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CN118335924A - Composite negative electrode material for potassium ion battery and preparation method and application thereof - Google Patents

Composite negative electrode material for potassium ion battery and preparation method and application thereof Download PDF

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Publication number
CN118335924A
CN118335924A CN202410228052.8A CN202410228052A CN118335924A CN 118335924 A CN118335924 A CN 118335924A CN 202410228052 A CN202410228052 A CN 202410228052A CN 118335924 A CN118335924 A CN 118335924A
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composite anode
anode material
ion battery
potassium ion
preparation
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李德平
夏伟豪
吉凤君
慈立杰
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Harbin Institute Of Technology shenzhen Shenzhen Institute Of Science And Technology Innovation Harbin Institute Of Technology
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Harbin Institute Of Technology shenzhen Shenzhen Institute Of Science And Technology Innovation Harbin Institute Of Technology
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Priority to CN202410228052.8A priority Critical patent/CN118335924A/en
Publication of CN118335924A publication Critical patent/CN118335924A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/134—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/621—Binders
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The application relates to the technical field of batteries, and discloses a composite anode material for a potassium ion battery, and a preparation method and application thereof. The preparation method comprises the following steps: providing a composite anode material precursor; pyrolyzing the precursor of the composite anode material in an inert atmosphere, and removing impurities to obtain an intermediate of the composite anode material; and mixing the composite anode material intermediate, the conductive agent and the binder in water to obtain a mixture, and drying the mixture to obtain the composite anode material for the potassium ion battery. The preparation method of the composite anode material for the potassium ion battery can realize the rapid preparation of the porous carbon material in situ, does not need additional template agent or pore-forming agent, and has the advantages of simple method, strong process operability and easy realization of large-scale production. The metal nano particles in the prepared composite anode material for the potassium ion battery are uniformly distributed on the porous carbon matrix, so that the problem of electrode failure caused by severe volume change of antimony, bismuth and tin in the charging and discharging process is effectively solved.

Description

Composite negative electrode material for potassium ion battery and preparation method and application thereof
Technical Field
The application relates to the technical field of batteries, in particular to a composite anode material for a potassium ion battery, and a preparation method and application thereof.
Background
Lithium ion batteries have experienced rapid growth over the past thirty years, promoting the development of the portable electronic device industry. In recent years, the application of lithium ion batteries is gradually expanded to large electric vehicles and energy storage stations, which pose challenges for cost and abundance. However, the low earth abundance of lithium fails to meet the ever-increasing cost and sustainability demands. Therefore, there is an urgent need to develop alternative battery systems with higher energy density or lower cost. The potassium element has relatively high earth abundance, and the commercial graphite can realize electrochemical reversible potassium storage, so that the potassium ion battery becomes a cost-effective electrochemical energy storage system. Recall that in the past, the emerging potassium ion cells were based on the discovery of potassium metal combined with graphite, intercalation graphite compounds, and the first K// KPB prototype potassium ion cell was published in 2004.
Since graphite proved to be useful for intercalation of potassium ions, there has been an increasing search for potassium ion batteries. The success of graphite in potassium ion batteries has contributed to a great deal of research into early high performance carbonaceous electrode materials, including porous carbon, hard carbon, soft carbon, graphite, and carbon nanotubes/nanofibers. But its relatively low reversible capacity and ramp charge-discharge plateau characteristics limit its application prospects. To meet future applications, various electrode materials have been excavated, including intercalation-type, organic-type, conversion-type, and alloying-type. Among the reported studies, carbon-based materials have been studied more because of their diversity in form and stable chemical properties. However, they are often limited by low theoretical specific capacity and slow kinetics when potassium ions are inserted/extracted rapidly. Higher capacities are typically provided for metal oxides/sulfides/selenides, but greater volume expansion occurs. For organic materials, they are often faced with problems of poor electronic conductivity and dissolution in the electrolyte. The alloy type negative electrode has the highest reversible capacity and a moderate discharge platform, and gradually attracts wide attention, and serious volume change is still an urgent problem to be solved.
Accordingly, there is a need in the art for improvement.
