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CN112018349A - CoTe2/MXene composite material and preparation method thereof - Google Patents

CoTe2/MXene composite material and preparation method thereof Download PDF

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CN112018349A
CN112018349A CN202010805118.7A CN202010805118A CN112018349A CN 112018349 A CN112018349 A CN 112018349A CN 202010805118 A CN202010805118 A CN 202010805118A CN 112018349 A CN112018349 A CN 112018349A
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mxene
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CN112018349B (en
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张业龙
徐晓丹
周健文
孙宏阳
陈浩
彭章泉
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Wuyi University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
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    • HELECTRICITY
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    • H01M10/00Secondary cells; Manufacture thereof
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a CoTe2The preparation method of the/MXene composite material comprises the following steps: adding MXene material into dispersant to prepare dispersion liquid with concentration of 1-10 mg/ml; adding a cobalt source and a reducing agent into the dispersion liquid, and stirring and dissolving to obtain a mixed solution; heating the mixed solution, cooling, centrifuging, washing and drying to obtain a precursor Co (OH)2/MXene; mixing the above precursor Co (OH)2The mol ratio of/MXene to tellurium source is 1: heating according to the proportion of 1-6, and cooling to obtain a crude product; centrifuging the crude product at a rotation speed of 5000-Washing for-10 min, and drying to obtain CoTe2the/MXene composite material. CoTe prepared by the invention2the/MXene composite material is applied to the potassium ion battery cathode, has good cycling stability, higher specific capacity and excellent rate capability, has the advantages of low cost, rich resources, simple preparation method and the like, and is suitable for large-scale production and application of the potassium ion battery.

Description

CoTe2/MXene composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to CoTe2a/MXene composite material and a preparation method thereof.
Background
Since the 21 st century, with the continuous improvement of energy demand of modern society, fossil energy is continuously consumed and becomes exhausted, environmental problems become serious, and the sustainable development of human society is seriously affected.
At present, a lithium ion battery has been used as a secondary battery energy storage system to achieve great success in the fields of electric vehicles, portable electronic devices and the like, and meanwhile, as the usage amount of the lithium ion battery is increased, a large amount of lithium resources are consumed, and the resources are distributed unevenly, so that the price of the lithium ion battery is increased, and the application of the lithium ion battery in the field of energy storage is limited. Therefore, the development of a novel secondary alkali metal battery has extremely high social value.
The potassium resource is abundant in nature (the abundance of potassium element in earth crust is 2.47%), the cost is low, the oxidation-reduction potential (K +/K, -2.936V is close to that of a standard hydrogen electrode) is close to lithium, and the lithium battery has the advantages of high energy density, long cycle service life, good rate capability and the like, while the commercial graphite with relatively low theoretical specific capacity and poor rate capability can not completely meet the energy density requirement of a high-performance battery. Therefore, the research on the negative electrode material of the potassium ion battery with high specific capacity and good cycling stability attracts people to pay attention.
The transition metal compound is an ideal candidate for the negative electrode material of the potassium ion battery due to the advantages of high reversible specific capacity, high conductivity, reversible redox reaction and the like. However, the transition metal compound is liable to exhibit a large volume expansion during charge and discharge cycles, resulting in pulverization of the electrode material, thereby causing problems of poor rate performance, rapid capacity fading, and the like during cycles. Therefore, how to solve the problems of poor rate capability, fast capacity fading and the like in the circulation process of the transition metal compound becomes a great technical obstacle in the field.
As a novel transition metal carbon or nitride, MXene has the advantages of excellent conductivity and mechanical property, high hydrophilic surface and ion transmission performance due to the unique layered structure and rich and adjustable components, and hopefully overcomes the problems of poor rate performance, fast capacity attenuation and the like in the circulation process of a transition metal compound, but the interlayer spacing is small, and a surface functional group has certain adsorbability, so that the MXene cannot achieve an ideal ion fast migration effect when being used alone.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a CoTe2the/MXene composite material. It is another object of the present invention to provide the CoTe2A preparation method of/MXene composite material. Further, the present invention provides a CoTe2Application of/MXene composite material and application of CoTe2the/MXene composite material is applied to the negative electrode of the potassium ion battery.
