CN112018357A - Electrode composite material - Google Patents

Electrode composite material Download PDF

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Publication number
CN112018357A
CN112018357A CN202010826513.3A CN202010826513A CN112018357A CN 112018357 A CN112018357 A CN 112018357A CN 202010826513 A CN202010826513 A CN 202010826513A CN 112018357 A CN112018357 A CN 112018357A
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composite material
sns
electrode composite
mxene
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张业龙
孙宏阳
周健文
徐晓丹
刘争
曾庆光
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Wuyi University
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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
    • H01M4/362—Composites
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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 discloses an electrode composite material, and the preparation method comprises the following steps: adding MXene material into dispersant, stirring for 1-10 hr to obtain 0.5-200mg/ml dispersion; adding a sulfur source material and a tin source material into the dispersion liquid, and stirring for 1-5 hours to obtain a mixed liquid; heating the mixed solution to 140 ℃ and 200 ℃, preserving the heat for 10-15 hours, cooling, centrifuging, washing and drying to obtain SnS2a/MXene composite; SnS2Respectively placing the/MXene composite material and the selenium source material in a protective atmosphere, heating to 600 ℃ at a heating speed of 3-5 ℃/min, preserving heat for 2-8 hours, cooling, and collecting to obtain the electrode composite material. The composite material is prepared by mixing SnSxSe2‑xNano meterThe sheet is anchored on MXene surface and passes through the pair SnSxSe2‑xAnd (5) S: the optimization of Se proportion realizes the SnSxSe2‑xAnd the excellent potassium storage performance is finally obtained by regulating and controlling the concentration of the middle anion vacancy.

Description

Electrode composite material
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to an electrode composite material and a preparation method thereof.
Background
Electrochemical energy storage devices have received a great deal of attention over the past few decades. Among them, Lithium Ion Batteries (LIBs) have been dominating in the rechargeable battery market in the fields of portable electronic devices, electric vehicles, and smart grids since their first commercialization in 1991. However, since it is difficult to reduce the cost of the battery due to scarcity and distribution unevenness of lithium in the earth's crust, development of a new generation of low-cost energy storage device is urgently required. The secondary battery based on potassium ions has a similar energy storage mechanism to the lithium ion secondary battery, and has abundant earth resources and low cost, so the secondary battery is particularly concerned by people. However, as an emerging system, there are many problems, such as a suitable positive electrode material and a suitable negative electrode material for accommodating potassium ions, an electrolyte system, and the like, wherein the negative electrode material as an important component of the battery greatly limits the practical application of the potassium ion battery, and therefore, research on the negative electrode material of the potassium ion battery needs to be further advanced.
MXene is a molecular formula of Mn+1XnTxWherein M represents a transition metal (Ti, V, Mo, etc.), X represents carbon and/or nitrogen (n ═ 1, 2, or 3), and T represents a functional group such as-O, -OH, -F, etc. MXene has a unique two-dimensional layered structure and abundant surface functional groups, so that the MXene shows the conductivity, good hydrophilicity and mechanical stability of metalloid, and has good application prospects in the fields of electrochemical energy storage, electromagnetic shielding, electrocatalysis, pressure sensors and the like, but the interlayer spacing is small, and the surface functional groups have certain adsorbability, so that an ideal ion rapid migration effect cannot be achieved when the MXene is used alone. SnS2Because of the unique phase transformation and alloying reaction, the potassium-storing alloy has extremely high potassium-storing performance; however, SnS2The high capacity characteristic of (a) is subject to a large volume change in the potassium ion intercalation and deintercalation process. Albeit with SnS2Anchored on the MXene surface and can utilize the high conductivity of MXeneMis mitigation2Volume change per se, but SnS2The semiconductor properties themselves are still not conducive to high performance potassium storage.
Disclosure of Invention
In view of the problems of the current potassium ion battery cathode materials, one of the objectives of the present invention is to provide an electrode composite material. The invention also aims to provide a preparation method of the electrode composite material. Further, the invention provides application of the electrode composite material, and the electrode composite material is used as a negative electrode of a potassium ion battery.
