CN113707845A - Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery - Google Patents

Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery Download PDF

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CN113707845A
CN113707845A CN202110998822.3A CN202110998822A CN113707845A CN 113707845 A CN113707845 A CN 113707845A CN 202110998822 A CN202110998822 A CN 202110998822A CN 113707845 A CN113707845 A CN 113707845A
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potassium
potassium metal
metal battery
gold
current collector
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CN113707845B (en
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颜蔚
李红伟
张久俊
王健宜
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

The invention relates to the technical field of potassium metal batteries, in particular to a potassium metal battery cathode, a preparation method and application thereof and a potassium metal battery. The potassium metal battery cathode comprises a gold-loaded foam copper current collector and a potassium sheet; the potassium plate is embedded in the pore structure of the gold-loaded copper foam current collector. In the invention, the three-dimensional porous structure in the foamy copper current collector limits the volume expansion of the potassium cathode in the circulation process; the gold has lower nucleation overpotential, is a preferential deposition site of potassium ions in the battery cycle process, and can enable the potassium metal to be deposited more uniformly, thereby inhibiting the growth of dendritic crystals. Therefore, the potassium metal battery negative electrode can remarkably reduce the volume expansion of potassium metal in the circulation process and inhibit the growth of dendritic crystals, and high coulombic efficiency, long circulation life and excellent rate performance are realized.

Description

Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery
Technical Field
The invention relates to the technical field of potassium metal batteries, in particular to a potassium metal battery cathode, a preparation method and application thereof and a potassium metal battery.
Background
Among the conventional secondary batteries, the lithium ion battery has advantages of very high energy density, high operating voltage, environmental friendliness, no memory effect, etc., and occupies a large share in the market. However, with continued development, the positive and negative electrodes of commercial lithium ion batteries have approached their theoretical capacities, and the energy density increase has met with a bottleneck. With the rapid development of portable electronic devices, electric vehicles, and smart grids, people increasingly demand high-capacity batteries. Thus, the metal battery is returned to the field of view of scientific researchers. The lithium metal negative electrode has ultrahigh theoretical specific capacity (3860 mA.h.g)-1) And a very low reduction potential (-3.04Vvs SHE) is considered an ideal anode material. But the lithium resource is relatively rare (0.0017% by mass on earth) and is not distributed locally, and the factors greatly limit the wide application of the lithium resource. Whereas potassium is abundant and chemically similar to lithium. Thus, potassium metal is suitable for large-scale application in battery devices. Potassium metal batteries are considered to be the next generation of energy storage devices. Furthermore, in organic solvents, K is an alkali metal+The standard potential of the/K redox couple (relative to SHE) is lowest, which means that it can provide higher operating voltages and current densities.
However, many challenges remain in practical application of potassium metal anodes, such as safety and stability. A key factor in the success of potassium metal battery systems is the achievement of dendrite-free charging/discharging processes. Similar to most metal anodes, non-uniform deposition of potassium ions during cycling leads to dendritic growth, which is a major cause of cell shorting and explosion. And because no host exists, the volume change of the metal potassium negative electrode is not limited in the electroplating and stripping processes. After a few cycles, the electrode becomes porous and cracks because a large amount of "dead potassium" that is not electrochemically active is released from the electrode. The key to improving the life and coulombic efficiency of potassium metal batteries is to inhibit the growth of dendrites.
In order to inhibit dendritic growth of the metallic negative electrode, various strategies have been proposed in many previous reports. The method can be mainly divided into three types: optimizing electrolyte composition, using solid electrolyte and designing a negative electrode structure. With respect to designing the structure of the negative electrode, currently when designing the structure of a metal negative electrode, a three-dimensional current collector is used as a host for potassium, and the relatively infinite volume change of potassium during deposition/stripping is limited. In addition, the three-dimensional current collector can increase the specific surface area of the electrode, reduce local effective current and inhibit the growth of dendritic potassium. But due to the poor affinity of potassium metal for copper, there is a large nucleation overpotential during potassium deposition. The electrochemical performance is not satisfactory.
Disclosure of Invention
The invention aims to provide a potassium metal battery cathode, a preparation method and application thereof, and a potassium metal battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a potassium metal battery cathode, which comprises a gold-loaded foam copper current collector and a potassium sheet;
the potassium plate is embedded in the pore structure of the gold-loaded copper foam current collector.
