CN113745474B - PANI @ CN/SnS lithium ion battery negative electrode material and preparation method thereof - Google Patents

PANI @ CN/SnS lithium ion battery negative electrode material and preparation method thereof Download PDF

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CN113745474B
CN113745474B CN202110929731.4A CN202110929731A CN113745474B CN 113745474 B CN113745474 B CN 113745474B CN 202110929731 A CN202110929731 A CN 202110929731A CN 113745474 B CN113745474 B CN 113745474B
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lithium ion
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CN113745474A (en
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侯朝辉
罗佳
尹红
王溦
陈梁
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Hunan Institute of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly discloses a PANI @ CN/SnS lithium ion battery cathode material and a preparation method thereof 3 N 4 The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of the carbon element is 30-40%. The PANI @ CN/SnS lithium ion battery cathode material has excellent electrochemical performance, the specific capacity of the material can still maintain about 760mAh/g after being circulated for 100 circles under the current density of 200mA/g, and the preparation method is simple and easy to implement and is suitable for popularization and application.

Description

PANI @ CN/SnS lithium ion battery negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a PANI @ CN/SnS lithium ion battery negative electrode material and a preparation method thereof.
Background
Lithium ion batteries have attracted attention in recent years as secondary rechargeable batteries because of their high energy density, wide operating voltage range, long operating life, and environmental friendliness. The synthetic elements of SnS are abundant in storage on earth, and are non-toxic and low in cost. Due to its great potential in batteries, it has received increasing attention as an energy storage material in the last decades. Due to its unique 2D layered structure and semiconductor properties, snS materials typically have excellent chemical stability and high theoretical specific capacity and reversibility. As a promising matrix material for storing different alkali metal ions through alloying/dealloying reactions, snS has broad electrochemical prospects in batteries. However, the volume expansion of tin-based sulfides during ion deintercalation can lead to poor cycling stability of the battery, which limits its development as a negative electrode material for lithium ion batteries.
g-C 3 N 4 Is composed of a structural unit triazine ring (C) 3 N 3 ) The structure of the graphite-like laminated planar structure formed by N connection has particularity, and g-C is carried out under the high temperature condition of more than 550 DEG C 3 N 4 Can be cracked to generate a porous structure, has large surface area, can be used as a soft template and shortens the path for the diffusion of ions and electrons. Chinese patent CN109286009A discloses a preparation method of a nanosheet self-assembled three-dimensional nanoflower tin sulfide/graphitized carbon nitride lithium ion battery cathode material, and g C coated on the surface of stannous sulfide in the prepared lithium ion battery cathode material 3 N 4 Can relieve SnS 2 Volume change during charging and discharging. Chinese patent document CN110311119A discloses a preparation method of a negative electrode material SnS/ND-CN of a lithium ion battery, the SnS/ND-CN prepared by the method realizes SnS nanocrystallization, and the SnS/ND-CN with a nano sheet structure is formed, has a larger specific surface area, increases the contact chance and the reaction active site with an electrolyte, is beneficial to the migration of lithium ions, and relieves the volume change in the charge and discharge process.
However, CN-SnS as negative electrode material of lithium ion battery, g-C 3 N 4 The conductivity of the tin-based sulfide is slightly weak, and the tin-based sulfide still has larger volume strain, so that the cycling stability of the lithium ion battery is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PANI @ CN/SnS lithium ion battery cathode material and a preparation method thereof, wherein high-conductivity polyaniline is coated on C 3 N 4 SnS electrode material surface, intended to solve the existing C 3 N 4 SnS electrode material due to g-C 3 N 4 Poor conductivity and poor electrochemical performance of the battery caused by large volume expansion of SnS in the charge and discharge processes.
In order to realize the purpose, the invention provides a PANI @ CN/SnS lithium ion battery anode material which comprises SnS and g-C 3 N 4 The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode materialIn the carbon element, the mass fraction of the carbon element is 30-40%.