The invention adopts the following technical scheme:
CoTe2The preparation method of the/MXene composite material comprises the following steps:
(1) adding MXene material into dispersant to prepare dispersion with concentration of 1-10mg/ml, preferably 1-8mg/ml, more preferably 3-9mg/ml, and further preferably 4-6mg/ml, and stirring for 2-6h, such as 2h, 3h, 4h, 5h, and 6 h;
(2) adding a cobalt source and a reducing agent into the dispersion liquid obtained in the step (1), and stirring for 3-12 hours, such as 6 hours, 8 hours, 10 hours and 12 hours;
(3) transferring the dispersion liquid obtained in the step (2) into a reaction kettle, putting the reaction kettle into an oven, heating to 80-220 ℃, for example 80 ℃, 100 ℃, 140 ℃,200 ℃, reacting for 8-24 hours, for example 8 hours, 12 hours, 14 hours, 20 hours and 24 hours, and naturally cooling to room temperature;
(4) centrifuging the product obtained in the step (3), and thoroughly cleaning the product by using a cleaning agent;
(5) putting the product obtained in the step (4) into a vacuum drying oven for drying to obtain a precursor Co (OH)2/MXene;
(6) The precursor Co (OH) obtained in the step (5)2The ratio of/MXene to tellurium source is 1: 1-6, preferably 1: 2-4, and more preferably 1: 3-6 mol ratio, respectively placing the quartz boats in two quartz boats;
(7) placing the quartz boat containing the tellurium source in a tube furnace, wherein the quartz boat containing the tellurium source is placed at the upstream of the tube furnace, introducing protective gas, heating to the temperature of 300-1000 ℃ at the heating rate of 4-6 ℃/min, preferably to the temperature of 400 ℃, 600 ℃, 800 ℃ and 1000 ℃, keeping the temperature for 2-10h, such as 3h, 5h, 8h and 10h, and then naturally cooling to the room temperature;
(8) centrifuging the product obtained in the step (7), thoroughly cleaning with a cleaning agent, and drying in vacuum to obtain CoTe2the/MXene composite material.
Further, MXene, a cobalt source and a reducing agent are mixed according to a molar ratio of 1: 1: 1-5, preferably 1: 1: 1 to 3, and more preferably 1: 1: 3 in a molar ratio.
Further, the cobalt source is CoCl2·6H2O、Co(NO3)2·6H2O、CoSO4·7H2At least one of O.
Further, the tellurium source is at least one of tellurium powder, biphenyl ditellurium and sodium tellurite, wherein the particle size is 80-120 meshes, such as 100 meshes.
Further, MXene is Ti3C2Tx、Ti2CTx、V3C2Tx、Mo3N2TxPreferably Ti3N2TxE.g. V3C2Tx,TxIs a surface functional group-O, -F or-OH.
Further, the reducing agent is urea and NH4F.
Further, the dispersant is at least one of N, N-dimethylformamide, ethanol and ethylene glycol.
Further, the temperature of the dispersion liquid in the step (3) is raised to 80-220 ℃, preferably 120-180 ℃, such as 130 ℃, 150 ℃, 160 ℃ and 180 ℃, and the reaction time is 8-24h, preferably 12-16h, such as 12h, 13h, 14h, 15h and 16h in the reaction kettle.
Further, the protective gas is N2Or Ar at a gas flow rate of 100-300ml/min, such as 100ml/min, 120ml/min, 140ml/min, 160ml/min, 180ml/min, 200ml/min, 220ml/min, 230ml/min, 240ml/min, 260ml/min, 280ml/min, 300 ml/min.
Further, the cleaning agent is at least one of water and ethanol, preferably the product obtained in the step (3) and the step (7) is thoroughly cleaned by deionized water and absolute ethanol, and the product can be alternately cleaned by the deionized water and the absolute ethanol for 2 to 12 times, preferably 3 to 8 times.
Further, the centrifugation rotation speed in the step (4) and the step (8) is 5000-.
Further, the temperature of vacuum drying in step (5) and step (8) is 50-80 ℃, preferably 60 ℃, and the drying time is 6-15h, such as 8h, 10h, 12h, 15h, preferably 10 h; the degree of vacuum does not exceed 130Pa, for example 130Pa, 120Pa, 110Pa, 100Pa, 95 Pa.
