CN114628623A - KFeSO with interpenetrated carbon nanotubes4Preparation method and application of F material - Google Patents

KFeSO with interpenetrated carbon nanotubes4Preparation method and application of F material Download PDF

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CN114628623A
CN114628623A CN202210141854.6A CN202210141854A CN114628623A CN 114628623 A CN114628623 A CN 114628623A CN 202210141854 A CN202210141854 A CN 202210141854A CN 114628623 A CN114628623 A CN 114628623A
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kfeso
carbon nano
nano tube
kfsf
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CN114628623B (en
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周小四
廖家英
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Nanjing Normal University
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    • 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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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a KFeSO with carbon nano-tubes inserted4The preparation method and the application of the F material are as follows: acidifying the carbon nano tube and dispersing the carbon nano tube in a polyhydric alcohol solvent to obtain a carbon nano tube dispersion liquid; stirring and dissolving an iron source and potassium fluoride in the carbon nano tube dispersion liquid to obtain a mixed liquid; carrying out solvothermal reaction on the mixed solution to generate a precipitate; calcining the precipitate in reducing atmosphere to obtain the catalyst. The method has simple process, and the used raw materials are green and environment-friendlyThe prepared KFSF @ CNTs material has excellent electrochemical performance and is a promising potassium ion battery anode material.

Description

KFeSO with interpenetrated carbon nanotubes4Preparation method and application of F material
Technical Field
The invention relates to a preparation method and application of a potassium ion battery anode material, in particular to KFeSO with carbon nano tubes interpenetrated4A preparation method and application of the F material.
Background
Lithium ion batteries have become electric vehicles, portable electronic devices, and even fixed due to their advantages of high energy density, long cycle life, and high operating voltageAnd a main power supply in the fields of energy storage systems and the like. However, the scarcity and high price of lithium resources are detrimental to its application in large-scale energy storage systems. In recent years, potassium ion batteries have attracted a great deal of interest as a promising alternative. Potassium and sodium are naturally higher in content and lower in price than lithium, and they are similar to the electrochemical mechanism of lithium ion batteries. In addition, the oxidation-reduction potential (K/K) of potassium+: -2.93V) to sodium (Na/Na)+: 2.71V) and the solvated potassium ion radius is smaller, so that the potassium ion battery has the potential of higher energy density, higher rate performance and larger potential in practical application.
KFeSO4The F is an ideal anode material of the potassium ion battery because the raw material is cheap and easy to obtain, and has a three-dimensional ion channel, high theoretical specific capacity, high working voltage and high structural stability. However, KFeSO4F is a polyanionic compound, which has poor electronic conductivity. However, due to the poor thermal stability of the sulphate (decomposition above 450 ℃), KFeSO4F is difficult to calcine at high temperatures during synthesis and cannot be carbon coated by such methods. Thus KFeSO4The development and application of the F material are limited by lower actual specific capacity, poorer cycle stability and poorer rate capability.
Conventional KFeSO4The F material is synthesized by reacting FeSO4Ball milling and mixing with KF, and calcining at about 380 deg.C at medium and low temperature for 4 days. The reaction takes a long time and there are often some heterogeneous phases in the product. In recent years, researchers have begun to attempt to synthesize KFeSO by solvothermal methods4F, by FeSO4·7H2The reaction time is only 6 hours. Followed by solid phase ball milling of KFeSO4F is mechanically mixed with graphene with high conductivity, and the obtained composite material shows higher specific capacity compared with the initial material, but the improvement of the cycle and rate performance is limited.
Thus, in conventional solid phase processes, FeSO4The reaction with KF takes a long time and the reaction products also contain some electrochemically inactive impuritiesAnd (4) phase(s). Second, the mechanical hybrid carbon coating process can damage the KFeSO4The original micro-morphology structure of F and the contact tightness between the material and the carbon material still need to be improved.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a carbon nanotube-interspersed KFeSO with excellent cycle performance and rate performance4A preparation method of the material F;
the second purpose of the invention is to provide a KFeSO with the carbon nano-tubes interpenetrated4KFeSO with interpenetrated carbon nanotubes prepared by preparation method of F material4And F, application of the material.