The invention also provides a preparation method of the potassium metal battery cathode in the technical scheme, which comprises the following steps:
soaking the foam copper in a chloroauric acid solution to obtain a gold-loaded foam copper current collector;
and pressing the gold-loaded foamy copper current collector and the potassium sheet to obtain the potassium metal battery cathode.
Preferably, the concentration of the chloroauric acid solution is 0.0085-0.0105 mol/L.
Preferably, the volume ratio of the mass of the copper foam to the chloroauric acid solution is 1 g: 4-6 mL.
Preferably, the dipping temperature is room temperature, and the time is 1-1.5 min.
Preferably, the ratio of the thickness of the gold-supported copper foam current collector to the thickness of the potassium sheet is 1: 0.4.
Preferably, the pressing pressure is 100-300 psi, and the pressure maintaining time is 30-40 s.
Preferably, before the copper foam is immersed in the chloroauric acid solution, the method further comprises the step of acid leaching the copper foam.
The invention also provides the application of the potassium metal battery cathode prepared by the technical scheme or the potassium metal battery cathode prepared by the preparation method in the technical scheme in a potassium metal battery.
The invention also provides a potassium metal battery, which comprises a negative electrode, a diaphragm, an electrolyte and a positive electrode, wherein the negative electrode is the potassium metal battery negative electrode in the technical scheme or the potassium metal battery negative electrode prepared by the preparation method in the technical scheme.
The invention provides a potassium metal battery cathode, which comprises a gold-loaded foam copper current collector and a potassium sheet; the potassium plate is embedded in the pore structure of the gold-loaded copper foam current collector. In the invention, the three-dimensional porous structure in the foamy copper current collector limits the volume expansion of the potassium cathode in the circulation process; the gold has lower nucleation overpotential, is a preferential deposition site of potassium ions in the battery cycle process, and can enable the potassium metal to be deposited more uniformly, thereby inhibiting the growth of dendritic crystals. Therefore, the potassium metal battery negative electrode can remarkably reduce the volume expansion of potassium metal in the circulation process and inhibit the growth of dendritic crystals, and high coulombic efficiency, long circulation life and excellent rate performance are realized.
Drawings
Fig. 1 is an SEM image of copper foam and the gold-loaded copper foam current collector prepared as described in example 1;
fig. 2 is a first-turn charge-discharge voltage-specific capacity curve of the potassium metal batteries described in example 1 and comparative example 1;
FIG. 3 is a graph of the cyclic coulombic efficiency of the potassium metal batteries described in example 1 and comparative example 1;
FIG. 4 is a graph of rate performance of the potassium metal batteries described in example 1 and comparative example 1;
fig. 5 is a first turn charge-discharge voltage-specific capacity curve for the potassium metal batteries described in example 2 and comparative example 2;
fig. 6 is a schematic view of a process for preparing the negative electrode of the potassium metal battery of the present invention.
Detailed Description
The invention provides a potassium metal battery cathode, which comprises a gold-loaded foam copper current collector and a potassium sheet;
the potassium plate is embedded in the pore structure of the gold-loaded copper foam current collector.
In the invention, the particle size of gold in the gold-loaded copper foam current collector is preferably 80-140 nm, and more preferably 120 nm.
In the invention, the potassium metal battery negative electrode is prepared by pressing a gold-loaded foam copper current collector and a potassium sheet; the ratio of the thickness of the gold-supported copper foam current collector to the thickness of the potassium plate is preferably 1: 0.4. In the present invention, the gold-loaded copper foam current collector and the potassium plate have the same planar dimensions.
As shown in fig. 6, the invention also provides a method for preparing the negative electrode of the potassium metal battery in the above technical scheme, which comprises the following steps:
soaking the foam copper in a chloroauric acid solution to obtain a gold-loaded foam copper current collector;
pressing the gold-loaded foamy copper current collector and the potassium sheet to obtain the potassium metal battery cathode;
the gold-loaded copper foam current collector and the potassium plate are the same in size.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
According to the invention, the foamy copper is soaked in the chloroauric acid solution to obtain the gold-loaded foamy copper current collector.
In the invention, the concentration of the chloroauric acid solution is preferably 0.0085-0.0105 mol/L, and more preferably 0.009-0.01 mol/L.