Further, the CoTe2CoTe in/MXene composite material2The loading amount is 50 to 150% by weight, preferably 50 to 90% by weight, more preferably 60 to 110% by weight, still more preferably 80 to 130% by weight, still more preferably 90 to 150% by weight.
CoTe2CoTe prepared by preparation method of/MXene composite material2the/MXene composite material.
CoTe2Application of/MXene composite material and application of CoTe2the/MXene composite material is applied to the negative electrode of the potassium ion battery.
The invention has the beneficial effects that:
(1) the invention tellurates transition metal CoTe2Growth on MXene nanosheets, CoTe2Can be grown inThe distance between the layers is enlarged, the MXene nanosheets are prevented from being stacked, and the specific surface area of MXene is increased; the laminated structure of MXene material can provide effective structural support and prevent CoTe2Agglomeration of the material.
(2) CoTe in the invention2The MXene material has a synergistic effect, so that the electrode material and the electrolyte can be fully infiltrated, more active sites and electron conduction channels can be provided, and the transfer and ion adsorption area and the vacancy are larger, so that the composite material can have outstanding performances in the aspects of specific capacity after 100 cycles of circulation, circulation stability and battery capacity. Has important significance for the development and the application of the potassium ion battery.
(3) The composite material has high production efficiency, simple preparation method and low raw material cost, and is suitable for large-scale development and application of potassium ion batteries.
Drawings
FIG. 1 is CoTe in example 12Scanning electron microscope images of the/MXene composite material;
FIG. 2 is CoTe in example 12A cycle performance graph of the potassium ion battery assembled by the Mxene composite material under the current density of 100 mA/g;
FIG. 3 is a graph of the measured cycle performance of a potassium ion battery assembled from MXene materials alone in comparative example 1 at a current density of 100 mA/g;
FIG. 4 is CoTe alone in comparative example 22Material assembly potassium ion battery cycling performance plots measured at a current density of 100 mA/g.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Wherein the materials are commercially available unless otherwise specified;
the Ti3C2TxNanoparticles were purchased from beijing beike science and technology ltd, code BK2020011814, size: 1-5 μm, purity: 99%, product application field: energy storage, catalysis, analytical chemistry, and the like.
The method is a conventional method unless otherwise specified.
The invention provides a CoTe2Method for producing/MXene composite materials, wherein CoTe2See:
synthesizing pattern CoTe _2 superfine nano-rod bundles [ C ] by using a Te nano-rod in-situ template method under the assistance of CTAB (cetyl trimethyl ammonium Bromide);
the Chinese instrument functional material society, the university of Jiangsu, the journal of functional materials, the journal of functional material information, the 2009 Chinese functional material science and technology and industry high-level forum discourse, is described;
the functional materials society of Chinese instruments, the university of Jiangsu, the journal of functional materials information, the instrument materials division of the Chinese instruments and meters society, 2009:799 and 800.
Example 1
CoTe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.1mmol of MXene (Ti) was taken3C2Tx) Adding the mixture into N, N-dimethylformamide to prepare 1mg/ml dispersion, and magnetically stirring for 2 hours;
(2) 0.1mmol of Co (NO)3)2·6H2Adding O and 0.1mmol of urea into the dispersion liquid in the step (1), and stirring for 3 hours;
(3) transferring the dispersion liquid obtained in the step (2) into a reaction kettle with the capacity of 50ml, sealing, placing in an oven, heating to 80 ℃, preserving heat for 8 hours, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 5 minutes under the condition of 5000r/min, and alternately washing filter residue for 3 times by using deionized water and absolute ethyl alcohol;
(5) drying the centrifugal product obtained in the step (4) in a vacuum drying oven at the drying temperature of 60 ℃ for 6 hours to obtain a precursor Co (OH)2/MXene。
(6) 0.1mmol of Co (OH) precursor2Placing the/MXene and 0.2mmol of tellurium powder in two quartz boats respectively;
(7) placing the quartz boat in a tube furnace, wherein the quartz boat with the tellurium powder is placed at the upstream of the tube furnace, introducing high-purity Ar at the flow rate of 100ml/min, heating to 400 ℃ at the heating rate of 4 ℃/min, preserving heat for 2h, and then naturally cooling to room temperature;
(8) centrifuging the product obtained in the step (7) for 5 minutes under the condition of 5000r/min, and alternately washing filter residue for 3 times by using deionized water and absolute ethyl alcohol;
(9) drying the centrifugal product obtained in the step (8) in a vacuum drying oven at the drying temperature of 60 ℃ for 6 hours to finally obtain CoTe2the/MXene composite material.