The technical scheme is as follows: the invention relates to a KFeSO with interpenetrated carbon nanotubes4The preparation method of the F material comprises the following steps:
(1) acidifying the carbon nano tube and dispersing the carbon nano tube in a polyhydric alcohol solvent to obtain a carbon nano tube dispersion liquid;
(2) stirring and dissolving an iron source and potassium fluoride in the carbon nano tube dispersion liquid to obtain a mixed liquid;
(3) carrying out a solvothermal reaction on the mixed solution in the step (2) to generate a precipitate;
(4) calcining the precipitate in the step (3) in a reducing atmosphere to obtain KFeSO with carbon nano tubes inserted4And F, materials.
Wherein the polyhydric alcohol in the step (1) is one of ethylene glycol, diethylene glycol, triethylene glycol or glycerol; the following ethylene glycol, diethylene glycol, triethylene glycol and glycerin are abbreviated as EG, DEG, TEG and Gly, respectively.
In the step (2), the mass ratio of the iron source to the potassium fluoride to the carbon nano tubes is 1: 0.21-0.23: 0.036-0.072.
Wherein the concentration of the carbon nano tube dispersion liquid in the step (1) is 1.0-2.0 g L-1。
And (2) acidifying the carbon nano tube in the step (1) by using a mixed solution of concentrated sulfuric acid/concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid/the concentrated nitric acid is preferably 3: 1.
Wherein the concentration of the iron source and the potassium fluoride in the step (2) is 0.1-0.2 mol L-1(ii) a The above-mentionedThe iron source is FeSO4·7H2O。
Wherein the reaction temperature in the step (3) is 150-180 ℃, and the reaction time is 2-6 h.
Wherein, the solvothermal reaction in the step (3) is carried out under the condition of stirring; the stirring mode is magnetic stirring, and the speed is controlled to be 1000-2000 rpm.
Wherein, the diameter of the carbon nano tube in the step (1) is 10-50 nm, and the length is 10-30 μm.
And (3) in the step (4), the reducing atmosphere is a hydrogen-argon mixed gas, and the volume percentage of hydrogen in the hydrogen-argon mixed gas is 5-10%.
Wherein the calcining method in the step (4) comprises the following steps: drying the precipitate obtained in the step (3), and then placing the dried precipitate in a tubular furnace for 3-5 ℃ min-1Heating to 350-380 ℃ at the speed, and keeping for 2-6 h.
The KFeSO with the carbon nano-tubes inserted4Preparation method of F material to obtain KFeSO with carbon nano-tubes inserted4And the F material is applied as a positive electrode material of the potassium ion battery.
In the synthesis process, the invention adopts the low-cost polyalcohol as the solvent to ensure that the FeSO is prepared4·7H2O and KF are dissolved and KFeSO is formed in the solvothermal process4F precipitates grow on the carbon nano tubes in situ, the reaction time is short, and the purity of the obtained product is high. The appearance of the product can be controllably changed by regulating and controlling different solvents. In addition, the method can induce KFeSO by using carbon nanotubes as nucleation additives4The F grows by uniform nucleation to form a unique appearance, the process is simple, and the raw materials are green and environment-friendly.
The KFSF @ CNTs material with the micron-sized carbon nano tubes inserted can be prepared by the method, electrons can be transmitted among particles along the carbon nano tubes by the material, the exertion of the material capacity is greatly promoted, and the cycle stability and the rate capability of the KFSF @ CNTs material are improved. Micron-sized particles also facilitate packing of materials, resulting in higher tap densities, corresponding to higher volumetric energy densities. Further, KFeSO obtained by the method4F is KTiOPO4Structure of the productThe lithium ion battery has a three-dimensional ion channel, can accelerate ion conduction, and reduces the energy barrier of the potassium ion battery in the charge and discharge process.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: the KFSF @ CNTs material prepared by the method has excellent electrochemical performance, and is used as a positive electrode material of a potassium ion battery at a multiplying power of 0.2C (1C is 128mA g)-1) Then, 110.9mAh g is provided-1Reversible capacity, average operating voltage reaches 3.73V. Can still provide 69.6mAh g under the large multiplying power of 20C-1The reversible capacity shows good cycle stability in 1000 cycles under the magnification of 1C, and the capacity retention rate is 88.9%. In addition, the potassium ion full cell of KFSF @ CNTs// graphite shows a reversible capacity of 110.1mAh g at a magnification of 0.2C-1The energy density reaches 370Wh kg-1The capacity retention after 300 cycles was 81.1%. Therefore, the carbon nanotube interpenetrating material has good application potential as a high-performance low-cost cathode material.
