CN110931731B - Two-dimensional carbide crystal-based antimony sulfide negative electrode material and preparation method and application thereof - Google Patents

Two-dimensional carbide crystal-based antimony sulfide negative electrode material and preparation method and application thereof Download PDF

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CN110931731B
CN110931731B CN201911087891.8A CN201911087891A CN110931731B CN 110931731 B CN110931731 B CN 110931731B CN 201911087891 A CN201911087891 A CN 201911087891A CN 110931731 B CN110931731 B CN 110931731B
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negative electrode
carbide crystal
antimony
antimony sulfide
mxene
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CN110931731A (en
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韩生
马健
胡晓敏
黄燕山
李晓斌
孔玥
李原婷
常宾
高丽
薛原
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Shanghai Institute of Technology
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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/58Selection 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
    • H01M4/5815Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a two-dimensional carbide crystal-based antimony sulfide negative electrode material and a preparation method and application thereof2S3Then the obtained Sb2S3And MXene is mixed and freeze-dried to obtain the two-dimensional carbide crystal-based antimony sulfide negative electrode material. Compared with the prior art, the Sb obtained by the invention2S3Uniformly dispersed on an MXene substrate, and has the advantages of low cost, simple process, mild conditions, high reversible capacity, good cycle stability and rate capability and the like.

Description

Two-dimensional carbide crystal-based antimony sulfide negative electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a two-dimensional carbide crystal-based antimony sulfide negative electrode material, and a preparation method and application thereof.
Background
With the development and progress of the automobile industry, the continuous development problem of human beings faces huge challenges. The combustion of non-renewable fuels can release various exhaust gases, leading to various problems. Therefore, it is important to find renewable and sustainable energy storage devices. The rechargeable battery is economical, environment-friendly, high in power and long in service life, and compared with non-renewable energy, the rechargeable battery realizes continuous utilization of energy. Particularly, the lithium ion battery has the advantages of high energy density, no memory effect, low maintenance cost, low self-discharge and self-discharge effect and the like, and is one of the most promising electrochemical energy storage battery technologies at present. And becomes one of the most important rechargeable batteries.
The lithium ion battery is composed of four most important parts, namely positive and negative electrode materials, electrolyte, a diaphragm and the like. The cathode materials of the lithium ion battery are transition state metal-based inorganic materials (such as cobalt, nickel, manganese and the like) with small earth reserves, and the cathode materials of the materials have the defects of expensive raw materials, poor conductivity and low capacity, and are one of the main bottlenecks in the development of the lithium ion battery. In contrast, sulfur or selenium can alloy in the chalcogenide to form lithium chalcogenide, thereby improving the charging capability of the negative electrode, SnS2、SnSe2、Sb2S3And its carbon composite as a negative electrode material, and thus these electrodes are a combination of a lithium/sulfur cell and an element (whether tin or antimony) that also contributes to the ability of the lithium alloy to charge at lower potentials. However, the cycling stability of emerging high capacity oxide and sulfide electrodes remains a problem, and the lithiation process is accompanied by a large volume change, resulting in film cracking, deterioration of electrical integrity, gradual capacity fade, and shortened lifetime.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a two-dimensional carbide crystal-based antimony sulfide negative electrode material which is low in cost, simple in process, mild in condition, high in reversible capacity, and excellent in cycle stability and rate capability, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a two-dimensional carbide crystal-based antimony sulfide negative electrode material, which is characterized by comprising the following steps of:
(1) adding an antimony source into deionized water, uniformly stirring, adding ethylene glycol, and stirring to obtain a solution A;
(2) adding sodium borohydride into the solution A obtained in the step (1), uniformly stirring, adding polyvinylpyrrolidone, and fully dissolving to obtain a solution B;
(3) adding the solution B obtained in the step (2) into a hydrothermal kettle lining containing sulfur powder for hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished, washing and drying to obtain Sb2S3
(4) Sb2S3Adding the obtained product into MXene solution, performing ultrasonic homogenization and freeze-drying to obtain the two-dimensional carbide crystal-based antimony sulfide negative electrode material.
As a preferable technical scheme of the invention, in the step (1), the antimony source is SbCl3
As a preferable technical scheme of the invention, in the step (1), the ratio of the dosage of the antimony source to the deionized water is 1g: 100-140 mL.
As a preferable technical scheme of the invention, in the step (1), the volume ratio of the ethylene glycol to the deionized water is 0.8-1.2: 1.
As a preferable technical scheme of the invention, in the step (2), since hydrogen is generated through reaction and the reaction is violent, sodium borohydride is slowly added into the solution A obtained in the step (1).