Disclosure of Invention
In view of the defects of the prior art, the application aims to provide a composite anode material for a potassium ion battery, a preparation method and application thereof, and aims to solve the problem that the electrode is invalid due to the severe volume change of antimony, bismuth and tin in the charging and discharging process.
The technical scheme of the application is as follows:
in a first aspect of the present application, there is provided a method for preparing a composite anode material for a potassium ion battery, comprising the steps of:
Providing a composite anode material precursor; pyrolyzing the precursor of the composite anode material in an inert atmosphere, and removing impurities to obtain an intermediate of the composite anode material; and mixing the composite anode material intermediate, the conductive agent and the binder in water to obtain a mixture, and drying the mixture to obtain the composite anode material for the potassium ion battery.
Optionally, the composite anode material precursor comprises at least one of antimonic potassium tartrate, bismuth subsalicylate, bismuth sodium citrate, antimony acetate and stannous disodium citrate.
Optionally, the step of removing impurities includes: and grinding the pyrolyzed composite anode material precursor into powder, repeatedly using water or absolute ethyl alcohol for rinsing, and removing impurities by suction.
Optionally, the mass ratio of the composite anode material intermediate to the conductive agent to the binder is 5-8:1-4:1.
Optionally, the conductive agent comprises at least one of SuperP and acetylene black; the binder is at least one of sodium carboxymethyl cellulose, polyvinylidene fluoride and styrene-butadiene rubber.
Optionally, before the drying, the mixture is coated, and the thickness of the coating is 50-250 μm.
In a second aspect of the application, a composite anode material for a potassium ion battery prepared by the preparation method is provided.
Optionally, the composite anode material for a potassium ion battery includes: a porous carbon matrix; and metal nanoparticles distributed on the porous carbon matrix, wherein the metal nanoparticles comprise at least one of antimony nanoparticles, bismuth nanoparticles and tin nanoparticles.
In a third aspect of the present application, there is provided a composite anode made of a raw material including the composite anode material for a potassium ion battery in the present application.
In a fourth aspect of the present application, there is provided a potassium ion battery comprising an electrolyte, a separator, a positive electrode, and a composite negative electrode of the present application.
Compared with the prior art, the application has the following advantages:
The preparation method of the composite anode material for the potassium ion battery can realize the rapid preparation of the porous carbon material in situ, does not need additional template agent or pore-forming agent, and has the advantages of simple method, strong process operability and easy realization of large-scale production. In the composite anode material for the potassium ion battery prepared by the preparation method of the composite anode material for the potassium ion battery, metal nano particles are uniformly distributed on a porous carbon matrix, so that the problem of electrode failure caused by severe volume change of antimony, bismuth and tin in the charge and discharge process is effectively solved, the problem of capacity attenuation of a battery prepared by using the electrode containing the metal material is solved, and the electrochemical performance of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is an X-ray diffraction chart of a composite anode material for a potassium ion battery provided by an embodiment of the application;
Fig. 2 is a transmission electron microscope image of a composite anode material for a potassium ion battery according to an embodiment of the present application;
fig. 3 is an element distribution spectrum of a composite anode material for a potassium ion battery according to an embodiment of the present application;
FIG. 4 is a transmission electron microscope image of another composite anode material for a potassium ion battery according to an embodiment of the present application;
FIG. 5 is a graph showing the element distribution of another composite anode material for a potassium ion battery according to an embodiment of the present application;
FIG. 6 is a transmission electron microscope image of a composite anode material for a potassium ion battery according to an embodiment of the present application;
fig. 7 is an element distribution spectrum of a composite anode material for a potassium ion battery according to an embodiment of the present application;
fig. 8 is a graph showing charge-discharge rate performance of a composite negative electrode material for a potassium ion battery and a commercial micron antimony material according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings and the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments of the present application. All other embodiments, which can be made by a person of ordinary skill in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application. The following embodiments and features in the embodiments may be combined with each other without conflict.
It should be noted that, if there is a description of "first," "second," etc. in the practice of the present application, the description of "first," "second," etc. is for descriptive purposes only and is not to be construed as indicating or implying any particular importance or implying any particular order among or between such descriptions. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to enable those skilled in the art to implement the embodiments as a basis, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist and is not within the scope of protection claimed by the present application.