The invention adopts the following technical scheme:
a preparation method of an electrode composite material comprises the following steps:
(1) adding MXene material into dispersant, stirring for 1-10 hr, preferably 8 hr, to obtain 0.5-200mg/ml dispersion, such as 0.5-5mg/ml, 0.8-12mg/ml, and 1.2-15 mg/ml;
(2) adding a sulfur source material and a tin source material into the dispersion liquid in the step (1) according to a certain molar ratio, wherein the molar ratio is (2-5): 1, preferably 2.5:1, and stirring for 1-5 hours, preferably 3 hours to obtain a mixed solution;
(3) transferring the mixed solution into a polytetrafluoroethylene reaction kettle, heating to 140-200 ℃, for example, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, preferably 160 ℃, preserving the heat for 8-24 hours, preferably 12 hours, and then cooling to room temperature;
(4) centrifuging the reaction product obtained in the step (3), discarding the supernatant, and cleaning the filter residue for multiple times by using a cleaning agent;
(5) vacuum drying the product obtained in the step (4) to obtain SnS2a/MXene composite;
(6) SnS2the/MXene composite material and the selenium source material are respectively placed in two corundum boats and transferred into a tube furnace, wherein the selenium source material is positioned at the side of an air inlet, and SnS2the/MXene composite material is positioned at the air outlet side;
(7) heating the tubular furnace to 300-600 ℃ at a heating speed of 3-5 ℃/min under the condition of protective atmosphere, such as 300 ℃, 320 ℃, 340 ℃, 360 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃; preserving the heat for 2 to 8 hours, and naturally cooling to room temperature;
(8) and collecting the corundum ark on the side of the air outlet to obtain the electrode composite material.
Further, MXene is Ti3C2Tx、V3C2Tx、W3N2TxOne or more of (a).
Further, the tin source material is SnCl2、SnCl4、SnCl4·5H2O、SnSO4One or more of (a).
Further, the sulfur source material is one or more of thioacetamide, thiourea and sublimed sulfur.
Further, the selenium source material is one or more of selenium powder, selenium tetrachloride, dimethyl selenium and phenylselenol.
Further, the dispersant is any one or two of ethanol and ethylene glycol, such as ethanol and ethylene glycol, preferably in a mass ratio of 3: 1.
Further, the cleaning agent is any one or two of water and absolute ethyl alcohol; preferably, the filter residue in the step (3) is washed for 3 to 5 times by using deionized water and absolute ethyl alcohol alternately.
Further, the electrode composite material is SnSxSe2-x/MXene, wherein SnSxSe2-xThe loading is 10 to 300 wt%, preferably 50 to 80 wt%.
Further, the temperature of the mixed dispersion in the step (3) is raised to 140-200 ℃, preferably 160 ℃, and the reaction is carried out for 10-15 hours, preferably 12 hours in the reaction kettle.
Further, the rotation speed of the centrifugation in the step (4) is 3000-11000r/min, preferably 4500r/min, and the time is 5-10min, preferably 6 min.
Further, the temperature of vacuum drying in the step (5) is 40-100 ℃, preferably 65 ℃, and the drying time is 8-12 hours, preferably 10 hours; the vacuum degree does not exceed 300 Pa.
Further, the protective atmosphere used in step (7) is either or both of nitrogen and argon, preferably nitrogen.
A potassium ion battery cathode comprises the electrode composite material prepared by the preparation method.
A potassium ion battery includes the above battery negative electrode.
The invention has the beneficial effects that:
(1) the electrode composite material prepared by the invention is prepared by mixing SnSxSe2-xThe nano-sheet is anchored on the MXene surface, thus relieving SnSxSe2-xLarge volume expansion in cyclic process and through SnSxSe2-xMedium Se: s proportion is optimized, and SnS is realizedxSe2-xThe concentration of the middle anion vacancy is regulated and controlled, and the introduction of the anion vacancy can improve SnSxSe2-xIs an alkali metal ion (K)+) The storage of the potassium-enriched potassium salt provides more active sites, and finally, the potassium storage performance is better.
(2) The electrode composite material provided by the invention is combined with a heat treatment method through a solvothermal method, the process difficulty is low, the required equipment is simple, and the electrode composite material is suitable for large-scale application.
Drawings
FIG. 1 shows SnS in comparative example 12Scanning electron micrographs of the material;
FIG. 2 is SnS in comparative example 22Scanning electron microscope images of the/MXene composite material;
FIG. 3 is a scanning electron micrograph of an electrode composite in example 1;
FIG. 4 shows SnS in comparative example 12A cycle performance profile of the material;
FIG. 5 shows SnS in comparative example 22A cycle performance diagram of the/MXene material;
FIG. 6 is a graph of the cycling performance of the electrode composite of example 1.
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.
Wherein the materials are commercially available unless otherwise specified;
the Ti3C2TxThe granules were purchased from beijing beike science and technology ltd, code BK2020011814, sheet stacking thickness: 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.