Mixing CoTe2The mass ratio of the/MXene composite material to the polyvinylidene fluoride and the carbon black is 8: 1: 1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a current collector, and performing vacuum drying and slicing to prepare the potassium ion battery negative plate.
CoTe prepared in this example2The specific surface area of the/MXene composite material is 140.9m2The reversible specific capacity is 345mAh/g after 100 cycles under the current density of 100mA/g, and is pure CoTe23.43 times of (100.7mAh/g), and CoTe in the present example2the/MXene composite material shows good cycling stability and excellent rate performance.
Example 2
CoTe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.2mmol of MXene (Ti) was taken3C2Tx) Adding the mixture into N, N-dimethylformamide to prepare 5mg/ml dispersion, and magnetically stirring for 4 hours;
(2) 0.2mmol of Co (NO)3)2·6H2Adding O and 0.25mmol of urea into the dispersion liquid in the step (1), and stirring for 9 hours;
(3) transferring the dispersion liquid obtained in the step (2) into a reaction kettle with the capacity of 50ml, sealing, placing in an oven, heating to 150 ℃, preserving heat for 15h, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 8 minutes under the condition of 6000r/min, and alternately washing filter residues for 3 times by using deionized water and absolute ethyl alcohol;
(5) drying the centrifugal product obtained in the step (4) in a vacuum drying oven at the drying temperature of 60 ℃ for 10 hours to obtain a precursor Co (OH)2/MXene。
(6) 0.2mmol of Co (OH) precursor2Placing the/MXene and 0.4mmol of tellurium powder in two quartz boats respectively;
(7) placing the quartz boat in a tube furnace, wherein the quartz boat containing tellurium powder is placed at the upstream of the tube furnace, introducing high-purity Ar at the flow rate of 200ml/min, heating to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 6h, and then naturally cooling to room temperature;
(8) centrifuging the product obtained in the step (7) for 8 minutes at 6000r/min, and washing filter residues for 3 times by using deionized water and absolute ethyl alcohol respectively;
(9) drying the centrifugal product obtained in the step (8) in a vacuum drying oven at the drying temperature of 60 ℃ for 10 hours to finally obtain CoTe2the/MXene composite material.
Mixing CoTe2The mass ratio of the/MXene composite material to the polyvinylidene fluoride and the carbon black is 8: 1: 1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a current collector, and performing vacuum drying and slicing to prepare the potassium ion battery negative plate.
CoTe prepared in this example2The specific surface area of the/MXene composite material is 211.9m2The reversible specific capacity is 450mAh/g after 100 cycles under the current density of 100mA/g, and is pure CoTe24.47 times (100.7mAh/g), and CoTe in the present example2the/MXene composite material shows good cycling stability and excellent rate performance.
Example 3
CoTe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.1mmol of MXene (Ti) was taken3C2Tx) Adding the mixture into N, N-dimethylformamide to prepare a dispersion liquid of 10mg/ml, and magnetically stirring the dispersion liquid for 6 hours;
(2) 0.1mmol Co(NO3)2·6H2Adding O and 0.2mmol of urea into the dispersion liquid in the step (1), and stirring for 12 hours;
(3) transferring the dispersion liquid obtained in the step (2) into a reaction kettle with the capacity of 50ml, sealing, placing in an oven, heating to 220 ℃, preserving heat for 24 hours, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 10 minutes under the condition of 8000r/min, and alternately washing filter residue for 3 times by using deionized water and absolute ethyl alcohol;
(5) drying the centrifugal product obtained in the step (4) in a vacuum drying oven at the drying temperature of 60 ℃ for 15 hours to obtain a precursor Co (OH)2/MXene。
(6) 0.1mmol of Co (OH) precursor2Placing the/MXene and 0.44mmol of tellurium powder in two quartz boats respectively;
(7) placing the quartz boat in a tube furnace, wherein the quartz boat with the tellurium powder is placed at the upstream of the tube furnace, introducing high-purity Ar at the flow rate of 300ml/min, heating to 1000 ℃ at the heating rate of 6 ℃/min, preserving heat for 10h, and then naturally cooling to room temperature;
(8) centrifuging the product obtained in the step (7) for 10 minutes at 8000r/min, and washing with deionized water and absolute ethyl alcohol for 3 times respectively;
(9) drying the centrifugal product obtained in the step (8) in a vacuum drying oven at the drying temperature of 60 ℃ for 15 hours to finally obtain CoTe2the/MXene composite material.