As a preferable technical scheme of the invention, in the step (2), the mass ratio of the sodium borohydride to the antimony source is 1-1.4: 1.
In a preferable embodiment of the present invention, in the step (2), the viscosity average molecular weight of the polyvinylpyrrolidone is 280000 to 320000.
As a preferable technical scheme of the invention, in the step (2), the mass ratio of the polyvinylpyrrolidone to the antimony source is 2.5-3.5: 1.
As a preferable technical scheme of the invention, in the step (3), the mass ratio of the sulfur powder to the antimony source is 1: 2-3.
As the preferable technical scheme of the invention, in the step (3), the sulfur powder is uniformly spread at the bottom of the lining of the hydrothermal kettle.
As a preferable technical scheme of the invention, in the step (3), the temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 10-15 h.
As a preferred technical scheme of the invention, in the step (3), a centrifugal separation mode is adopted for solid-liquid separation, and a method of firstly high speed, then low speed and then high speed is adopted for the rotating speed during centrifugal separation; the high-speed rotating speed is 7000rmp-8000 rmp; the low speed is 2000rmp-3000 rmp.
As a preferred technical scheme of the invention, in the step (3), deionized water is adopted for washing.
As a preferable technical scheme of the invention, in the step (3), drying is carried out in a drying mode.
As a preferable embodiment of the present invention, in the step (4), Sb2S3The mass ratio of MXene to MXene is 1.5-2.5: 1.
As a preferable embodiment of the present invention, in the step (4), Ti3C2、Ti2C、Ta4C3、V2C or Nb2C。
The invention provides a two-dimensional carbide crystal-based antimony sulfide negative electrode material obtained by the preparation method.
As a preferred technical scheme of the invention, antimony sulfide Sb2S3Present as a kind of nanowire rod and evenly distributed on the two-dimensional carbide crystal MXene.
The third aspect of the invention provides the application of the two-dimensional carbide crystal-based antimony sulfide negative electrode material in the aspect of a lithium ion battery negative electrode material.
Two-dimensional carbide crystals (MXene) are a new two-dimensional material, belonging to the transition metal carbon/nitride, the precursor of which is MAX-phase. The MAX-phase is a general term of a series of ternary layered compounds, wherein M represents a transition group metal element, A is a main group element, X is carbon and/or nitrogen in the MAX phase, X atoms are filled into an octahedral structure formed by close stacking of M atoms, and A atoms are positioned between MX layers. In 2011 scientists found that the appearance of MXene is very sandwich-like, and as a new class of two-dimensional materials, MXene, which is a two-dimensional carbide crystal nano material composed of oxide, carbon and metal filler, has good hydrophilicity imparted to MXene by functional groups generated in the MAX-phase etching process, and the conductivity of MXene is not significantly influenced. Therefore, due to the intrinsic two-dimensional nano-layered structure, good hydrophilicity, excellent conductivity and mechanical property of MXene, the Mxene-based material is widely applied to compounding of electrode materials in the fields of energy storage and conversion, and has wide application prospects in various fields such as lithium ion batteries, supercapacitors, photocatalyst electrodes and the like.
The composite material obtained by adding the Mxene has a two-dimensional structure, can improve the originally insufficient circulation stability, and increases the conductivity of the composite material to ensure that the composite material has better electrochemical performance.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares the two-dimensional carbide crystal-based antimony sulfide negative electrode material by a hydrothermal and ultrasonic mixing method, and the Sb obtained after hydrothermal is finished2S3The mixed solution is evenly mixed with MXene solution by ultrasonic, and the method is simple and convenient;
2. the invention takes antimony sulfide, sodium borohydride and the like as raw materials, and the raw materials are designable and have low cost;
3. the two-dimensional carbide crystal-based antimony sulfide negative electrode material prepared by the method has low lithium ion diffusion barrier of Mxene, so that the migration speed of lithium ions in the negative electrode is high, and the charge-discharge speed is high. The single-layer or multi-layer graphene-like large-surface-area nano material obtained by layered MXene stripping can be used as a good carrier for efficient electron transmission and enhanced lithium storage in a battery system, has high reversible capacity and very good circulation stabilityThe sexual and rate capability is 100mA g-1The capacity of the battery can reach 600 mAh.g under charging and discharging current-1At 4A · g-1The lower capacity is 150mAh g-1The excellent rate performance efficiency of the device is stabilized to be more than 90 percent. Has wide application prospect in the field of lithium ion batteries. Provides good experimental data and theoretical support for the research and application of MXene and inorganic materials in the field of electrochemistry.