In the present invention, the chloroauric acid solution is preferably prepared; the preparation method of the chloroauric acid solution is preferably obtained by mixing chloroauric acid and water; in the present invention, the chloroauric acid is preferably chloroauric acid trihydrate; the water is preferably deionized water; the mixing is preferably carried out under stirring; in the present invention, the stirring conditions are not particularly limited, and may be those well known to those skilled in the art.
The copper foam of the present invention is not particularly limited, and those known to those skilled in the art can be used.
Before the soaking, the invention preferably performs acid leaching on the copper foam; the acid solution used for acid leaching is preferably 1mol/L hydrochloric acid solution. The acid leaching time is not limited at all, and the oxide on the surface of the foam copper can be removed.
After the acid leaching is finished, the invention also preferably comprises washing and drying which are carried out in sequence; the washing is preferably carried out by sequentially adopting deionized water and absolute ethyl alcohol. The drying process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the present invention, the ratio of the mass of the copper foam to the volume of the chloroauric acid solution is preferably 1 g: 4-6 mL, more preferably 1 g: 6 mL.
In the present invention, the impregnation is preferably performed under a condition of standing. In the invention, the dipping temperature is preferably room temperature, and the time is preferably 1-1.5 min, and more preferably 1.2-1.3 min.
After the impregnation is finished, the invention also preferably comprises washing and drying which are carried out in sequence; the washing liquid selected for washing is preferably deionized water; the drying mode is preferably vacuum drying, and the temperature of the vacuum drying is preferably 80 ℃; the time is preferably 9 to 11 hours, and more preferably 10 hours.
After the gold-loaded foamy copper current collector is obtained, the gold-loaded foamy copper current collector and the potassium sheet are pressed together to obtain the potassium metal battery cathode.
In the present invention, the ratio of the thickness of the gold-supported copper foam current collector to the thickness of the potassium sheet is preferably 1: 0.4. The invention has no special limitation on the plane size of the gold-loaded foamy copper current collector and the potassium sheet, and the gold-loaded foamy copper current collector and the potassium sheet can be ensured to have the same plane size by adopting the plane size known by the technical personnel in the field. In a specific embodiment of the invention, the gold-loaded copper foam current collector and the potassium sheet both have a diameter of 12 mm; the thickness of the gold-loaded foamy copper current collector is 1mm, and the thickness of the potassium sheet is 0.4 mm. This is preferably achieved by trimming when the planar dimensions of the copper and potassium foam sheets differ from the desired dimensions.
In the invention, the pressure of the pressing is preferably 100-300 psi, and more preferably 150 psi; the dwell time is preferably 30 to 40s, and more preferably 30 s. In the present invention, the pressing is preferably performed in a protective atmosphere; the protective atmosphere is preferably an argon atmosphere.
In the present invention, controlling the pressing conditions within the above range allows the potassium sheet to be completely embedded into the pores of the gold-supported copper foam current collector.
The invention also provides the application of the potassium metal battery cathode prepared by the technical scheme or the potassium metal battery cathode prepared by the preparation method in the technical scheme in a potassium metal battery.
The invention also provides a potassium metal battery, which comprises a negative electrode, a diaphragm, an electrolyte and a positive electrode, wherein the negative electrode is the potassium metal battery negative electrode in the technical scheme or the potassium metal battery negative electrode prepared by the preparation method in the technical scheme.
In the present invention, the active material of the positive electrode is preferably prussian blue.
In the present invention, the prussian blue is preferably prepared; the preparation of the prussian blue preferably comprises the following steps:
will K4Fe(CN)6Mixing with water to obtain solution A;
FeCl is added3Mixing with water to obtain solution B;
and mixing the solution A and the solution B, and aging to obtain the Prussian blue.
The invention relates to K4Fe(CN)6And water to obtain solution A. In the present invention, the water is preferably deionized water; said K4Fe(CN)6The ratio of the amount of water to the amount of water is preferably (2-2.5) mmol: 150mL, more preferably (2.1 to 2.3) mmol: 150 mL. The mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
The invention uses FeCl3And water to obtain solution B. In the present invention, the water is preferably deionized water; the FeCl3The amount ratio of water to water is preferably 4mmol:50 mL. The mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
After the solution A and the solution B are obtained, the solution A and the solution B are mixed and aged to obtain the Prussian blue.
In the present invention, K in the solution A4Fe(CN)6And FeCl in solution B3Preferably 1:2 or 5: 8.