According to another aspect of the invention, the invention also provides a preparation method of the PANI @ CN/SnS lithium ion battery cathode material, which comprises the following steps:
s1, preparation g-C 3 N 4 ；
S2, mixing the g-C prepared in the step S1 3 N 4 Directly mixing and stirring the polyaniline and a tin source and a sulfur source for reaction, and then adding protonic acid, an aniline monomer and an initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Preferably, in step S1, g-C is prepared 3 N 4 The specific process is as follows: heating the raw materials to 500-600 ℃ at a heating rate of 3-5 ℃/min, and calcining for 2-4 h to obtain g-C 3 N 4 (ii) a Wherein the raw material is at least one of dicyandiamide, urea, melamine and thiourea.
Preferably, in step S2, the sulfur source is at least one of thioacetamide and thiourea.
Preferably, in the step S2, the Sn source and the S source are mixed according to the molar ratio of the Sn element to the S element of 1 (1-2).
Preferably, in step S2, the protonic acid is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate, and hydrogen peroxide.
Preferably, the protonic acid is hydrochloric acid, the initiator is ammonium persulfate, and the molar ratio of the hydrochloric acid to the aniline monomer to the ammonium persulfate is (1-1.5): 1 (1-3).
Preferably, in step S2, the temperature during the synthesis of polyaniline is controlled below 5 ℃, and the reaction time is 10h-14h.
Preferably, in the step S3, the PANI @ CN/SnS precursor is heated and insulated for 10h-12h in an oil bath, and the temperature of the oil bath is 60-85 ℃.
Preferably, in the step S3, the protective atmosphere is argon-hydrogen mixed gas, and the high-temperature carbonization process is performed at a temperature rise rate of 5 ℃/min to 10 ℃/min, and after the temperature is raised to 700 ℃ to 900 ℃, the temperature is maintained for 2h to 4h.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) The invention coats C by using polyaniline with high conductivity as a carbon layer 3 N 4 The negative electrode material of the lithium ion battery is obtained by the SnS compound, the volume expansion of the material in the SnS charge and discharge process can be effectively relieved by the porous lamellar structure of the material, more active sites are exposed, and the transmission path of ions and electrons is shortened, so that the material has higher specific capacity and excellent cycling stability, the specific capacity can still be maintained at about 760mAh/g after being cycled for 100 circles under the current density of 200mA/g, and the material has important reference value for the practical application of lithium ion energy storage equipment with excellent electrochemical performance.
(2) At present, g-C is generally 3 N 4 Preparing C with a tin source and a sulfur source by a hydrothermal method 3 N 4 SnS complex, but the hydrothermal method requires high temperature and pressure steps, making it more dependent on production equipment; and the hydrothermal method has poor experimental repeatability and is not convenient to be amplified into batch experiments due to the lack of deep research on the control of influencing factors in the crystal nucleus forming process and the crystal growth process of the hydrothermal method. The method utilizes the one-step method of solution to prepare the high-conductivity PANI-coated C in situ 3 N 4 The SnS electrode material has the advantages of simple operation steps, good repeatability, high yield of the obtained product, uniform dispersion of components and excellent electrochemical performance.
(3) The preparation method has the advantages of abundant available synthetic raw materials, no strict limitation, no pollution, simple equipment, low energy consumption and low cost.
(4) The preparation method of the invention strictly controls the concentration of reactants for polyaniline polymerization and the reaction temperature to be C 3 N 4 And a polyaniline carbon layer with uniform shape and high conductivity is formed on the surface of the SnS composite, so that the performance of the battery cathode material is improved.
Drawings
FIG. 1 is a process flow diagram for preparing a PANI @ CN/SnS lithium ion battery anode material according to the present invention;
FIG. 2 is an SEM image of the cathode material of the PANI @ CN/SnS lithium ion battery prepared in example 1 of the present invention under the scale of 500 nm;
FIG. 3 is an SEM image of the cathode material of the PANI @ CN/SnS lithium ion battery prepared in example 1 of the present invention under the scale of 200 nm;
FIG. 4 is an X-ray diffraction pattern of the negative electrode material of PANI @ CN/SnS lithium ion battery prepared in example 1 of the present invention;
FIG. 5 is a charge-discharge curve diagram of the cathode material of PANI @ CN/SnS lithium ion battery prepared in example 1 of the present invention;
FIG. 6 is a cycle performance diagram of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a PANI @ CN/SnS lithium ion battery cathode material which comprises SnS and g-C 3 N 4 The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of carbon element is 30-40%.