Specific surface area test: the obtained sample was subjected to N2 adsorption desorption test by an ASAP2460 analyzer and the specific surface area was calculated based on the BET theory.
And (3) testing the battery performance: mixing the prepared negative electrode material with conductive carbon black and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, vacuum drying at 80 ℃, and slicing to obtain the potassium ion battery negative electrode sheet. The negative pole piece, the metal potassium foil and the diaphragm (Whatman, GF/F) are assembled into a 2032 type button cell in a glove box, and a Wuhan blue battery test system is utilized to test the battery performance.
The ratio of each atom: x-ray photoelectron spectroscopy (XPS).
Example 1
A preparation method of an electrode composite material comprises the following steps:
(1) 60mg of MXene (Ti) was taken3C2Tx) Adding into mixed solution of 7.5ml ethylene glycol and 21.5ml ethanol, and magnetically stirring for 8 hr to obtain 2mg/ml dispersion;
(2) 0.25mol of Thioacetamide (TAA) and 0.1mol of SnCl4Adding the dispersion liquid obtained in the step (1), and stirring for 5 hours to obtain a mixed liquid;
(3) transferring the mixed solution into a polytetrafluoroethylene reaction kettle, heating to 160 ℃, preserving heat for 12 hours, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 6min at 4500r/min by using a centrifuge, discarding the supernatant, and alternately cleaning the filter residue for 5 times by using deionized water and absolute ethyl alcohol;
(5) drying the product obtained in the step (4) in a vacuum drying oven at the drying temperature of 65 ℃ for 10 hours to obtain SnS2a/MXene composite;
(6) adding 100mg SnS2the/MXene composite material and 200mg selenium powder are respectively placed in two corundum arks and transferred into a tube furnace, wherein the selenium powder is positioned at the side of an air inlet, and SnS2the/MXene composite material is positioned on the gas outlet side;
(7) heating the tube furnace to 400 ℃ at a heating speed of 5 ℃/min under the condition of nitrogen atmosphere, preserving heat for 3 hours, and naturally cooling;
(8) and collecting the corundum ark on the side of the air outlet to obtain the electrode composite material.
Mixing the electrode composite material, a polyvinylidene fluoride binder and SuperP according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, performing vacuum drying at 70 ℃, and slicing to obtain the potassium ion battery negative electrode piece.
The reversible capacity of the electrode composite material prepared in the embodiment after 200 cycles is 376mAh/g under the current density of 100 mA/g.
Example 2
A preparation method of an electrode composite material comprises the following steps:
(1) 600mg of MXene (Ti) was taken3C2Tx) Adding into a mixed solution of 15ml of ethylene glycol and 43ml of ethanol, and magnetically stirring for 8 hours to prepare a dispersion liquid of 10 mg/ml;
(2) mixing 1.5mol Thioacetamide (TAA) with 0.5mol SnCl4Adding the dispersion liquid obtained in the step (1), and stirring for 6 hours to obtain a mixed liquid;
(3) transferring the mixed solution into a polytetrafluoroethylene reaction kettle, heating to 180 ℃, preserving heat for 8 hours, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 5 minutes by using a centrifuge under the condition of 5500r/min, removing supernatant, and alternately cleaning for 5 times by using deionized water and absolute ethyl alcohol;
(5) subjecting the centrifuged product obtained in step (4) toDrying in a vacuum drying oven at 75 ℃ for 10 hours to obtain SnS2a/MXene composite;
(6) adding 100mg SnS2the/MXene composite material and 400mg of selenium tetrachloride are respectively placed in two corundum arks and transferred into a tube furnace, wherein the selenium powder is positioned at the air inlet side, and SnS2the/MXene composite material is positioned on the gas outlet side;
(7) heating the tube furnace to 600 ℃ at a heating speed of 3 ℃/min under the condition of nitrogen atmosphere, preserving heat for 2 hours, and naturally cooling;
(8) and collecting the corundum ark on the side of the air outlet to obtain the electrode composite material.
Mixing the electrode composite material, a polyvinylidene fluoride binder and SuperP according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, performing vacuum drying at 70 ℃, and slicing to obtain the potassium ion battery negative electrode piece.
The reversible capacity of the electrode composite material prepared in the embodiment after circulation for 200 circles is 306mAh/g under the current density of 100 mA/g.