In the present invention, the mixing is preferably to add the solution B dropwise to the solution a under stirring; in the present invention, the stirring conditions are not particularly limited, and may be those well known to those skilled in the art. After the addition is complete, the invention also preferably includes continuing stirring for 2 hours. In the present invention, the temperature of the aging is preferably room temperature; the aging time is preferably 12 hours. After the aging is finished, the invention also preferably comprises filtering, washing and drying which are carried out in sequence; the filtration is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art. The washing is preferably carried out by washing the precipitate obtained by the filtration with water and ethanol in this order. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 80 ℃, and the time is preferably 12 h.
In the present invention, the positive electrode is preferably a prussian blue electrode; the Prussian blue electrode is preferably prepared; the preparation of the prussian blue electrode preferably comprises: the Prussian blue, the carbon black, the polyvinylidene fluoride and the N-methyl pyrrolidone which are prepared by the technical scheme are uniformly coated on an aluminum foil after being mixed, and the mixture is dried to obtain the Prussian blue electrode.
In the present invention, the mass ratio of the prussian blue to the carbon black to the polyvinylidene fluoride is preferably 6:3:1 or 8:1:1, the amount of the N-methylpyrrolidone used in the present invention is not particularly limited, and the amount used in the process of preparing the positive electrode, which is well known to those skilled in the art, is such that a paste slurry is formed after the mixing.
In the present invention, the mixing is preferably performed under stirring; the stirring process is not particularly limited, and may be performed by a method known to those skilled in the art.
The coating process is not particularly limited in the present invention, and a coating process in the preparation process of the positive electrode, which is well known to those skilled in the art, may be used.
In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 80 ℃, and the time is preferably 12 h.
After the drying is completed, the present invention preferably includes a cutting process, and the cutting process is not limited in any way by the present invention, and a process well known to those skilled in the art can be used to obtain a circular piece with a diameter of 10 mm.
In the present invention, the material of the separator is preferably glass fiber. In the embodiment of the invention, the diaphragm is specifically CATNO.1820-090.
In the present invention, the electrolyte is preferably 3mol/L dimethyl ether solution of potassium bis (fluorosulfonyl) imide (KFSI-DME).
The preparation process of the potassium metal battery is not limited in any way, and can be carried out by adopting a process well known to a person skilled in the art.
The following will explain the potassium metal battery negative electrode, the preparation method and application thereof, and the potassium metal battery provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 200mg of chloroauric acid trihydrate with 60mL of deionized water, and uniformly stirring to obtain a chloroauric acid solution;
placing the foamy copper (with the thickness of 1mm) in 1mol/L hydrochloric acid solution for 5min, removing surface oxides, then washing with deionized water and absolute ethyl alcohol in sequence, and drying to obtain pretreated foamy copper;
soaking 15g of pretreated foamy copper in 60mL of the chloroauric acid solution for 1min under a standing condition, washing with deionized water, and drying for 9h under vacuum at 80 ℃ to obtain a gold-loaded foamy copper current collector;
cutting the gold-loaded foamy copper current collector and a potassium sheet (with the thickness of 0.4mm) into a round shape with the diameter of 12mm under the argon atmosphere, then stacking, and pressing by adopting a tablet press, wherein the pressing pressure is 150psi, and the pressure maintaining time is 30s, so that the potassium sheet is completely embedded into the pores of the gold-loaded foamy copper current collector to obtain the potassium metal battery cathode;
2mmol of K4Fe(CN)6Mixing with 150mL of deionized water to obtain a solution A;
4mmol of FeCl3Mixing with 50mL of deionized water to obtain a solution B;
dropwise adding the solution B into the solution A under the stirring condition, continuously stirring for 2h, aging for 12h, filtering, sequentially washing with water and ethanol, and vacuum drying at 80 ℃ for 12h to obtain Prussian blue;
mixing the Prussian blue, the carbon black and the polyvinylidene fluoride according to the mass ratio of 6:3:1, adding N-methyl pyrrolidone, and stirring to form paste slurry;
coating the paste slurry on an aluminum foil, carrying out vacuum drying at 80 ℃ for 12h, and cutting into a wafer with the diameter of 10mm to obtain a Prussian blue electrode;
and (3) assembling the potassium metal battery with the model CR2032 by taking the negative electrode of the potassium metal battery as the negative electrode, the Prussian blue electrode as the positive electrode, the glass fiber of CAT 1820-090 as the diaphragm and the KFSI-DME with the concentration of 3mol/L as the electrolyte.