Polyaniline (PANI) has the characteristics of high specific capacity, good redox reversibility, high conductivity, simple synthesis method, low cost and the like, and is used as C 3 N 4 The coated carbon layer of the SnS precursor can improve the electrode conductivity and well relieve the volume expansion of SnS in the charge-discharge reaction process. g-C 3 N 4 And in combination with the polyaniline carbon layer, nitrogen atoms can be doped in the PANI crystal lattice, and the nitrogen-doped carbon matrix can further reduce the energy barrier of lithium ion penetration and promote the rapid diffusion of lithium ions and electrons. Meanwhile, the polyaniline carbon layer can form a C-S-C heterocyclic configuration with SnS, so that the material is improvedReaction kinetics of the charge.
By utilizing thermogravimetric analysis and battery performance tests, a large number of experiments prove that if the content of carbon in the negative electrode material is too high, the specific discharge capacity of the material is low; if the content of the carbon element is too low, the capacity fading is fast. The PANI @ CN/SnS lithium ion battery cathode material provided by the invention has excellent electrochemical performance, and the specific capacity of the PANI @ CN/SnS lithium ion battery cathode material can still maintain about 760mAh/g after being cycled for 100 circles under the current density of 200 mA/g.
As shown in FIG. 1, the preparation method of the PANI @ CN/SnS lithium ion battery anode material provided by the invention comprises the following steps:
s1, preparation of g-C 3 N 4 ；
S2, mixing g-C prepared in the step S1 3 N 4 Directly mixing and stirring the polyaniline and a tin source and a sulfur source for reaction, and then adding protonic acid, an aniline monomer and an initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
In some embodiments, step S1 employs a calcination process to prepare g-C 3 N 4 The preparation raw materials can be selected from various nitrogen-rich precursors, and the method has the characteristics of short process flow, less used equipment, low requirement on equipment, short preparation time and the like. The raw material can be at least one of dicyandiamide, urea, melamine and thiourea. The specific preparation process comprises heating the raw materials to 500-600 deg.C at a heating rate of 3-5 deg.C/min, calcining for 2-4 h, and naturally cooling to room temperature to obtain g-C 3 N 4 。
In some embodiments, in step S2, the tin source may be stannous chloride dihydrate, and the sulfur source may be at least one of thioacetamide and thiourea. The tin source and the sulfur source are mixed according to the molar ratio 1 (1-2) of the Sn element to the S element.
The invention adopts a chemical oxidative polymerization method to synthesize polyaniline, and uses an initiator to perform oxidative polymerization on aniline monomers under an acidic condition. Protonic acids effecting oxidative polymerization of anilinesImportant factors, on the one hand, providing the desired pH of the reaction medium; on the other hand, the polyaniline skeleton is given a certain conductivity in the form of a dopant. The polymerization is carried out simultaneously with in-situ doping, and the polymerization and doping are completed simultaneously. The synthesis reaction is influenced by the type and concentration of protonic acid, the type and concentration of initiator, the concentration of aniline monomer, the reaction temperature, the reaction time and other factors. The protonic acid used for synthesizing polyaniline is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate and hydrogen peroxide, so that the reaction temperature is controlled to be C 3 N 4 The surface of the SnS compound is used for synthesizing polyaniline more uniformly, and a surfactant can be added in the synthesis process, wherein the surfactant can adopt at least one of polyvinylpyrrolidone (PVP), dodecylbenzene sulfonic acid (DBSA) and sodium dodecylbenzene sulfonate (SDBS). Because the polyaniline of the coating layer is synthesized in situ in the cathode material, the reaction environment is complicated, and the method is used for preparing the polyaniline in C 3 N 4 The method has the advantages that a polyaniline carbon skeleton with uniform shape, high conductivity and stable hollow structure is formed on the surface of the SnS compound, a large number of experiments are carried out, the preferred embodiment is screened out, the protonic acid is hydrochloric acid, the initiator is ammonium persulfate, and the molar ratio of the hydrochloric acid to aniline monomer to the ammonium persulfate is (1-1.5) to 1 (1-3); the temperature is controlled below 5 ℃ in the synthesis process, and the reaction time is 10-14 h. If the reaction temperature is too high, side reactions during the production of polyaniline may increase, and more by-products may be produced.