Drawings
FIG. 1 is a schematic representation of the XRD refinement and crystal structure of the KFSF @ CNTs/DEG material of example 1 of the present invention;
FIG. 2 is an XPS survey of KFSF @ CNTs/DEG material of example 1 of the present invention;
FIG. 3 is a Mossbauer spectrum of KFSF @ CNTs/DEG material of example 1 of the present invention;
FIG. 4 is an SEM image of a KFSF @ CNTs/DEG material of example 1 of the present invention;
FIG. 5 is a TEM and HRTEM image of KFSF @ CNTs/DEG material of example 1 of the present invention;
FIG. 6 is a plot of cyclic voltammetry for KFSF @ CNTs/DEG electrodes of example 1 of the present invention;
FIG. 7 is a graph of the charge/discharge curve and dQ/dV curve for a KFSF @ CNTs/DEG electrode of example 1 of the present invention;
FIG. 8 is a graph of the rate capability and charge-discharge curves of KFSF @ CNTs/DEG of example 1 of the present invention and the materials of comparative examples 1 and 2 at different current densities;
FIG. 9 is a plot of charge-discharge curves and cycle performance at 0.2C rate for KFSF @ CNTs/DEG of example 1 of the invention and for the materials of comparative examples 1 and 2;
FIG. 10 is a graph of the cycle performance of KFSF @ CNTs/DEG at 1C magnification in example 1 of the present invention;
FIG. 11 is an SEM image of KFSF @ CNTs/EG material of example 4 of the present invention;
FIG. 12 is an SEM image of KFSF @ CNTs/TEG material of example 5 of the present invention;
FIG. 13 is an SEM image of KFSF @ CNTs/Gly material of example 6 of the present invention;
FIG. 14 is an SEM photograph of KFSF/DEG of comparative example 1 of the present invention;
FIG. 15 is an XRD spectrum of comparative example 3 of the present invention;
FIG. 16 is an XRD spectrum of comparative example 4 of the present invention.
Detailed Description
The present invention is described in further detail below.
Example 1
Preparation of KFSF @ CNTs material:
(1) adding 1g of carbon nano tubes with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 hours. After cooling, diluting with 400mL of deionized water, and separating by suction filtration;
(2) adding 50mg of acidified carbon nano tube into 50mL of diethylene glycol solvent, and performing ultrasonic treatment for 1h to obtain a carbon nano tube with a concentration of 1g L-1The uniform carbon nanotube dispersion liquid;
(3) 1.39g of FeSO4·7H2O and 0.29g KF were added to the carbon nanotube dispersion, and sufficiently dissolved by stirring for 0.5h, both concentrations being 0.1mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling. Due to the reaction solutionThe reagent diethylene glycol is DEG, and the sample is marked KFSF @ CNTs/DEG.
The KFSF @ CNTs/DEG material is characterized by:
FIG. 1 is a schematic representation of the XRD structure refinement and corresponding crystal structure of a KFSF @ CNTs/DEG material, showing that the material is a phase pure compound with the KTP structure; FIG. 2 is an XPS survey of KFSF @ CNTs/DEG showing the presence of K, Fe, S, O, F and C elements; FIG. 3 is a Mossbauer spectrum of KFSF @ CNTs/DEG, demonstrating the valence of Fe therein as + 2.
