and a certain agglomeration phenomenon, and the grain size is submicron. FIG. 3 shows K0.5VOPO4·1.5H2The charge-discharge curve a) and the cycle performance curve b) of O/GO are tested to prove that the material has higher discharge voltage and equivalent discharge capacity.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention.
Claims (10)
1. A preparation method of a high-potential positive electrode material of a potassium ion battery is characterized by comprising the following steps:
s1, mixing vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (2-8): (10-20) mixing and dissolving in deionized water, and stirring to obtain a precipitate;
s2, drying the precipitate to obtain a final product K0.5VOPO4·1.5H2O。
2. The method for preparing a high-potential positive electrode material of a potassium ion battery according to claim 1, wherein in step S1, vanadium pentoxide is 4mmol, and the amount of deionized water is controlled to 10-50 ml.
3. The method for preparing a high-potential positive electrode material of a potassium ion battery according to claim 2, wherein in step S1, the amount of deionized water is controlled to be 20 to 40 ml.
4. The method for producing a high-potential positive electrode material for a potassium ion battery according to any one of claims 1 to 3, wherein in step S1, the precipitate is obtained by stirring the mixed solution at room temperature for 12 to 24 hours.
5. The method for producing a high-potential positive electrode material for a potassium-ion battery according to any one of claims 1 to 3, wherein the drying temperature is not higher than 80 ℃ and the drying time is 24 hours or longer in step S2.
6. A preparation method of a high-potential positive electrode material of a potassium ion battery is characterized by comprising the following steps:
s1, mixing vanadium pentoxide, oxalic acid dihydrate, potassium hydroxide and phosphoric acid in a molar ratio of 1: (1-2): (4-8) mixing and dissolving in deionized water and uniformly stirring;
s2, adding a Graphene Oxide (GO) aqueous solution in a matching amount, stirring, adding phosphoric acid with a molar ratio of 10-20, and continuously stirring to obtain a precipitate;
s3, drying the obtained precipitate to obtain a final product K0.5VOPO4·1.5H2O/GO。
7. The method for preparing a high-potential positive electrode material of a potassium ion battery according to claim 6, wherein in step S1, vanadium pentoxide is 4mmol, and the amount of deionized water is controlled to 10-50 ml; in step S2, the 2.5 wt% Graphene Oxide (GO) aqueous solution is controlled to be 10-50 ml.
8. The method for preparing a high-potential positive electrode material of a potassium ion battery according to claim 7, wherein in step S1, the amount of deionized water is controlled to be 20-40 ml; in step S2, the 2.5 wt% Graphene Oxide (GO) aqueous solution is controlled to 20-40 ml.
9. The method for producing a high-potential positive electrode material for a potassium ion battery according to any one of claims 6 to 8, wherein in step S1, the mixed solution is stirred at room temperature; in the step S2, adding a Graphene Oxide (GO) aqueous solution, stirring at room temperature for 2-4 hours, adding phosphoric acid, and continuing stirring for 12-24 hours to obtain a precipitate.
10. The method for producing a high-potential positive electrode material for a potassium-ion battery according to any one of claims 6 to 8, wherein the drying temperature is not higher than 80 ℃ and the drying time is 24 hours or longer in step S3.
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| CN112490421B (en) * | 2020-11-05 | 2021-09-07 | 西安交通大学 | Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof |
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