In some embodiments, in step S3, the PANI @ CN/SnS precursor is heated and kept in an oil bath for 10h-12h, and the temperature of the oil bath is 60 ℃ to 85 ℃. The oil bath makes PANI @ CN/SnS precursor be heated more evenly, can not produce steam in the heating process, is favorable to SnS better crystallization. The protective atmosphere in the carbonization process is argon-hydrogen mixed gas, the temperature is raised to 700-900 ℃ at the temperature raising rate of 5-10 ℃/min, and then the temperature is kept for 2-4 h. Ar/H 2 The carbon skeleton with uniform appearance and large specific surface area can be obtained by controlling proper carbonization temperature in the reducing atmosphere of gas, and the electrical property and specific capacity of the battery cathode material can be effectively improved by carbonization treatment.
The above technical solution is described in detail below with reference to specific examples.
Example 1
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C 3 N 4 the preparation of (1): heating urea to 550 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to room temperature to obtain g-C 3 N 4 。
(2) Preparation of PANI @ CN/SnS precursor: adding 0.5mmol g-C to 50mL of ethanol 3 N 4 Ultrasonic dispersing, then adding 1mmol SnCl 2 ·2H 2 And performing O ultrasonic treatment for 2h, then adding 1mmol thioacetamide, and stirring for reaction for 2h. Adding 0.1mmol PVP, 0.5mmol hydrochloric acid and 0.5mmol aniline monomer into the original system, slowly adding 0.5mmol ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 12h to obtain a PANI @ CN/SnS precursor.
(3) Preparing the cathode material of the PANI @ CN/SnS lithium ion battery: and (3) directly stirring the polymerized system prepared in the step (2) in an oil bath kettle at 65 ℃ for reaction for 12 hours. Then placed in a tube furnace at Ar/H 2 And (3) heating to 800 ℃ at the heating rate of 5 ℃/min in the gas atmosphere, calcining at the constant temperature for 2h, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
The PANI @ CN/SnS lithium ion battery cathode material prepared in the embodiment is observed by using a scanning electron microscope, and as can be seen from figures 2 and 3, the whole material is of a lamellar structure, and holes are visible on the surface. The lamellar structure can provide convenience for lithium ion de-intercalation and can relieve volume expansion in the SnS charge-discharge process; the surface defects expose more active sites, and shorten the transmission path of ions and electrons, so that the material as a lithium ion negative electrode shows excellent electrochemical performance. An X-ray diffraction pattern (XRD) is shown in figure 4, and the lithium ion battery cathode material has obvious characteristic peaks of SnS besides obvious carbon peaks, which indicates that the carbon layer successfully coats SnS.
Electrochemical tests are carried out on the lithium ion battery cathode material of the embodiment, as can be seen from fig. 5, the charge and discharge curves of the cycle 2 nd circle and the cycle 10 th circle almost coincide, which indicates that the electrode has high reversibility; as can be seen from FIG. 6, under the current density of 200mA/g, the specific discharge capacity of the PANI @ CN/SnS electrode is maintained to be stable, and after 100 cycles, 760mAh/g can be maintained.
Example 2
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C 3 N 4 the preparation of (1): heating melamine to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation and calcination for 4h, and naturally cooling to room temperature to obtain g-C 3 N 4 。
(2) Preparation of PANI @ CN/SnS precursor: adding 0.5 mmol-C into 50mL of ethanol 3 N 4 Ultrasonic dispersing, adding 1mmol SnCl 2 ·2H 2 Performing O ultrasonic treatment for 2 hours, then adding 1.5mmol of thioacetamide, and stirring for reaction for 2 hours. Adding 0.75mmol of hydrochloric acid and 0.5mmol of aniline monomer into the original system, then slowly adding 1mmol of ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 10 hours to obtain a PANI @ CN/SnS precursor.
(3) Step (3) of this example is the same as step (3) of example 1.
Through detection, the PANI @ CN/SnS lithium ion battery negative electrode material prepared by the embodiment has excellent electrochemical performance, the cycle is 100 times under the current density of 200mA/g, and the discharge capacity of the PANI @ CN/SnS lithium ion battery negative electrode material is maintained at 760mAh/g.