The size, morphology and microstructure of the obtained KFSF @ CNTs/DEG material were analyzed by SEM, TEM and HRTEM images. FIGS. 4a and 4b are SEM images of KFSF @ CNTs/DEG material, and FIG. 4a shows that the secondary particles of KFSF @ CNTs/DEG are uniform rugby-ball structures with a particle size of about 2 μm; FIG. 4b shows KFSF @ CNTs/DEG stacked with diamond-shaped primary particles of around 200nm interspersed with some carbon nanotubes. FIGS. 5a and 5b are TEM images of KFSF @ CNTs/DEG, again showing carbon nanotubes interspersed in the primary particles of KFSF; FIG. 5c is a HRTEM image of KFSF @ CNTs/DEG showing that the lattice spacing of the (201) and (011) crystal planes in KFSF @ CNTs/DEG are both 0.562nm, and the angle between the two crystal planes is 74.5 DEG.
And (3) electrochemical performance testing:
the KFSF @ CNTs/DEG prepared in this example, carbon black and polyvinylidene fluoride in a mass ratio of 70:20:10 were ground and mixed uniformly with 1-methyl-2-pyrrolidone as a solvent, and the resulting uniform slurry was spread on an Al foil and vacuum-dried at 80 ℃ for 12 hours. Using 1mol L-1KPF6The Ethylene Carbonate (EC) and Propylene Carbonate (PC) (volume ratio is 1:1) solution is used as the electrolyte of the potassium ion battery, and the glass fiber and the metal potassium are respectively used as the diaphragm and the counter electrode of the potassium ion battery. The electrochemical performance was tested using a CR2032 cell. The cell assembly was carried out in a glove box filled with an argon atmosphere, both water and oxygen concentrations being less than 0.1 ppm. Constant current charge and discharge test of battery at room temperature, using blue CT2001A multi-channel battery test system, at 2.0-4.5V (vs.K)+and/K) in a fixed voltage range. Specific properties are shown in fig. 6 to 10.
FIG. 6 shows KFSF @ CNTs/DEG electrodes at 2.0-4.5V(vs.K+K) voltage interval, scan rate of 0.1mV s-1The cyclic voltammetry curves of the first three circles are basically overlapped, which shows that the reversibility of the material for potassium intercalation is good; FIG. 7 shows KFSF @ CNTs/DEG at 2.0-4.5V (vs+K) voltage interval, current density of 0.2C, reversible specific capacity of 110.9mAh g-1The average working voltage is 3.73V, wherein 1C-128 mA g-1Wherein the dQ/dV curve shows four pairs of redox peaks corresponding to four voltage plateaus of the charge-discharge curve; FIG. 8a is a graph of the rate performance of KFSF @ CNTs/DEG at different current densities, as compared to KFSF/DEG without carbon nanotube interpenetration in comparative example 1 and KFSF/DEG +5 wt% CNTs with mechanically ball-milled mixed carbon nanotubes in comparative example 2, showing that the KFSF @ CNTs/DEG has a capacity of 69.6mAh g even at a high current density of 20C-1FIG. 8b is a charge-discharge curve of KFSF @ CNTs/DEG at different current densities; FIGS. 9a and 9b are graphs of the charge-discharge curve and the cycle performance of KFSF @ CNTs/DEG and the material of comparative example 1 at a current density of 0.2C, respectively, and it is clear that the KFSF @ CNTs/DEG has a higher capacity; FIG. 10 is a cycle performance diagram of KFSF @ CNTs/DEG at a current density of 1C, and the diagram shows that after KFSF @ CNTs/DEG cycles for 1000 cycles, the capacity retention rate reaches 88.9%.
Example 2
(1) Adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 100mg of acidified carbon nano tube into 50mL of diethylene glycol solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 2g L-1The uniform carbon nanotube dispersion.
(3) 2.78g of FeSO4·7H2O and 0.58g KF were added to the carbon nanotube dispersion, and sufficiently dissolved by stirring for 0.5h, both concentrations being 0.2mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling.
The obtained KFSF @ CNTs material was subjected to structural characterization and electrochemical performance testing in the same manner as in example 1, and the structural characterization results are substantially the same as in example 1, and the electrochemical performance testing results are shown in table 1.
Example 3
(1) Adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 100mg of acidified carbon nano tube into 50mL of diethylene glycol solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 2g L-1The uniform carbon nanotube dispersion.
