CN108615884B - KFeF with hollow structure3Nano material and preparation method and application thereof - Google Patents
KFeF with hollow structure3Nano material and preparation method and application thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a KFeF with a hollow structure3The nanometer material and its preparation process and application include the first reaction of KF.2H2O microemulsion dropwise added to FeCl2·4H2Reacting in O microemulsion for 0.5-60min, adding reaction terminator to terminate the reaction, separating precipitate, and cleaning; KFeF3The nano material is a hollow structure with the particle size of 10-50nm, and the volume ratio of the hollow structure inside is 25-80%; has wide application prospect in the cathode material of the potassium ion button cell. The invention only comprises KF.2H2O microemulsion dropwise added to FeCl2·4H2In O microemulsion, simultaneous control of KF.2H2O and FeCl2·4H2The concentration and the dropping rate of the O microemulsion realize the controllable synthesis of KFeF3 nano materials with hollow structures of different sizes and different hollow sizes; the preparation condition is mild, the process is simple and controllable, the efficiency is high, and the method is suitable for large-scale production and is wide in application.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to KFeF with a hollow structure3A nano material and a preparation method and application thereof.
Background
With the rapid development of social economy, energy crisis and environmental pollution become two major social problems facing people, and various novel energy sources attract the wide attention of researchers. Secondary batteries have been the subject of extensive research by researchers due to their high voltage and energy density, with lithium ion batteries being the most widely studied and commercially used secondary batteries at present. However, due to the small reserves in the crust, the lithium resource cannot meet the wide future worldwide use of lithium ion batteries; researchers are beginning to gradually move research interest to alkali metal-rich batteries.
Potassium ion batteries are of interest because they have potentials close to those of lithium ion batteries. For the negative electrode material of the potassium ion battery, the carbon material becomes the preferred electrode material due to reasonable specific capacity and reversible charge and discharge performance, but has the defects of low capacity ratio and low cycle life, and the practical application is greatly limited, so that the research and development of the more suitable negative electrode material of the potassium ion battery have important theoretical significance and practical value.
Perovskite fluoride KFeF3They have attracted much attention from researchers because of their excellent ferromagnetism, electric polarization characteristics, and electroluminescence characteristics. KFeF3Due to the fact that the potassium ion battery is rich in K ions, the potassium ion battery has the potential of being used as a potassium ion battery cathode material and has hollow KFeF with a specific size3The nano material can better store and release potassium ions in charge-discharge cycles of the potassium ion battery, and the cycle performance and the rate performance of the nano material are greatly improved; however, so far, KFeF of hollow structure has been concerned3The preparation method of the nano material is not reported yet.
In summary, how to prepare KFeF with hollow structure by simple method3The nanometer material is applied to the cathode material of the potassium ion button cell, which is a key technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides KFeF with a hollow structure3A nano material and a preparation method and application thereof.
According to one aspect of the invention, a KFeF with a hollow structure is provided3A process for preparing nm-class material includes such steps as mixing KF.2H2O microemulsion dropwise added to FeCl2·4H2Reacting in O microemulsion for 0.5-60min, adding reaction terminating agent to terminate the reaction, separating precipitate, and cleaning.
In the above reaction process, KF.2H is followed2Dropwise addition of O microemulsion, KFeF3The crystal nucleus grows around the surface active groups in the microemulsion gradually to form KFeF taking the active groups as the center3The nanometer material is added with a reaction terminator to terminate the reaction and carry out the subsequent cleaning process, and after the surface active groups in the original microemulsion are cleaned, KFeF with a hollow structure is formed3And (3) nano materials.
In the above technical scheme, the FeCl2·4H2The molar concentration of the O microemulsion is 0.01-0.1mol/L, and the KF.2H2O microemulsion and said FeCl2·4H2The molar concentration ratio of the O microemulsion is (3-5): 1, and corresponds to every 10mL of said FeCl2·4H2O microemulsion of KF.2H2The dropping rate of the O microemulsion is 0.05-0.15 mL/min.
Preferably, in the above technical solution, the FeCl2·4H2The molar concentration of the O microemulsion is 0.05-0.08mol/L, and the KF.2H2O microemulsion and said FeCl2·4H2The molar concentration ratio of the O microemulsion is 4: 1, and corresponds to every 10mL of said FeCl2·4H2O microemulsion of KF.2H2The dropping rate of the O microemulsion is 0.08-0.12 mL/min.