SEM test is carried out on the copper foam (Cu) and the prepared gold-loaded copper foam current collector (Au @ Cu), and the test result is shown in figure 1, as can be seen from figure 1, the copper foam has a three-dimensional structure and a smooth surface, and in the gold-loaded copper foam current collector, a plurality of gold particles are arranged on the surface of the copper foam.
Example 2
Mixing 200mg of chloroauric acid trihydrate with 60mL of deionized water, and uniformly stirring to obtain a chloroauric acid solution;
placing the foamy copper (with the thickness of 1mm) in 1mol/L hydrochloric acid solution for 5min, removing surface oxides, then washing with deionized water and absolute ethyl alcohol in sequence, and drying to obtain pretreated foamy copper;
soaking 10g of pretreated foamy copper in 60mL of the chloroauric acid solution for 1.5min under the standing condition, washing with deionized water, and drying in vacuum at 80 ℃ for 11h to obtain a gold-loaded foamy copper current collector;
cutting the gold-loaded foamy copper current collector and a potassium sheet (with the thickness of 0.4mm) into a round shape with the diameter of 12mm under the argon atmosphere, then stacking, and pressing by adopting a tablet press, wherein the pressing pressure is 150psi, and the pressure maintaining time is 30s, so that the potassium sheet is completely embedded into the pores of the gold-loaded foamy copper current collector to obtain the potassium metal battery cathode;
2mmol of K4Fe(CN)6Mixing with 150mL of deionized water to obtain a solution A;
4mmol of FeCl3Mixing with 50mL of deionized water to obtain a solution B;
dropwise adding the solution B into the solution A under the stirring condition, continuously stirring for 2h, aging for 12h, filtering, sequentially washing with water and ethanol, and vacuum drying at 80 ℃ for 12h to obtain Prussian blue;
mixing the Prussian blue, the carbon black and the polyvinylidene fluoride according to the mass ratio of 8:1:1, adding N-methyl pyrrolidone, and stirring to form paste slurry;
coating the paste slurry on an aluminum foil, carrying out vacuum drying at 80 ℃ for 12h, and cutting into a wafer with the diameter of 10mm to obtain a Prussian blue electrode;
and (3) assembling the potassium metal battery with the model CR2032 by taking the negative electrode of the potassium metal battery as the negative electrode, the Prussian blue electrode as the positive electrode, the glass fiber of CAT 1820-090 as the diaphragm and the KFSI-DME with the concentration of 3mol/L as the electrolyte.
Comparative example 1
Placing the foamy copper (with the thickness of 1mm) in 1mol/L hydrochloric acid solution for 5min, removing surface oxides, then washing with deionized water and absolute ethyl alcohol in sequence, and drying to obtain pretreated foamy copper;
cutting the pretreated foamy copper and a potassium sheet (with the thickness of 0.4mm) into a round shape with the diameter of 12mm under the argon atmosphere, then stacking, and pressing by adopting a tablet press, wherein the pressing pressure is 150psi, the pressure maintaining time is 30s, so that the potassium sheet is completely embedded into the pores of the pretreated foamy copper, and the potassium metal battery cathode is obtained;
procedure for preparing a potassium metal battery model CR2032 referring to example 1.
Comparative example 2
The procedure for preparing the negative electrode of the potassium metal battery was referred to comparative example 1;
procedure for preparing a potassium metal battery model CR2032 referring to example 2.