According to a first aspect of the embodiment of the application, a preparation method of a composite anode material for a potassium ion battery in the embodiment of the application is provided, which comprises the following steps:
S1, providing a composite anode material precursor.
In some embodiments, the composite anode material precursor includes at least one of potassium antimonate tartrate, bismuth subsalicylate, sodium bismuth citrate, antimony acetate, disodium stannous citrate. For example, the precursor of the composite anode material is antimonial potassium tartrate, antimony acetate, bismuth sodium citrate, stannous disodium citrate, a mixture of antimonial potassium tartrate and bismuth subsalicylate, a mixture of any two or three of the other materials, and the like. Of course, the composite anode material precursor may also be a hydrate of the above materials, for example, the composite anode material precursor is antimony potassium tartrate trihydrate. The composite anode material precursor may be in the form of powder, block, or the like.
S2, pyrolyzing the precursor of the composite anode material in an inert atmosphere, and removing impurities to obtain the intermediate of the composite anode material.
The method comprises the following specific steps: and (3) placing the composite anode material precursor in a tube furnace, heating and pyrolyzing under inert atmosphere. Wherein the flow rate of the inert gas is 50-200cm 3/min. For example, the flow rate of the inert gas is 50cm3/min、60cm3/min、80cm3/min、100cm3/min、120cm3/min、140cm3/min、150cm3/min、160cm3/min、180cm3/min or 200cm 3/min or the like. The temperature rising rate is 2-10 ℃/min. For example, the rate of temperature rise is 2℃per minute, 3℃per minute, 4℃per minute, 5℃per minute, 6℃per minute, 7℃per minute, 8℃per minute, 9℃per minute, 10℃per minute, or the like. The final temperature of the temperature rise is 500-800 ℃. For example, the final temperature of the temperature rise is 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like. The incubation time at the final temperature is 2-6h. For example, the incubation time is 2h, 3h, 4h, 5h, 6h, or the like. The pyrolysis temperature of the composite anode material precursor used in the preparation method is 500-800 ℃, and compared with the pyrolysis temperature of 1000 ℃ of a hard carbon material, the preparation method has the advantage of low energy consumption.
In some embodiments, the inert atmosphere comprises at least one of argon, nitrogen.
The composite anode material precursor is pyrolyzed in a mode of combining inert atmosphere and heating, and the product comprises metal nano particles, a porous carbon matrix and other impurities. Further, the products after pyrolysis are subjected to impurity removal. In some embodiments, the specific steps of removing the impurities include:
And S21, fully grinding the pyrolyzed composite anode material precursor into powder, dissolving the powder in water to obtain a mixture, and stirring the mixture by using a stirrer.
Stirring time is 8-16h. For example, the stirring time is 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, or the like. The stirrer and the rotation speed can be selected by those skilled in the art according to actual needs, and are not limited herein. The pyrolyzed composite anode material precursor is ground into powder, so that impurities generated in the pyrolysis process can be more easily dissolved in deionized water, and the impurity removal efficiency is improved.
S22, removing waste liquid from the stirred mixture by a vacuum suction filtration method, respectively rinsing with deionized water and/or absolute ethyl alcohol, and removing the waste liquid by a vacuum suction filtration method after rinsing. And (5) cleaning for multiple times to obtain the composite anode material intermediate. The number of times of rinsing is 3-5, which includes at least one rinsing with water and at least one rinsing with absolute ethanol. The number of rinses may also be greater. The impurities generated by pyrolysis can be removed as much as possible by repeated rinsing and suction filtration of water and absolute ethyl alcohol, so that the purity of the precursor of the composite anode material is improved.
S3, mixing the composite anode material intermediate, the conductive agent and the binder in water to obtain a mixture, and drying the mixture to obtain the composite anode material for the potassium ion battery.
The method comprises the following specific steps: and mixing and dissolving the intermediate of the composite anode material, the conductive agent and the binder in deionized water according to a certain mass ratio, uniformly stirring, and drying to obtain the composite anode material for the potassium ion battery.