Drawings
FIG. 1(a) is an SEM topography of the antimony sulfide material obtained in example 1, from which a significant rod-like structure of antimony sulfide nanowires can be seen;
FIG. 1(b) SEM topography of the obtained two-dimensional carbide crystal-based antimony sulfide negative electrode material in example 1, from which it is apparent that antimony sulfide nanowires are uniformly distributed on the two-dimensional carbide crystals;
FIG. 2 is an XRD pattern of the two-dimensional carbide crystal-based antimony sulfide negative electrode material obtained in example 1 as a negative electrode material of a lithium ion battery, and the two-dimensional carbide crystal-based antimony sulfide negative electrode material has an accurate antimony sulfide peak position;
FIG. 3 is a graph of the cycle performance of the two-dimensional carbide crystal-based antimony sulfide negative electrode material and antimony sulfide negative electrode material obtained in example 1 as a lithium ion battery negative electrode material, and it can be seen that the cycle performance is improved after MXene is added;
fig. 4 is a graph of rate performance of the two-dimensional carbide crystal-based antimony sulfide negative electrode material obtained in example 1 and the antimony sulfide negative electrode material as a negative electrode material of a lithium ion battery, and it can be seen that the rate performance is improved after MXene is added.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The preparation method of the two-dimensional carbide crystal-based antimony sulfide negative electrode material comprises the following steps:
step one, preparing an antimony sulfide material:
(1) 0.25g of SbCl3Adding the mixture into 30mL of deionized water and stirring the mixture evenly; then adding 30mL of glycol into the solution and stirring for 10 min;
(2) 0.3g of sodium borohydride was then added(NaBH4) Slowly adding into the solution, stirring, adding 0.75g polyvinylpyrrolidone (PVP) with molecular weight of 300000 into the solution, and dissolving completely;
(3) finally, the solution is poured into a lining of a hydrothermal kettle containing 0.1g of sulfur powder (paved at the bottom of the lining) for hydrothermal reaction, and the temperature is kept at 180 ℃ for 12 hours.
Step two, preparing a two-dimensional carbide crystal-based antimony sulfide negative electrode material:
(1) after hydrothermal treatment, washing solid-liquid separation with deionized water and then drying to obtain Sb2S3Adding the obtained Sb2S3Adding the mixture into MXene solution, performing ultrasonic homogenization, and finally performing freeze-drying to obtain a two-dimensional carbide crystal-based antimony sulfide negative electrode material, wherein the morphology of the two-dimensional carbide crystal-based antimony sulfide negative electrode material is shown in a figure 1(a) and a figure 1 (b);
wherein Sb is added2S3The mass and dosage ratio of the MXene to the MXene is 2: 1. MXene may be Ti3C2、Ti2C、Ta4C3、V2C or Nb2C and the like.
The solid-liquid separation adopts a centrifugal separation mode, and the rotating speed during the centrifugal separation adopts a method of firstly high speed, then low speed and then high speed; the high-speed rotating speed is 7000rmp-8000 rmp; the low speed is 2000rmp-3000 rmp.
(2) The obtained composite material is used as a negative electrode material of a lithium ion battery to assemble a lithium ion button type half battery, the composite material, carbon black (Super-P) and sodium carboxymethyl cellulose (CMC) are mixed according to the weight ratio of 7:2:1, and then the mixture is uniformly coated on pure aluminum foil (99.6%) by a coating method to prepare a negative electrode, and a pure lithium sheet is used as a counter electrode. Electrochemical tests were performed using a button type half cell, and the cycle performance diagram and the rate performance diagram are shown in fig. 3 and fig. 4, respectively. It can be seen that the cycle performance and rate performance are improved after MXene is added.
Example 2
This example is substantially the same as example 1 except that in the first step (1), 25mL of deionized water was added.
Example 3
This example is substantially the same as example 1 except that in the first step (1), 35mL of deionized water was added.
Example 4
This example is substantially the same as example 1 except that in the first step (1), the amount of ethylene glycol added was 24 mL.
Example 5
This example is substantially the same as example 1 except that in the first step (1), the amount of ethylene glycol added was 36 mL.
Example 6
This example is substantially the same as example 1 except that in the first step (2), 0.25g of sodium borohydride was added.
Example 7
This example is substantially the same as example 1 except that in the first step (2), 0.35g of sodium borohydride was added.
Example 8
This example is substantially the same as example 1 except that in the first step (2), the viscosity average molecular weight of polyvinylpyrrolidone in this example was 280000.
Example 9
This example is substantially the same as example 1 except that in the first step (2), the viscosity average molecular weight of polyvinylpyrrolidone is 320000.