Test example 1
Carrying out constant-current charge and discharge tests on the potassium metal batteries in the embodiment 1 and the comparative example 1 at a current density of 0.5mA/g, wherein the voltage range is set to be 2-4V;
wherein, fig. 2 is a first-turn charge-discharge voltage-specific capacity curve of the potassium metal batteries described in example 1 and comparative example 1, wherein Cu-K corresponds to the potassium metal battery described in comparative example 1, Au @ Cu-K corresponds to the potassium metal battery described in example 1, and as can be seen from fig. 2, the potassium metal battery described in example 1 shows a higher specific mass capacity of 65mA · h/g during the first-turn charge-discharge process, while the potassium metal battery described in comparative example 1 only has 48mA · h/g;
FIG. 3 is a cyclic coulombic efficiency curve of the potassium metal batteries of example 1 and comparative example 1, wherein Cufoam-K corresponds to the potassium metal battery of comparative example 1, and Au @ Cufoam-K corresponds to the potassium metal battery of example 1, and as can be seen from FIG. 3, the potassium metal battery of example 1 has a coulombic efficiency as high as 93% after 250 cycles, and shows good cyclic performance; compared with the potassium metal battery in the comparative example 1, the coulombic efficiency is only 59 percent after the circulation of 150 circles;
the potassium metal batteries described in example 1 and comparative example 1 are subjected to rate performance tests, the current density is 0.1, 0.2, 0.5, 1, 3 and 5A/g in sequence, and the test results are shown in FIG. 4, wherein Cu-K corresponds to the potassium metal battery described in comparative example 1, Au @ Cu-K corresponds to the potassium metal battery described in example 1, as can be seen from FIG. 4, the rate performance of the potassium metal battery described in example 1 is superior to that of the potassium metal battery described in comparative example 1, and when the current density is gradually increased from 0.1A/g to 5A/g, the specific capacity is reduced, but the specific capacity of the potassium metal battery described in example 1 is stable, the fluctuation similar to that of the potassium metal battery described in comparative example 1 does not occur, and the specific capacity is obviously higher than that of comparative example 1. Therefore, the surface of the foamy copper is modified (gold is loaded), so that the overpotential of potassium deposition can be reduced, the potassium deposition process is more uniform, a uniform and stable SEI film is formed, dendritic growth of potassium and electrolyte consumption are inhibited, and in addition, the three-dimensional framework structure of the foamy copper limits serious volume expansion in the potassium deposition process, so that the cycle life of the battery is prolonged, and the safety performance is improved.
Test example 2
Carrying out constant-current charge and discharge tests on the potassium metal batteries in the embodiment 2 and the comparative example 2 at a current density of 0.5mA/g, wherein the voltage range is set to be 2-4V;
fig. 5 is a first-turn charge-discharge voltage-specific capacity curve of the potassium metal batteries described in example 2 and comparative example 2, wherein Cu-K corresponds to the potassium metal battery described in comparative example 2, and Au @ Cu-K corresponds to the potassium metal battery described in example 2, and it can be seen from fig. 5 that the potassium metal battery described in example 1 exhibits a higher specific mass capacity of 73mA · h/g during the first-turn charge-discharge process, while the potassium metal battery described in comparative example 1 has only 50mA · h/g.
In conclusion, the potassium metal battery cathode can improve the specific capacity, the coulombic efficiency and the excellent rate capability of the potassium metal battery, improves the cycling stability and the safety of the potassium metal battery, and prolongs the service life of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The potassium metal battery negative electrode is characterized by comprising a gold-loaded foam copper current collector and a potassium sheet;
the potassium plate is embedded in the pore structure of the gold-loaded copper foam current collector.
2. The method for preparing the negative electrode of the potassium metal battery as claimed in claim 1, comprising the steps of:
soaking the foam copper in a chloroauric acid solution to obtain a gold-loaded foam copper current collector;
and pressing the gold-loaded foamy copper current collector and the potassium sheet to obtain the potassium metal battery cathode.
3. The method according to claim 2, wherein the concentration of the chloroauric acid solution is 0.0085-0.0105 mol/L.
4. The method according to claim 3, wherein the ratio of the mass of the copper foam to the volume of the chloroauric acid solution is 1 g: 4-6 mL.
5. The method according to claim 2, wherein the impregnation is carried out at room temperature for 1 to 1.5 min.
6. The method of claim 2, wherein the ratio of the thickness of the gold-supported copper foam current collector to the thickness of the potassium sheet is 1: 0.4.
7. The method of claim 2, wherein the pressure of the pressing is 100 to 300psi and the dwell time is 30 to 40 s.
8. The method of claim 2, further comprising pickling the copper foam prior to immersing the copper foam in the chloroauric acid solution.
9. The potassium metal battery cathode as claimed in claim 1 or the potassium metal battery cathode prepared by the preparation method as claimed in any one of claims 2 to 6 is applied to a potassium metal battery.
10. A potassium metal battery, which comprises a negative electrode, a diaphragm, an electrolyte and a positive electrode, and is characterized in that the negative electrode is the potassium metal battery negative electrode in claim 1 or the potassium metal battery negative electrode prepared by the preparation method in any one of claims 2 to 5.
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CN110828828A (en) * 2018-08-14 2020-02-21 中南大学 3D porous zinc-loaded current collector, sodium-or potassium-philic battery cathode, and preparation and application thereof
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