(3) 1.39g of FeSO4·7H2Adding O and 0.32g KF into the carbon nanotube dispersion, stirring for 0.5 hr for dissolving, wherein the concentrations of O and KF are 0.1mol L and 0.11mol L respectively-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling.
The obtained KFSF @ CNTs material was subjected to structural characterization and electrochemical performance testing in the same manner as in example 1, and the structural characterization results are substantially the same as in example 1, and the electrochemical performance testing results are shown in table 1.
Example 4
(1) Adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 50mg of acidified carbon nano tube into 50mL of glycol solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 1g L-1The uniform carbon nanotube dispersion.
(3) 1.39g of FeSO4·7H2O and 0.29g KF were added to the carbon nanotube dispersion, and sufficiently dissolved by stirring for 0.5h, both concentrations being 0.1mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling. Since the reaction solvent was EG, the sample was labeled KFSF @ CNTs/EG.
The KFSF @ CNTs/EG material prepared is subjected to structural characterization and electrochemical performance test according to the same method as the embodiment 1. The morphology is shown in FIG. 11, the secondary particles of KFSF @ CNTs/EG are also uniform rugby-shaped structures, the particle size is about 2 μm, but the primary particles are irregular particles, and a small amount of carbon nanotubes are attached to the surface. The results of the electrochemical performance test are shown in Table 1.
Example 5
(1) Adding 1g of carbon nano tubes with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 hours. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 50mg of acidified carbon nano tube into 50mL of triethylene glycol solvent, and performing ultrasonic treatment for 1h to obtain the concentration of 1g L-1The uniform carbon nanotube dispersion.
(3) 1.39g of FeSO4·7H2O and 0.29g KF were added to the carbon nanotube dispersion, and sufficiently dissolved by stirring for 0.5hAll the concentrations of (b) are 0.1mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling. Since the reaction solvent was TEG, the sample was labeled KFSF @ CNTs/TEG.
The KFSF @ CNTs/TEG material prepared is subjected to structural characterization and electrochemical performance test according to the same method as the embodiment 1. The morphology is shown in FIG. 12, KFSF @ CNTs/TEG is micron-sized diamond-shaped particles, and carbon nano tubes are inserted in the particles. The results of the electrochemical performance test are shown in Table 1.
Example 6
(1) Adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 50mg of acidified carbon nano tube into 50mL of glycerol solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 1g L-1The uniform carbon nanotube dispersion.
(3) 1.39g of FeSO4·7H2O and 0.29g KF were added to the carbon nanotube dispersion, and sufficiently dissolved by stirring for 0.5h, both concentrations being 0.1mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling. Due to the fact thatThe reaction solvent is Gly, and the sample is marked as KFSF @ CNTs/Gly.
The KFSF @ CNTs/Gly material prepared is subjected to structural characterization and electrochemical performance test according to the same method as the embodiment 1. The morphology is shown in FIG. 13, the secondary particle of KFSF @ CNTs/Gly is an olive-shaped structure with a larger length-diameter ratio, the length is about 4 μm, the diameter is about 1 μm, the primary particle is a rod-shaped particle, and a small amount of carbon nano-tubes are attached to the surface. The results of the electrochemical performance test are shown in Table 1.
Comparing the electrochemical performances of examples 1, 4, 5 and 6, it is known that the KFSF sample prepared in diethylene glycol in example 1 has better performances. Although the mass ratio of the initial iron source, the potassium fluoride and the carbon nano tube is the same, the mass ratio of the initial iron source, the potassium fluoride and the carbon nano tube is 1: 0.21: 0.036. however, the carbon nanotube contents of the samples of examples 1, 4, 5, and 6 were 4.6%, 1.5%, 2.1%, and 2.5%, respectively, according to the carbon content test. This indicates that KFSF is more likely to adhere to the carbon nanotubes in the diethylene glycol solvent, causing more precipitation of the carbon nanotubes. The KFSF is in closer contact with the carbon nano-tubes, so that the final electrochemical performance of the sample is better. As can be seen from FIGS. 4 and 11, the spherical shape is also rugby, but KFeSO4F nucleates faster in ethylene glycol and does not grow easily along the carbon nanotubes, thus example 4 has less carbon nanotubes than the sample of example 1. From this, it is found that the higher the content of the carbon nanotubes in the final sample is, the more closely the KFSF and the carbon nanotubes are bonded to each other, and the more excellent electrochemical performance is advantageously obtained. Compared with the rhombic shape of the sample in the embodiment 5 and the rod-shaped shape of the sample in the embodiment 6, the football shape of the samples in the embodiments 1 to 4 is easier for the close packing of materials, and is more favorable for improving the volume energy density.