In the above reaction process, the FeCl2·4H2O microemulsion and KF.2H2Concentration of O microemulsion and KF.2H2Dropping speed of O microemulsion on KFeF with hollow structure3The formation process of the nano material has important influence, and the high concentration of the microemulsion or the high dropping speed of the microemulsion can cause K in the reaction environment+、F-And Fe2+Is too high relative to the concentration of surface active groups, thereby rapidly forming micron-sized KFeF with solid structure3A material; and the KFeF with a hollow structure cannot be generated when the concentration of the microemulsion is too low or the dropping speed is too slow3And (3) nano materials.
Further, in the above technical solution, the FeCl2·4H2O microemulsion and KF.2H2O microemulsion from FeCl2·4H2O and KF.2H2O is respectively added into the mixed emulsion to prepare; the mixed emulsionComprises n-butyl alcohol, octane, deionized water and CTAB;
preferably, in the above technical solution, in the mixed emulsion, the volume ratio of n-butanol, octane and deionized water is (1.5-2.5): (8-12): 1, the molar concentration of CTAB is 0.07-0.4 mol/L.
In the reaction process, the n-butanol and the octane provide a microemulsion environment, and the deionized water is KFeF3Nucleation sites in favor of KFeF3Nucleation and growth of crystal nucleus; in addition, CTAB is selected to provide a reactive group for the surfactant, which functions to modulate KFeF3The morphology of (A) to finally form the KFeF with a hollow structure3And (3) nano materials.
Further, in the above technical scheme, the reaction time is 1-30min, preferably 8-15 min.
Further, in the above technical solution, the reaction terminator is a mixed solution of chloroform and methanol.
Preferably, in the above technical solution, the volume ratio of chloroform to methanol is (1-3): 1, more preferably 2: 1.
and/or, preferably, in the above technical solution, the cleaning process sequentially adopts methanol and deionized water as the cleaning agent.
According to another aspect of the invention, the KFeF with a hollow structure obtained by the preparation method is provided3And (3) nano materials.
Specifically, the KFeF3The nano material is a hollow structure with the particle size of 10-50nm, and the volume percentage of the internal hollow structure in the whole structure is 25-80%.
The KFeF with the grain diameter range and the hollow structure with the volume percentage of 25-80 percent3The nano material has a high specific surface area, is used as a battery cathode material, has a large contact area with an electrolyte, has high reaction activity, and can bring high specific capacity of the battery.
According to still another aspect of the present invention, there is provided the above-mentioned production method or the above-mentioned KFeF3The application of the nano material as a negative electrode material of a potassium ion button cell.
In addition, the invention also provides a potassium ion button battery negative electrode material which specifically comprises a pole piece, wherein the pole piece is made of KFeF with the hollow structure3And preparing the slurry of the nano material.
Preferably, in the slurry, the KFeF3The mass ratio of the nano material to the PVDF to the acetylene black is (6-8): (1.8-2.4): 1.
further preferably, the preparation method of the pole piece is as follows: using DMF as solvent, adding KFeF3Dissolving the nano material, PVDF and acetylene black in the solvent to prepare slurry, coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven at 80 ℃ for drying for 10-14h, and punching to obtain the copper foil.
In addition, the invention also provides a potassium ion button battery which comprises a negative electrode made of the negative electrode material.
Preferably, the electrolyte of the potassium ion button battery is 1.0mol/L ethyl carbonate solution of KPF6, and the diaphragm is a celgard2400 membrane.
The invention has the advantages that:
(1) the invention only comprises KF.2H2O microemulsion dropwise added to FeCl2·4H2In O microemulsion, simultaneous control of KF.2H2O microemulsion and FeCl2·4H2The KFeF with different sizes and different hollow sizes can be prepared by the concentration of the O microemulsion and the dripping acceleration rate of the O microemulsion3Nano material, thereby realizing KFeF with hollow structure3Controllable synthesis of nano materials;
(2) the KFeF with the hollow structure prepared by the method provided by the invention3The nano material has small size, the grain diameter is 10-50nm, the hollow structure accounts for 20-80% of the volume ratio of the whole structure, and the KFeF3The specific surface area of the nano material particles is large, the nano material particles are used as a battery cathode material, the contact area with an electrolyte in the reaction process is large, and the reaction activity is extremely high, so that the specific capacity of the battery is effectively improved;
(3) the KFeF with a hollow structure developed by the invention3The method of the nano material has mild condition, simple and controllable process, stable chemical structure and performance of the product,the adopted raw materials are easy to obtain and have low price, the production equipment is simple, the production efficiency is high, the method is suitable for large-scale industrial production, and the prepared KFeF with a hollow structure3The nanometer material product has excellent electrical performance, wide application foreground and great theoretical and practical significance.