Example 3
A preparation method of an electrode composite material comprises the following steps:
(1) taking 800mg MXene (Ti)3C2Tx) Adding into mixed solution of 40ml ethylene glycol and 120ml ethanol, magnetically stirring for 6 hr to obtain 5mg/ml dispersion;
(2) 5mol of thiourea and 2mol of SnCl4·5H2Adding O into the dispersion liquid obtained in the step (1), and stirring for 6 hours to obtain a mixed liquid;
(3) transferring the mixed solution into a polytetrafluoroethylene reaction kettle, heating to 140 ℃, preserving heat for 16 hours, and then cooling to room temperature;
(4) centrifuging the product obtained in the step (3) for 4 minutes by using a centrifuge under the condition of 7000r/min, removing supernatant, and alternately cleaning filter residue for 4 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 12 hours to obtain the productTo SnS2a/MXene composite;
(6) adding 100mg SnS2the/MXene composite material and 300mg selenium powder are respectively placed in two corundum arks and transferred into a tube furnace, wherein the selenium powder is positioned at the side of an air inlet, and SnS2the/MXene composite material is positioned on the gas outlet side;
(7) heating the tube furnace to 500 ℃ at a heating speed of 3 ℃/min under the condition of nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling;
(8) and collecting the corundum ark on the side of the air outlet to obtain the electrode composite material.
Mixing the electrode composite material, a polyvinylidene fluoride binder and SuperP according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, performing vacuum drying at 70 ℃, and slicing to obtain the potassium ion battery negative electrode piece.
The reversible capacity of the electrode composite material prepared in the embodiment after 200 cycles is 246mAh/g under the current density of 100 mA/g.
Comparative example 1:
SnS2The preparation method of the material comprises the following steps:
(1) 0.6mol of Thioacetamide (TAA) and 0.2mol of SnCl4·5H2O is added into a mixed solution of 21.5ml of ethanol and 7.5ml of glycol, and the mixture is magnetically stirred for 3 hours;
(2) transferring the mixed dispersion liquid obtained in the step (1) into a stainless steel reaction kettle, heating to 160 ℃, preserving heat for 15 hours, and then cooling to room temperature;
(3) cleaning the target product obtained in the step (3) by using deionized water and absolute ethyl alcohol alternately for 3 times, and then centrifuging the target product for 5 minutes by using a centrifuge under the condition of 7000 r/min;
(4) and (3) drying the centrifugal product obtained in the step (4) in a vacuum drying oven at the temperature of 80 ℃ for 6 hours.
SnS2Mixing the material with a polyvinylidene fluoride binder and SuperP according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, drying in vacuum at 70 ℃, and slicingAnd obtaining the negative pole piece of the potassium ion battery.
SnS made by the embodiment2The reversible capacity of the composite material after circulation for 200 circles is 2.3mAh/g under the current density of 100 mA/g.
Comparative example 2:
SnS2the preparation method of the/MXene material comprises the following steps:
(1) taking 30mg of MXene (Ti)3C2Tx) Adding into a mixed solution of 21.5ml ethanol and 7.5ml ethylene glycol, and magnetically stirring for 8 hours to obtain a 1mg/ml dispersion;
(2) 0.25mol of Thioacetamide (TAA) and 0.1mol of SnCl4Adding the dispersion liquid obtained in the step (1) and stirring for 5 hours;
(3) transferring the mixed dispersion liquid obtained in the step (2) into a polytetrafluoroethylene reaction kettle, heating to 160 ℃, preserving heat for 12 hours, and then cooling to room temperature;
(4) washing the product obtained in the step (3) by using deionized water and absolute ethyl alcohol alternately for 5 times, and then centrifuging for 6 minutes by using a centrifuge under the condition of 4500 r/min;
(5) drying the centrifugal product obtained in the step (4) in a vacuum drying oven at the drying temperature of 65 ℃ for 10 hours to obtain SnS2a/MXene composite;
SnS2Mixing the MXene material, the polyvinylidene fluoride binder and the SuperP according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, performing vacuum drying at 70 ℃, and slicing to obtain the potassium ion battery negative pole piece.
SnS manufactured by this comparative example2The reversible capacity of the/MXene material after 200 cycles is 216mAh/g under the current density of 100 mA/g.
See table 1 for the results of the performance tests of each group.