In some embodiments, the mass ratio of the composite anode material intermediate, the conductive agent, and the binder is 5-8:1-4:1. For example, the mass ratio of the composite anode material intermediate, the conductive agent, and the binder is 5:1:1, 5:2:1, 6:3:1, 7:4:1, 6:2:1, or 8:4:1, etc. Preferably, the mass ratio of the composite anode material intermediate to the conductive agent to the binder is 7:2:1.
In some embodiments, the stirring time is from 6 to 12 hours. For example, the stirring time is 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc. The middle of the composite anode material, the conductive agent and the binder can form uniform slurry through stirring, so that metal nano particles in the prepared composite anode material are uniformly distributed on the porous carbon matrix.
In some embodiments, the conductive agent includes at least one of SuperP, acetylene black. The binder can be at least one of sodium carboxymethyl cellulose, polyvinylidene fluoride and styrene butadiene rubber.
In some embodiments, the mixture obtained in S2 is coated to a thickness of 50-250 μm before drying in step S2. For example, the thickness of the coating is 50 μm, 100 μm, 150 μm, 200 μm or 250 μm, etc. Coating the mixture may be coated on a copper foil current collector and the thickness controlled using a four-sided applicator. The loading amount of active substances in the finally prepared composite anode material for the potassium ion battery can be controlled by adjusting the coating thickness, and when the coating thickness is 50-250 mu m, the metal nano particles are ensured to be uniformly distributed on the porous carbon matrix, and meanwhile, the composite anode material has better electrochemical performance. If the active material loading is too large, the resistance of the battery including the composite anode in the embodiment of the present application becomes large, making ion transport difficult, and resulting in deterioration of the cycle performance and rate performance of the battery.
The second aspect of the embodiment of the application provides a composite anode material for a potassium ion battery, which is prepared by adopting the preparation method of the composite anode material for the potassium ion battery. The composite anode material for the potassium ion battery comprises a porous carbon matrix and metal nano particles distributed on the porous carbon matrix. The metal nanoparticles comprise at least one of antimony nanoparticles, bismuth nanoparticles, tin nanoparticles. The metal nano particles are uniformly distributed on the porous carbon matrix, so that the problem of electrode failure caused by severe volume change of antimony, bismuth and tin materials in the charge and discharge process is effectively solved, the problem of capacity attenuation of a battery made of the electrode containing the metal materials is solved, and the electrochemical performance of the battery is improved.
In a third aspect of the embodiment of the application, a composite anode is provided, which is made from raw materials including the composite anode material for the potassium ion battery provided by the embodiment of the application.
In some embodiments, the method of preparing a composite anode includes the steps of: and (3) preparing the composite anode material for the non-dried potassium ion battery into a specified thickness, drying in a vacuum box, and cutting according to the requirement after drying to obtain the composite anode.
Wherein the temperature of the drying is 80-110 ℃. For example, the temperature of the drying is 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, or the like. The drying time is 8-12h. For example, the drying time is 8h, 9h, 10h, 11h, 12h, or the like. The shape after cutting can be round, and the diameter is 12-16mm.
In a fourth aspect of the embodiments of the present application, a potassium ion battery is provided, comprising an electrolyte, a separator, a positive electrode, and a composite negative electrode according to the embodiments of the present application.
In some embodiments, the electrolyte includes, but is not limited to, a mixed solution of potassium lithium bis-fluorosulfonamide and ethylene glycol dimethyl ether, the separator includes, but is not limited to, a glass fiber membrane (GF/D), and the material of the positive electrode includes, but is not limited to, potassium.
In some embodiments, a method of making a potassium ion battery includes the steps of:
In a glove box filled with high-purity argon, wherein the content of H 2O、O2 is less than 0.1ppm, the composite negative electrode, the metal potassium as the negative electrode and the glass fiber film (GF/D) as the diaphragm in the embodiment of the application are used as electrolyte (the concentration of the electrolyte is 5 mol/L) to assemble the CR2032 button cell.
Further description will be given below by way of specific examples.