Drawings
FIG. 1 is a KFeF of hollow structure prepared in example 1 of the present invention3An X-ray diffraction pattern of the nanomaterial;
FIG. 2 is a KFeF of hollow structure prepared in example 1 of the present invention3Transmission electron microscope and high resolution transmission electron microscope images of the nano material;
FIG. 3 is a KFeF of hollow structure prepared in example 1 of the present invention3And (3) a charge-discharge performance result graph of the nano material as a potassium ion battery cathode material.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
In the following examples, X-ray diffraction patterns were obtained using an X-ray diffractometer (Bruker D8 Focus); the transmission electron microscope and the high-resolution transmission electron microscope photos are obtained by a Hitachi S-4800 transmission electron microscope; the charge and discharge performance test of the potassium ion battery cathode material is obtained by a Wuhan blue tester.
Example 1
The embodiment of the invention provides KFeF with a hollow structure3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 0.1g FeCl was weighed2·4H2O and 0.19g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion；
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.1mL/min2·4H2Reacting in O microemulsion for 30min, adding 30ml of mixed solution of chloroform and methanol with the volume ratio of 1:1 to terminate the reaction, separating and taking brown precipitate, and cleaning by adopting methanol and deionized water with the volume ratio of 5:1 to obtain the final product of KFeF with a hollow structure3And (3) nano materials.
KFeF for potassium ion battery prepared by the invention3Use of a nanoparticulate anode material, KFeF3The nano-particle negative electrode material is applied to a button cell, DMF is used as a solvent for a negative electrode, and the formula of a pole piece is KFeF according to the mass ratio3Nano-particles: PVDF: acetylene black is 7: 2: 1, then uniformly coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃, punching to obtain a pole piece for an experimental battery, taking metal potassium as a counter electrode, using a solution of ethyl carbonate (EC and dimethyl carbonate with the volume ratio of 1:1) with an electrolyte of 1.0M KPF6, and using a diaphragm as a celgard2400 membrane, and filling the solution in a glove box filled with argon atmosphere to prepare the button battery.
And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.01-2.6V, and the charge-discharge current is 500 mA/g.
Example 2
The embodiment of the invention provides KFeF with a hollow structure3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 0.2g FeCl was weighed2·4H2O and 0.19g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion;
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.1mL/min2·4H2In O microemulsion, reaction 30miAfter n, adding 30ml of mixed solution of trichloromethane and methanol with the volume ratio of 1:1 to terminate the reaction, separating and taking brown precipitate, and cleaning by adopting methanol and deionized water with the volume ratio of 5:1 to obtain the final product of KFeF with a hollow structure3And (3) nano materials.
KFeF for potassium ion battery prepared by the invention3Use of a nanoparticulate anode material, KFeF3The nano-particle negative electrode material is applied to a button cell, DMF is used as a solvent for a negative electrode, and the formula of a pole piece is KFeF according to the mass ratio3Nano-particles: PVDF: acetylene black is 7: 2: 1, then uniformly coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃, punching to obtain a pole piece for an experimental battery, taking metal potassium as a counter electrode, using a solution of ethyl carbonate (EC and dimethyl carbonate with the volume ratio of 1:1) with an electrolyte of 1.0M KPF6, and using a diaphragm as a celgard2400 membrane, and filling the solution in a glove box filled with argon atmosphere to prepare the button battery.
And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.01-2.6V, and the charge-discharge current is 500 mA/g.
Example 3
The embodiment of the invention provides KFeF with a hollow structure3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 0.2g FeCl was weighed2·4H2O and 0.19g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion;
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.1mL/min2·4H2Reacting in O microemulsion for 30min, adding 30ml of mixed solution of chloroform and methanol at a volume ratio of 1:1 to terminate the reaction, separating to obtain brown precipitate, cleaning with methanol and deionized water at a volume ratio of 5:1,obtaining the final product of KFeF with a hollow structure3And (3) nano materials.
KFeF for potassium ion battery prepared by the invention3Use of a nanoparticulate anode material, KFeF3The nano-particle negative electrode material is applied to a button cell, DMF is used as a solvent for a negative electrode, and the formula of a pole piece is KFeF according to the mass ratio3Nano-particles: PVDF: acetylene black is 7: 2: 1, then uniformly coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃, punching to obtain a pole piece for an experimental battery, taking metal potassium as a counter electrode, using a solution of ethyl carbonate (EC and dimethyl carbonate with the volume ratio of 1:1) with an electrolyte of 1.0M KPF6, and using a diaphragm as a celgard2400 membrane, and filling the solution in a glove box filled with argon atmosphere to prepare the button battery.