Example 10
This example is substantially the same as example 1 except that in the first step (2), polyvinylpyrrolidone was added in an amount of 0.625 g.
Example 11
This example is substantially the same as example 1 except that in the first step (2), polyvinylpyrrolidone was added in an amount of 0.875.
Example 12
This example is substantially the same as example 1, except that in the first step (3), 0.125g of sulfur powder was used.
Example 13
This example is substantially the same as example 1, except that in the first step (3), the amount of sulfur powder used was 0.833 g.
Example 14
This example is substantially the same as example 1, except that in the first step (3), the hydrothermal reaction temperature was 150 ℃ and the reaction time was 15 hours.
Example 15
This example is substantially the same as example 1, except that in the first step (3), the hydrothermal reaction temperature was 200 ℃ and the reaction time was 10 hours.
Example 16
This example is substantially the same as example 1, except that in the second step (1) in this example, Sb is added2S3The mass ratio to MXene was 1.5: 1.
Example 17
This example is substantially the same as example 1, except that in the second step (1) in this example, Sb is added2S3The mass ratio to MXene was 2.5: 1.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. A preparation method of a two-dimensional carbide crystal-based antimony sulfide negative electrode material is characterized by comprising the following steps:
(1) adding an antimony source into deionized water, uniformly stirring, adding ethylene glycol, and stirring to obtain a solution A;
(2) adding sodium borohydride into the solution A obtained in the step (1), uniformly stirring, adding polyvinylpyrrolidone, and fully dissolving to obtain a solution B;
(3) adding the solution B obtained in the step (2) into a hydrothermal kettle lining containing sulfur powder for hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished, washing and drying to obtain Sb2S3
(4) Sb2S3Adding the obtained product into MXene solution, performing ultrasonic homogenization and freeze-drying to obtain the two-dimensional carbide crystal-based antimony sulfide negative electrode material.
2. The method for preparing the two-dimensional carbide crystal-based antimony sulfide negative electrode material as claimed in claim 1, wherein the step (1) comprises any one or more of the following conditions:
(1-1) the antimony source is SbCl3
(1-2) the ratio of the dosage of the antimony source to the deionized water is 1g: 100-140 mL;
(1-3) the volume ratio of the ethylene glycol to the deionized water is 0.8-1.2: 1.
3. The method for preparing the two-dimensional carbide crystal-based antimony sulfide negative electrode material as claimed in claim 1, wherein the step (2) comprises any one or more of the following conditions:
(2-1) slowly adding sodium borohydride into the solution A obtained in the step (1);
(2-2) the mass ratio of the sodium borohydride to the antimony source is 1-1.4: 1;
(2-3) the viscosity average molecular weight of the polyvinylpyrrolidone is 280000-320000;
(2-4) the mass ratio of the polyvinylpyrrolidone to the antimony source is 2.5-3.5: 1.
4. The method for preparing the two-dimensional carbide crystal-based antimony sulfide negative electrode material as claimed in claim 1, wherein the step (3) comprises any one or more of the following conditions:
(3-1) the mass ratio of the sulfur powder to the antimony source is 1: 2-3;
(3-2) uniformly spreading sulfur powder at the bottom of the lining of the hydrothermal kettle;
(3-3) the temperature of the hydrothermal reaction is 150-;
(3-4) solid-liquid separation adopts a centrifugal separation mode, and the rotating speed during centrifugal separation adopts a method of firstly high speed, then low speed and then high speed; the high-speed rotating speed is 7000rmp-8000 rmp; the low-speed rotating speed is 2000rmp-3000 rmp;
(3-5) washing with deionized water;
and (3-6) drying in a drying mode.
5. The method for preparing the two-dimensional carbide crystal-based antimony sulfide negative electrode material as claimed in claim 1, wherein the step (4) comprises any one or more of the following conditions:
(4-1)Sb2S3the mass ratio of MXene to MXene is 1.5-2.5: 1;
(4-2) MXene comprising Ti3C2、Ti2C、Ta4C3、V2C or Nb2C。
6. The two-dimensional carbide crystal-based antimony sulfide negative electrode material obtained by the preparation method of any one of claims 1 to 5.
7. The two-dimensional carbide crystal-based antimony sulfide negative electrode material of claim 6, wherein Sb is Sb2S3Present as a kind of nanowire rod and evenly distributed on the two-dimensional carbide crystal MXene.
8. The application of the two-dimensional carbide crystal-based antimony sulfide negative electrode material as claimed in claim 6 in the aspect of negative electrode materials of lithium ion batteries.
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