Mixing CoTe2The mass ratio of the/MXene composite material to the polyvinylidene fluoride and the carbon black is 8: 1: 1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a current collector, and performing vacuum drying and slicing to prepare the potassium ion battery negative plate.
CoTe prepared in this example2The specific surface area of the/MXene composite material is 197.5m2The reversible specific capacity is 403mAh/g after 100 cycles under the current density of 100mA/g, and is pure CoTe24.01 times (100.7mAh/g), and CoTe in the present example2the/MXene composite material shows good circulation stabilityGood performance and excellent rate performance.
Comparative example 1
Weighing 80mg of MXene material, 10mg of super P and 10mg of polyvinylidene fluoride binder, mixing, adding a small amount of N-methylpyrrolidone, stirring, coating on a copper foil, drying at 90 ℃ for 3 hours, cutting the copper foil into a round shape by using a slicing machine to serve as a working electrode, drying, putting the round shape into an inert atmosphere glove box with oxygen and water contents lower than 0.4ppm, and assembling into a 2032 type button battery by using a metal potassium sheet as a counter electrode and glass fiber as a diaphragm.
FIG. 4 is a graph of the cycle performance of MXene material assembled potassium ion batteries measured at a current density of 100 mA/g. As can be seen from the figure, the MXene material assembled potassium ion battery has good cycling stability in the charging and discharging processes under the current density of 100mA/g, but the specific capacity is smaller and is 61.1mA h/g.
Comparative example 2:
NiTe alone2The preparation method of the material comprises the following steps:
(1) 0.1mmol of Co (NO)3)2·6H2Adding O and 0.1mmol of urea into N, N-dimethylformamide to prepare 1mg/ml of dispersion, and stirring for 3 hours;
(2) transferring the dispersion liquid obtained in the step (1) into a reaction kettle with the capacity of 100ml, sealing, placing in an oven, heating to 80 ℃, preserving heat for 8 hours, and then cooling to room temperature;
(3) centrifuging the product obtained in the step (2) for 5 minutes under the condition of 5000r/min, and washing filter residues for 3 times by using deionized water and absolute ethyl alcohol respectively;
(4) drying the centrifugal product obtained in the step (3) in a vacuum drying oven at the drying temperature of 60 ℃ for 6 hours to obtain a precursor Co (OH)2/MXene。
(5) 0.1mmol of Co (OH) precursor2Placing the/MXene and 0.2mmol of tellurium powder in two quartz boats respectively;
(6) placing the quartz boat in a tube furnace, wherein the quartz boat with the tellurium powder is placed at the upstream of the tube furnace, introducing high-purity Ar at the flow rate of 100ml/min, heating to 400 ℃ at the heating rate of 4 ℃/min, preserving heat for 2h, and then naturally cooling to room temperature;
(7) centrifuging the product obtained in the step (6) for 5 minutes under the condition of 5000r/min, and washing with deionized water and absolute ethyl alcohol for 3 times respectively;
(8) drying the centrifugal product obtained in the step (7) in a vacuum drying oven at the drying temperature of 60 ℃ for 6 hours to finally obtain CoTe2the/MXene composite material.
Pure CoTe2The material, polyvinylidene fluoride and carbon black are mixed according to the mass ratio of 8: 1: 1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a current collector, and preparing the potassium ion battery negative pole piece after vacuum drying and slicing.
CoTe prepared in this comparative example2The specific surface area of the material is 45.6m2Per g, 100 cycles at a current density of 100mA/g, a reversible capacity of 100.7mAh/g
Subjecting each group of materials to specific surface area, CoTe2The test method for the load capacity and the specific capacity after 100 cycles comprises the following steps:
BET specific surface area test method for specific surface area, CoTe2The specific capacity after 100 cycles is shown in each specific example. See table 1 for the results of the performance tests of each group.