And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.01-2.6V, and the charge-discharge current is 500 mA/g.
Example 4
The embodiment of the invention provides KFeF with a hollow structure3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 0.4g FeCl was weighed2·4H2O and 0.19g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion;
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.1mL/min2·4H2Reacting in O microemulsion for 30min, adding 30ml of mixed solution of chloroform and methanol with the volume ratio of 1:1 to terminate the reaction, separating and taking brown precipitate, and cleaning by adopting methanol and deionized water with the volume ratio of 5:1 to obtain the final product of KFeF with a hollow structure3And (3) nano materials.
KFeF for potassium ion battery prepared by the invention3Nanoparticle negative electrode materialApplication of KFeF3The nano-particle negative electrode material is applied to a button cell, DMF is used as a solvent for a negative electrode, and the formula of a pole piece is KFeF according to the mass ratio3Nano-particles: PVDF: acetylene black is 7: 2: 1, then uniformly coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃, punching to obtain a pole piece for an experimental battery, taking metal potassium as a counter electrode, using a solution of ethyl carbonate (EC and dimethyl carbonate with the volume ratio of 1:1) with an electrolyte of 1.0M KPF6, and using a diaphragm as a celgard2400 membrane, and filling the solution in a glove box filled with argon atmosphere to prepare the button battery.
And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.01-2.6V, and the charge-discharge current is 500 mA/g.
Example 5
The embodiment of the invention provides KFeF with a hollow structure3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 0.2g FeCl was weighed2·4H2O and 0.38g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion;
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.1mL/min2·4H2Reacting in O microemulsion for 30min, adding 30ml of mixed solution of chloroform and methanol with the volume ratio of 1:1 to terminate the reaction, separating and taking brown precipitate, and cleaning by adopting methanol and deionized water with the volume ratio of 5:1 to obtain the final product of KFeF with a hollow structure3And (3) nano materials.
KFeF for potassium ion battery prepared by the invention3Use of a nanoparticulate anode material, KFeF3The nano-particle negative electrode material is applied to a button cell, DMF is used as a solvent for a negative electrode, and the formula of a pole piece is KFeF according to the mass ratio3Nano-particles: PVDF:acetylene black is 7: 2: 1, then uniformly coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃, punching to obtain a pole piece for an experimental battery, taking metal potassium as a counter electrode, using a solution of ethyl carbonate (EC and dimethyl carbonate with the volume ratio of 1:1) with an electrolyte of 1.0M KPF6, and using a diaphragm as a celgard2400 membrane, and filling the solution in a glove box filled with argon atmosphere to prepare the button battery.
And (3) carrying out charge-discharge cycle test on the button cell: the charge-discharge cut-off voltage is 0.01-2.6V, and the charge-discharge current is 500 mA/g.
Comparative example
The invention provides a KFeF3The preparation method of the nano material comprises the following specific steps:
(1) respectively measuring 1.5ml of n-butyl alcohol, 7.5ml of octane, 0.75ml of deionized water and 0.1mol of CTAB in two times, and mixing to obtain two parts of mixed emulsion;
(2) 2.5g FeCl was weighed2·4H2O and 0.76g KF.2H2O powder is respectively added into the two parts of mixed emulsion prepared in the step (1), and the mixture is stirred uniformly by ultrasonic waves, thus obtaining FeCl2·4H2O microemulsion and KF.2H2O microemulsion;
(3) KF.2H2The O microemulsion was added dropwise to FeCl at a dropping rate of 0.4mL/min2·4H2Reacting in O microemulsion for 30min, adding 30ml of mixed solution of chloroform and methanol with the volume ratio of 1:1 to terminate the reaction, separating and taking brown precipitate, and cleaning by adopting methanol and deionized water with the volume ratio of 5:1 to obtain a final product KFeF3And (3) nano materials.
FIG. 1 shows KFeF with hollow structure prepared in example 1 of the present invention3Comparing the XRD pattern of the nano material with that of a standard card (PDF #20-0895) in figure 1, the prepared product is KFeF3A phase.