Table 1: performance testing
Figure BDA0002636390050000071
The inventionPrepared electrode composite material of SnSxSe2-xMaterials synthesis methods please see:
Won J K,Hwang C,Ahn K,et al.Controlled synthesis of SnSxSe2-x nanoplate alloys via synergetic control of reactant activity and surface defect passivation control with surfactant and co-surfactant mixture[J].Journal of Solid State Chemistry,2019.
as can be seen from FIGS. 1-3, SnS2The material is in a large block shape and is obviously agglomerated; SnS2the/MXene composite material is flaky and still partially agglomerated; the electrode composite material prepared by the invention has larger interlayer spacing and no agglomeration phenomenon.
As can be seen from FIGS. 4-6, SnS2The material has a low specific capacity and poor cycling stability, which may be due to SnS2The agglomeration of the material is serious; SnS2Pure SnS of/MXene composite material2The specific capacity and the cycling stability of the material are improved, but the material is still not ideal; the electrode composite material prepared by the invention is prepared by the method of adding SnS2In the presence of Se atom, SnS can be regulated2The electronic structure improves the conductivity, generates more active sites, and shows that the specific capacity is greatly increased, and the cycling stability completely meets the requirements of the potassium ion battery, thereby being beneficial to improving the rate capability and the cycling stability 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. The preparation method of the electrode composite material is characterized by comprising the following steps of:
(1) adding MXene material into dispersant to prepare dispersion liquid with concentration of 0.5-200 mg/ml;
(2) adding a sulfur source material and a tin source material into the dispersion liquid in the step (1), and stirring for 1-5 hours to obtain a mixed liquid;
(3) will be provided withHeating the mixed solution to 140 ℃ and 200 ℃, preserving the heat for 10-15 hours, cooling, centrifuging, washing and drying to obtain SnS2a/MXene composite;
(4) SnS2Respectively placing the MXene composite material and the selenium source material in a protective atmosphere, heating to 600 ℃ at a heating speed of 3-5 ℃/min, preserving heat for 2-8 hours, and cooling;
(5) and collecting to obtain the electrode composite material.
2. The method for preparing the electrode composite material according to claim 1, wherein MXene is Ti3C2Tx、V3C2Tx、W3N2TxOne or more of (a).
3. The method of claim 1, wherein the tin source material is SnCl2、SnCl4、SnCl4·5H2O、SnSO4One or more of; preferably, the sulfur source material is one or more of thioacetamide, thiourea and sublimed sulfur; further preferably, the selenium source material is one or more of selenium powder, selenium tetrachloride, dimethyl selenium and phenylselenol.
4. The method for preparing an electrode composite material according to claim 1, wherein the dispersant is an organic solvent: one or more of dimethylformamide, ethanol and glycol.
5. The method of preparing the electrode composite of claim 1, wherein the electrode composite is SnSxSe2-x/MXene, wherein SnSxSe2-xThe loading amount of the catalyst is 10-300 wt%; preferably, the atomic ratio of S to Se in the electrode composite material is 1 (0.1-10).
6. The method for preparing an electrode composite material as claimed in claim 1, wherein the rotation speed of the centrifugation in the step (3) is 3000-11000r/min, and the time is 5-10 min.
7. The method for preparing an electrode composite material according to claim 1, wherein the drying in the step (3) is vacuum drying at a temperature of 40 to 100 ℃ for 8 to 12 hours under a vacuum of less than 300 Pa.
8. The method for preparing an electrode composite material according to claim 1, wherein the protective atmosphere in the step (4) is either or both of nitrogen and argon.
9. A potassium ion battery negative electrode, characterized in that it comprises an electrode composite obtained by the production method according to any one of claims 1 to 8.
10. A potassium ion battery comprising the battery negative electrode of claim 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114678579A (en) * 2022-03-10 2022-06-28 郑州大学 Lithium-sulfur battery electrolyte containing selenophenol additive and lithium-sulfur battery

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CN108695499A (en) * 2018-05-22 2018-10-23 安徽师范大学 A kind of nanocomposite of the hierarchical structure of controllable epitaxial growth, preparation method and applications
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CN107123800A (en) * 2017-05-20 2017-09-01 西南大学 Ti3C2@SnSx（x=1、2）The preparation method of negative material
CN108695499A (en) * 2018-05-22 2018-10-23 安徽师范大学 A kind of nanocomposite of the hierarchical structure of controllable epitaxial growth, preparation method and applications
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CN114678579A (en) * 2022-03-10 2022-06-28 郑州大学 Lithium-sulfur battery electrolyte containing selenophenol additive and lithium-sulfur battery
CN114678579B (en) * 2022-03-10 2023-05-05 郑州大学 Lithium-sulfur battery electrolyte containing phenylselenol additive and lithium-sulfur battery

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