Example 3
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C 3 N 4 the preparation of (1): heating thiourea to 600 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to room temperature to obtain g-C 3 N 4 。
(2) Step (2) of this example is the same as step (2) of example 1;
(3) Preparing the cathode material of the PANI @ CN/SnS lithium ion battery: and (3) directly stirring the polymerized system prepared in the step (2) in a 75 ℃ oil bath for reaction for 10 hours. Then placed in a tube furnace at Ar/H 2 In air atmosphere at 10 ℃And (3) heating to 800 ℃ at a min heating rate, calcining for 3h at a constant temperature, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Through detection, the PANI @ CN/SnS lithium ion battery cathode material prepared by the embodiment has excellent electrochemical performance, the cycle is 100 times under the current density of 200mA/g, and the discharge capacity of the PANI @ CN/SnS lithium ion battery cathode material is maintained at 758mAh/g.
Example 4
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C 3 N 4 the preparation of (1): step (1) of this example is the same as step (1) of example 1.
(2) Preparation of PANI @ CN/SnS precursor: adding 0.5mmol g-C to 50mL of ethanol 3 N 4 Ultrasonic dispersing, then adding 1mmol SnCl 2 ·2H 2 And performing O ultrasonic treatment for 1h, then adding 2mmol thioacetamide, and stirring for reaction for 2h. And adding 0.1mmol of PVP, 0.5mmol of hydrochloric acid and 0.5mmol of aniline monomer into the original system, slowly adding 1.5mmol of ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 14 hours to obtain a PANI @ CN/SnS precursor.
(3) Preparing the cathode material of the PANI @ CN/SnS lithium ion battery: and (3) directly stirring the polymerized system prepared in the step (2) in an oil bath kettle at 65 ℃ for reaction for 12 hours. Then placed in a tube furnace at Ar/H 2 Heating to 700 ℃ at a heating rate of 8 ℃/min in a gas atmosphere, calcining at a constant temperature for 4h, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Through detection, the PANI @ CN/SnS lithium ion battery cathode material prepared by the embodiment has excellent electrochemical performance, the cycle is 100 circles under the current density of 200mA/g, and the discharge capacity of the PANI @ CN/SnS lithium ion battery cathode material is maintained at 778mAh/g.
The embodiments show that the PANI @ CN/SnS lithium ion battery cathode material prepared by the invention has excellent electrochemical performance, high specific capacity and good cycling stability.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The utility model provides a PANI @ CN/SnS lithium ion battery cathode material which characterized in that: comprising SnS and g-C 3 N 4 The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the cathode material, the mass fraction of carbon element is 30-40%;
the preparation method of the PANI @ CN/SnS lithium ion battery negative electrode material comprises the following steps:
s1, preparation of g-C 3 N 4 ；
S2, mixing the g-C prepared in the step S1 3 N 4 Directly mixing and stirring the polyaniline and a tin source and a sulfur source for reaction, and then adding protonic acid, an aniline monomer and an initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
2. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein in step S1, g-C is prepared 3 N 4 The specific process is as follows: heating the raw materials to 500-600 ℃ at a heating rate of 3-5 ℃/min, and calcining for 2-4 h to obtain g-C 3 N 4 (ii) a Wherein the raw material is at least one of dicyandiamide, urea, melamine and thiourea.
3. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in step S2, the sulfur source is at least one of thioacetamide and thiourea.
4. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in the step S2, the tin source and the sulfur source are mixed according to the molar ratio of the Sn element to the S element of 1 (1-2).
5. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in step S2, the protonic acid is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate, and hydrogen peroxide.
6. The PANI @ CN/SnS lithium ion battery anode material of claim 5, wherein: the protonic acid is hydrochloric acid, the initiator is ammonium persulfate, and the molar ratio of the hydrochloric acid to aniline monomer to the ammonium persulfate is (1-1.5) to 1 (1-3).
7. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in the step S2, the temperature is controlled below 5 ℃ in the process of synthesizing the polyaniline, and the reaction time is 10-14 h.
8. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in the step S3, the PANI @ CN/SnS precursor is heated and insulated for 10h-12h in an oil bath, and the temperature of the oil bath is 60 ℃ to 85 ℃.
9. The PANI @ CN/SnS lithium ion battery anode material of claim 1, wherein: in the step S3, the protective atmosphere is argon-hydrogen mixed gas, and the high-temperature carbonization process is performed for 2-4 h at a constant temperature after the temperature is increased to 700-900 ℃ at a temperature increase rate of 5-10 ℃/min.
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