Comparative example 1
Preparation of KFSF/DEG without carbon nanotube interpenetration:
(1) 1.39g of FeSO4·7H2O and 0.29g KF were added to 50mL of diethylene glycol, and sufficiently dissolved by stirring for 0.5h, both at a concentration of 0.1mol L-1；
(2) Adding the dispersion liquid obtained in the step (1) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(3) placing the precipitate obtained in the step (2) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling. Since the reaction solvent was DEG and no carbon nanotubes, the sample was labeled KFSF/DEG.
The obtained KFSF/DEG material was subjected to structural characterization and electrochemical performance test in the same manner as in example 1. The morphology of the carbon nano tube is shown in FIG. 14, the KFSF/DEG is micron-sized diamond-shaped particles, and the comparison of the morphology of the KFSF @ CNT/DEG shows that the carbon nano tube can be used as a nucleating agent, so that the KFSF grows into smaller grains along the carbon nano tube by nucleation. FIG. 9a is a graph of the rate performance of KFSF/DEG versus KFSF @ CNT/DEG at different current densities, with the reversible capacity of KFSF @ CNT/DEG being higher than that of KFSF/DEG; FIG. 8b is a comparison of the cycling performance plots of KFSF @ CNTs/DEG and KFSF/DEG at 0.2C current density showing that the cycling stability of KFSF/DEG is much later than that of KFSF @ CNTs/DEG; as can be seen from the above tests, the KFSF/DEG electrochemical performance is far inferior to that of KFSF @ CNTs/DEG.
Comparative example 2
Preparation of KFSF sample with mechanical mixing of carbon nanotubes:
(1) 1.39g of FeSO4·7H2O and 0.29g KF were added to 50mL of diethylene glycol, and sufficiently dissolved by stirring for 0.5h, both at a concentration of 0.1mol L-1；
(2) Adding the dispersion liquid obtained in the step (1) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(3) placing the precipitate obtained in the step (2) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is increased to 350 ℃ and calcined for 2h, and then the temperature is cooled to room temperature;
(4) and (3) ball-milling and mixing the product obtained in the step (3) with 5 wt% of carbon nanotubes in a planetary ball mill at 500rpm for 12 hours, wherein the obtained sample is marked as KFSF/DEG +5 wt% CNTs.
Electrochemical performance tests were performed on the prepared KFSF/DEG +5 wt% CNTs material in the same manner as in example 1, and the results are shown in Table 1, as shown in FIGS. 8 and 9, and although the electrochemical performance was improved compared to the KFSF/DEG without carbon nanotubes, the electrochemical performance was significantly inferior to that of the KFSF @ CNTs/DEG sample with carbon nanotube interpenetration.
Comparative example 3
KFSF samples were prepared with monohydric alcohols:
(1) adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 50mg of acidified carbon nano tube into 50mL of ethylene glycol monomethyl ether solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 1g L-1The uniform carbon nanotube dispersion.
(3) 1.39g of FeSO4·7H2Adding O and 0.29g KF into the carbon nanotube dispersion liquid, stirring for 0.5h to fully dissolve, wherein the concentrations of both are 0.1mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) placing the precipitate obtained in the step (4) in a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen at 3 ℃ for min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling.
The obtained material was subjected to structural characterization and electrochemical performance test in the same manner as in example 1. The XRD structure of the product is characterized as shown in figure 15, and K can be obviously present in the product2SO4Mainly due to the low solubility of the potassium salt in the monohydric alcohol. The electrochemical performance test results are shown in table 1, and are obviously inferior to the samples prepared in other polyols. Therefore, the preparation using polyols is essential.