Table 1: performance testing
Figure BDA0002628841480000081
FIG. 1 is CoTe in example 12Scanning electron microscope images of the/MXene composite material. As can be seen from FIG. 1, there are some CoTe2The nano particles are uniformly grown on the surface of the MXene material, and some CoTe is also existed2The nano particles uniformly grow between the lamella and at the edge, have no agglomeration phenomenon, and present an accordion-shaped layered structure with one closed end and one open end. CoTe2The growth distribution of (2) can enlarge the distance between the sheets and the specific surface area; the laminated structure of MXene material can provide effective structural support and prevent CoTe2Agglomeration of the material.
FIG. 3 is a graph of the measured cycle performance of a potassium ion battery assembled from MXene materials alone in comparative example 1 at a current density of 100 mA/g; as can be seen, the MXene material has good cycling stability, but the specific capacity is small, which is caused by the small interlayer distance of the MXene material itself.
FIG. 4 is CoTe alone in comparative example 22Material assembly potassium ion battery cycling performance plots measured at a current density of 100 mA/g. As can be seen, CoTe alone2The material has certain potassium storage capacity, but the specific capacity is reduced quickly due to easy agglomeration in the charging and discharging processes, and the cycle performance is unstable.
FIG. 2 is CoTe in example 12A cycle performance graph of the potassium ion battery assembled by the Mxene composite material under the current density of 100 mA/g; in contrast to FIGS. 3-4, CoTe2the/MXene composite material shows high battery capacity and good cycle performance. This is because the transition metal telluride CoTe2Growth on MXene nanosheets, CoTe2The growth distribution of the MXene nano-film can enlarge the distance between the sheet layers, prevent the MXene nano-films from stacking and increase the specific surface area of the MXene; the laminated structure of MXene material can provide effective structural support and prevent CoTe2Agglomeration of the material. The two interact, which is beneficial to the full infiltration between the electrode material and the electrolyte, can provide more active sites and electron conduction channels, and larger transfer and ion adsorption areas and vacancies, so that the composite material can have outstanding performance in the aspects of specific capacity after 100 cycles of circulation, circulation stability and battery capacity. Has important significance for the development and the application of the potassium ion battery.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.

Claims (10)

1. CoTe2The preparation method of the/MXene composite material is characterized by comprising the following preparation steps:
(1) adding MXene material into dispersant to prepare dispersion liquid with concentration of 1-10 mg/ml;
(2) mixing a cobalt source and a reducing agent according to a molar ratio of 1: adding the mixture into the dispersion liquid obtained in the step (1) in a ratio of 1-5, and stirring and dissolving to obtain a mixed liquid;
(3) heating the mixed solution in the step (2) to 80-220 ℃, reacting for 8-24h, cooling, centrifuging, washing and drying to obtain a precursor Co (OH)2/MXene;
(4) The precursor Co (OH) in the step (3)2The mol ratio of/MXene to tellurium source is 1: 1-6, respectively placing the quartz boats in the two quartz boats, heating to 1000 ℃ in a nitrogen atmosphere, preserving heat for 2-10h, and cooling to obtain a crude product;
(5) centrifuging, washing and drying the crude product obtained in the step (4) to obtain CoTe2the/MXene composite material.
2. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the MXene is Ti3C2Tx、Ti2CTx、V3C2Tx、Mo3N2TxAt least one of (1).
3. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the cobalt source is CoCl2·6H2O、Co(NO3)2·6H2O、CoSO4·7H2And O, preferably, the tellurium source is at least one of tellurium powder, biphenyl ditellurium and sodium tellurite.
4. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the reducing agent is urea and NH4At least one of F; preferably, the cleaning agent is at least one of water and ethanol.
5. The method of claim 1CoTe2The preparation method of the/MXene composite material is characterized in that the CoTe is2CoTe in/MXene composite material2The loading amount is 50-150 wt%.
6. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the dispersing agent is at least one of N, N-dimethylformamide, ethanol and glycol.
7. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the protective gas is N2Or Ar, the gas flow rate is 100-300 ml/min.
8. CoTe according to claim 12The preparation method of the/MXene composite material is characterized in that the temperature of vacuum drying in the step (3) and the step (5) is 50-80 ℃, the drying time is 6-15h, and the vacuum degree is not more than 130 Pa.
9. CoTe produced by the production method according to any one of claims 1 to 82the/MXene composite material.
10. A potassium ion battery negative electrode comprising the CoTe according to claim 92the/MXene composite material.
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