Example 1
(1) Putting the antimonial potassium tartrate trihydrate powder into a tube furnace, taking argon as carrier gas, controlling the flow rate to be 100cm 3/min, controlling the heating rate to be 6 ℃/min, gradually increasing the temperature from room temperature to 600 ℃, and preserving the temperature at the set temperature for 3 hours;
(2) After the calcined sample is fully ground into fine powder, adding the fine powder into a beaker filled with deionized water, and placing the beaker on a stirrer to stir for 12 hours at a certain rotating speed;
(3) And removing waste liquid from the powder after stirring and cleaning by a vacuum suction filtration method, rinsing with deionized water for 2 times, removing the waste liquid by suction filtration, rinsing with absolute ethyl alcohol for 1 time, removing the waste liquid by suction filtration, and drying to obtain the composite anode material for the potassium ion battery.
The obtained composite anode material for potassium ion battery was subjected to X-ray diffraction analysis, and the result is shown in fig. 1. As can be seen from fig. 1, the XRD spectrum of the composite anode material for potassium ion battery matches with the characteristic peaks of Sb. The obtained composite negative electrode material for potassium ion battery was observed by a transmission electron microscope, and the results are shown in fig. 2. As can be seen from fig. 2, antimony exhibits nano-size and is uniformly distributed on the porous carbon matrix. The element distribution in the prepared composite anode material for potassium ion battery was analyzed, and the result is shown in fig. 3. As can be seen from fig. 3, in the composite anode material for potassium ion battery, the nano particles are antimony elements, and the matrix is porous carbon. From the analysis, nano antimony in the prepared composite negative electrode is uniformly distributed on the porous carbon matrix.
Example 2
(1) Placing bismuth potassium citrate powder into a tube furnace, taking argon as carrier gas, controlling the flow rate to be 50cm 3/min, controlling the heating rate to be 2 ℃/min, gradually increasing the temperature from room temperature to 500 ℃, and preserving the temperature at the set temperature for 6 hours;
(2) After the calcined sample is fully ground into fine powder, adding the fine powder into a beaker filled with deionized water, and placing the beaker on a stirrer to stir for 8 hours at a certain rotating speed;
(3) And removing waste liquid from the powder after stirring and cleaning by a vacuum suction filtration method, rinsing with deionized water for 2 times, removing the waste liquid by suction filtration, rinsing with absolute ethyl alcohol for 1 time, removing the waste liquid by suction filtration, and drying to obtain the composite anode material for the potassium ion battery.
The obtained composite anode material for potassium ion battery was observed with a transmission electron microscope and the element distribution therein was analyzed, and the results are shown in fig. 4 and 5. As can be seen from fig. 4 and 5, nano bismuth is uniformly distributed on the porous carbon matrix in the prepared composite anode.
Example 3
(1) Putting stannous citrate disodium powder into a tube furnace, taking argon as carrier gas, controlling the flow rate to be 200cm 3/min, controlling the heating rate to be 10 ℃/min, gradually increasing the temperature from room temperature to 800 ℃, and preserving the temperature at the set temperature for 2 hours;
(2) After the calcined sample is fully ground into fine powder, adding the fine powder into a beaker filled with deionized water, and placing the beaker on a stirrer to stir for 16 hours at a certain rotating speed;
(3) And removing waste liquid from the powder after stirring and cleaning by a vacuum suction filtration method, rinsing with deionized water for 2 times, removing the waste liquid by suction filtration, rinsing with absolute ethyl alcohol for 1 time, removing the waste liquid by suction filtration, and drying to obtain the composite anode material for the potassium ion battery.
The obtained composite anode material for potassium ion battery was observed with a transmission electron microscope and the element distribution therein was analyzed, and the results are shown in fig. 6 and 7. As can be seen from fig. 6 and 7, the nano tin in the prepared composite anode is uniformly distributed on the porous carbon matrix.