Comparative example 4
KFSF @ CNTs prepared at high stock concentration:
(1) adding 1g of carbon nano tube with the diameter of 10-30 nm and the length of 20-30 mu m into a mixed solvent of 20mL of concentrated nitric acid and 60mL of concentrated sulfuric acid, and heating and stirring at 70 ℃ for 8 h. After cooling, diluting with 400mL of deionized water, and performing suction filtration separation;
(2) adding 200mg of acidified carbon nano tube into 50mL of diethylene glycol solvent, and performing ultrasonic treatment for 1h to obtain the carbon nano tube with the concentration of 4g L-1The uniform carbon nanotube dispersion.
(3) 5.56g of FeSO4·7H2O and 1.16g KF were added to the carbon nanotube dispersion and were not sufficiently dissolved by stirring for 0.5 hour, the theoretical concentrations of both were 0.4mol L-1；
(4) Adding the dispersion liquid obtained in the step (3) into a 100mL hydrothermal kettle, placing the hydrothermal kettle in an oil bath kettle, heating to 160 ℃, and keeping the temperature for 6 hours, wherein the magnetic stirring speed is kept at 1500 rpm. After cooling to room temperature, the obtained precipitate is centrifugally separated, washed for 3 times by acetone, and finally dried in vacuum at 80 ℃;
(5) putting the precipitate obtained in the step (4) into a hydrogen-argon mixed gas tube furnace containing 5 vol% of hydrogen and heating the mixture for 3 min-1The temperature is raised to 350 ℃ at the speed of the reaction, the mixture is calcined for 2 hours, and the product is obtained after cooling.
The prepared KFSF @ CNTs material is subjected to structural characterization and electrochemical performance test according to the same method as the embodiment 1. The XRD structure of the product is characterized as shown in figure 16, and FeSO can be found in the product4·H2The impure phase of O, mainly FeSO as raw material4·7H2O is not sufficiently dissolved at a high concentration and is subsequently dehydrated in a solvothermal process. The results of the electrochemical performance tests are shown in table 1 and are clearly inferior to other samples made in the given concentration range.
TABLE 1 electrochemical Performance data
Figure BDA0003506679640000121

Claims (10)

1. KFeSO with interpenetrated carbon nanotubes4The preparation method of the F material is characterized by comprising the following steps:
(1) acidizing the carbon nano tube, and dispersing the acidized carbon nano tube in a polyhydric alcohol solvent to obtain a carbon nano tube dispersion liquid;
(2) stirring and dissolving an iron source and potassium fluoride in the carbon nano tube dispersion liquid to obtain a mixed liquid;
(3) carrying out a solvothermal reaction on the mixed solution in the step (2) to generate a precipitate;
(4) calcining the precipitate in the step (3) in a reducing atmosphere to obtain KFeSO with carbon nano tubes inserted4And F, materials.
2. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the polyalcohol in the step (1) is one of ethylene glycol, diethylene glycol, triethylene glycol or glycerol.
3. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that in the step (2), the mass ratio of the iron source to the potassium fluoride to the carbon nano tube is 1: 0.21-0.23: 0.036-0.072.
4. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the concentration of the carbon nano tube dispersion liquid in the step (1) is 1.0-2.0 g L-1。
5. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the concentration of the iron source and the potassium fluoride in the step (2) is 0.1-0.2 mol L-1。
6. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the reaction temperature in the step (3) is 150-180 ℃, and the reaction time is 2-6 h.
7. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the solvothermal reaction in the step (3) is carried out under the condition of stirring.
8. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the diameter of the carbon nano tube in the step (1) is 10-50 nm, and the length of the carbon nano tube is 10-30 mu m.
9. The carbon nanotube-interspersed KFeSO of claim 14The preparation method of the F material is characterized in that the reducing atmosphere in the step (4) is a hydrogen-argon mixed gas, and the volume percentage of hydrogen in the hydrogen-argon mixed gas is 5-10%.
10. The carbon nanotube-interspersed KFeSO of any one of claims 1-94Preparation method of F material to obtain KFeSO with carbon nano-tubes inserted4And the F material is applied as a positive electrode material of the potassium ion battery.
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