FIG. 2 shows KFeF with hollow structure prepared in example 1 of the present invention3TEM image of the nanomaterial, KFeF can be seen in FIG. 23The particle size of the nano material is between 10 and 50nm, and the nano material is in a hollow structure; in thatIn the HRTRM graph, the measured interplanar spacing was found to be 0.41nm, corresponding to the (100) interplanar in the standard card (PDF #20-0895), by measuring the interplanar spacing of the product.
FIG. 3 shows KFeF of hollow structure prepared in example 1 of the present invention3The nano material is used as a charge-discharge test curve of the cathode of the potassium ion button battery, the specific capacity of the battery reaches 344mAh/g in the first circle of discharge process, and the specific capacity of the battery is still as high as 172mAh/g after 100 circles of charge-discharge.
Meanwhile, KFeF prepared in the comparative example3TEM test of the nano material shows that the prepared KFeF3The nano material is of a solid structure, the particle size is between 150nm and 0.2 mu m, and the particle size distribution is large and has no obvious rule.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (15)
1. KFeF with hollow structure3The preparation method of the nano material is characterized by comprising the steps of mixing KF.2H2O microemulsion dropwise added to FeCl2·4H2Reacting in O microemulsion for 0.5-60min, adding reaction terminator to terminate the reaction, separating precipitate, and cleaning;
the FeCl2·4H2The molar concentration of the O microemulsion is 0.01-0.1mol/L, and the KF.2H2O microemulsion and said FeCl2·4H2The molar concentration ratio of the O microemulsion is (3-5): 1, and corresponds to every 10mL of said FeCl2·4H2O microemulsion of KF.2H2The dropping rate of the O microemulsion is 0.05-0.15 mL/min;
the FeCl2·4H2O microemulsion and KF.2H2O microemulsion from FeCl2·4H2O and KF.2H2O is respectively added into the mixed emulsion to prepare; the mixed emulsion comprises n-butyl alcohol, octane, deionized water and CTAB, and the volume ratio of the n-butyl alcohol, the octane and the deionized water in the mixed emulsion is (1.5-2.5): (8-12): 1, the molar concentration of CTAB is 0.07-0.4 mol/L.
2. The method of claim 1, wherein the FeCl is2·4H2The molar concentration of the O microemulsion is 0.05-0.08mol/L, and the KF.2H2O microemulsion and said FeCl2·4H2The molar concentration ratio of the O microemulsion is 4: 1, and corresponds to every 10mL of said FeCl2·4H2O microemulsion of KF.2H2The dropping rate of the O microemulsion is 0.08-0.12 mL/min.
3. The method according to claim 1 or 2, wherein the reaction time is 1 to 30 min.
4. The method according to claim 3, wherein the reaction time is 8 to 15 min.
5. The production method according to claim 1 or 2, wherein the reaction terminator is a mixed solution of chloroform and methanol;
and/or methanol and deionized water are sequentially adopted as cleaning agents in the cleaning process.
6. The method according to claim 5, wherein the volume ratio of chloroform to methanol is (1-3): 1.
7. the method according to claim 6, wherein the volume ratio of chloroform to methanol is 2: 1.
8. rights to be given byKFeF having a hollow structure obtained by the production method according to any one of claims 1 to 73And (3) nano materials.
9. The KFeF of claim 83Nanomaterial characterized in that the KFeF3The nano material is a hollow structure with the particle size of 10-50nm, and the volume percentage of the internal hollow structure in the whole structure is 25-80%.
10. The method of any one of claims 1 to 7 or the KFeF of any one of claims 8 to 93The application of the nano material as a negative electrode material of a potassium ion button cell.
11. A potassium ion button cell negative electrode material, which is characterized by comprising a pole piece, wherein the pole piece is made of a material containing KFeF of claim 8 or 93And preparing the slurry of the nano material.
12. The potassium ion button cell anode material of claim 11, wherein in the slurry, the KFeF is3The mass ratio of the nano material to the PVDF to the acetylene black is (6-8): (1.8-2.4): 1.
13. the potassium ion button cell negative electrode material as claimed in claim 11, wherein the preparation method of the pole piece is as follows: using DMF as solvent, adding KFeF3Dissolving the nano material, PVDF and acetylene black in the solvent to prepare slurry, coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven at 80 ℃ for drying for 10-14h, and punching to obtain the copper foil.
14. A potassium ion button battery is characterized in that: comprising a negative electrode made of the negative electrode material of claim 11.
15. The potassium ion button cell as claimed in claim 14, wherein the electrolyte of the potassium ion button cell is 1.0mol/L KPF6 ethyl carbonate solution, and the separator is a celgard2400 membrane.
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