Test example 1
The composite negative electrode material for the potassium ion battery in example 1 and commercial micron antimony are respectively prepared into a negative electrode plate of 150 mu m, the obtained negative electrode plate is assembled in a glove box filled with high-purity argon gas and having H 2O、O2 content of less than 0.1ppm, a metal potassium is used as a negative electrode, a glass fiber film (GF/D) is used as a diaphragm, a mixed solution of potassium lithium difluorosulfimide and ethylene glycol dimethyl ether is used as an electrolyte (the concentration of the electrolyte is 5 mol/L), and the CR2032 button cell is assembled. The assembled battery was subjected to electrochemical performance test after standing for 12 hours in air, the test equipment was a Land battery test system, the test voltage range was 0.01-2.5V, and as a result, as shown in fig. 8, μsb represents a battery made of commercial micron antimony as a negative electrode, and sb@c represents a battery made of a composite negative electrode material for a potassium ion battery in example 1 as a negative electrode. As can be seen from fig. 8, the reversible capacity of the battery prepared from the composite anode material for a potassium ion battery in example 1 after 100 cycles at 0.2C was 465.0mah·g -1, the capacity retention rate was almost 100%, while the capacity of the battery prepared from the commercial micron antimony as an anode rapidly decayed after the 20 th cycle, and only the reversible capacity of 60.3mah·g -1 was retained after the completion of 100 cycles.
In summary, the preparation method of the composite anode material for the potassium ion battery provided by the application can realize the rapid preparation of the porous carbon material in situ, does not need additional template agent or pore-forming agent, and has the advantages of simple method, strong process operability and easiness in realizing large-scale production. In the composite anode material prepared by the preparation method of the composite anode material, metal nano particles are uniformly distributed on the porous carbon matrix, so that the problem of electrode failure caused by severe volume change of antimony, bismuth and tin in the charge and discharge process is effectively solved, the problem of capacity attenuation of a battery prepared by using the electrode containing the metal material is solved, and the electrochemical performance of the battery is improved.
It is to be understood that the application is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (10)

1. The preparation method of the composite anode material for the potassium ion battery is characterized by comprising the following steps:
Providing a composite anode material precursor;
pyrolyzing the composite anode material precursor in inert atmosphere, and removing impurities to obtain a composite anode material intermediate;
and mixing the composite anode material intermediate, the conductive agent and the binder in water to obtain a mixture, and drying the mixture to obtain the composite anode material for the potassium ion battery.
2. The method of claim 1, wherein the composite negative electrode material precursor comprises at least one of potassium antimonate tartrate, bismuth subsalicylate, sodium bismuth citrate, antimony acetate, and disodium stannous citrate.
3. The method of claim 1, wherein the step of removing impurities comprises:
And grinding the pyrolyzed composite anode material precursor into powder, repeatedly using water or absolute ethyl alcohol for rinsing, and removing impurities by suction.
4. The preparation method according to claim 1, wherein the mass ratio of the composite anode material intermediate, the conductive agent and the binder is 5-8:1-4:1.
5. The method according to claim 1, wherein the conductive agent comprises at least one of SuperP and acetylene black;
The binder comprises at least one of sodium carboxymethyl cellulose, polyvinylidene fluoride and styrene-butadiene rubber.
6. The method according to claim 1, wherein the mixture is coated with a thickness of 50 to 250 μm before the drying.
7. A composite anode material for a potassium ion battery prepared by the preparation method of any one of claims 1 to 6.
8. The composite anode material for a potassium ion battery according to claim 7, wherein the composite anode material for a potassium ion battery comprises:
A porous carbon matrix;
and metal nanoparticles distributed on the porous carbon matrix, wherein the metal nanoparticles comprise at least one of antimony nanoparticles, bismuth nanoparticles and tin nanoparticles.
9. A composite anode, characterized in that the composite anode is made of a raw material comprising the composite anode material for a potassium ion battery according to claim 7.
10. A potassium ion battery comprising an electrolyte, a separator, a positive electrode, and the composite negative electrode of claim 9.
CN202410228052.8A 2024-02-29 2024-02-29 Composite negative electrode material for potassium ion battery and preparation method and application thereof Pending CN118335924A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118720158A (en) * 2024-09-03 2024-10-01 中国科学技术大学 Hierarchical porous carbon composite tin-antimony alloy material for alkali metal ion secondary battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118720158A (en) * 2024-09-03 2024-10-01 中国科学技术大学 Hierarchical porous carbon composite tin-antimony alloy material for alkali metal ion secondary battery

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