CN112133899B - Preparation method of tin-antimony sulfide/graphene composite material and application of tin-antimony sulfide/graphene composite material in sodium ion battery cathode - Google Patents
Preparation method of tin-antimony sulfide/graphene composite material and application of tin-antimony sulfide/graphene composite material in sodium ion battery cathode Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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Abstract
A preparation method of a tin-antimony sulfide/graphene composite material and application of the tin-antimony sulfide/graphene composite material in a sodium ion battery cathode. The preparation method comprises the steps of uniformly dispersing stannic chloride, a sulfur source and graphene oxide into a solvent, and carrying out one-step hydrothermal reaction to prepare stannic disulfide/graphene (SnS) 2 /GNS). Then SnS 2 the/GNS is dispersed in the mixed aqueous solution of tartaric acid and antimony potassium tartrate, and the tin antimony sulfide/graphene (SnSbS) is prepared by hydrothermal reaction again x /GNS, x =2 to 3). The preparation process is simple and easy to implement, mild in reaction condition, easy to control and high in repeatability, and is suitable for large-scale production. The excellent conductivity and structural stability of the graphene can be complemented with the high-capacity advantage of the tin antimony sulfide, so that the sodium storage performance of the tin antimony sulfide is comprehensively improved.
Description
Technical Field
The invention belongs to the field of preparation of a sodium ion battery cathode material, and particularly relates to preparation and regulation of a multilayer graphene composite material.
Background
Sodium Ion Batteries (SIBs) have received much attention in the new energy field due to its widespread distribution, low cost and easy extraction. Due to the larger radius of sodium ions, the active material has the problem of volume expansion in the charging and discharging process, so that the active material is pulverized and has poor contact with a current collector and a conductive agent. Therefore, it is important to develop a negative electrode material capable of stably storing sodium.
Many experimental results prove that the tin-based compound can perform alloying reaction with sodium, and the sodium storage performance of the tin-based compound is obviously superior to that of the traditional carbon material. Unfortunately, this process has severe volume expansion (Sn turns)Converted to Na 3.75 The volume expansion amplitude of Sn is 520%), which causes great limitation to the practical application of the anode of SIBs. Among the numerous tin-based compounds, tin disulfide (SnS) 2 ) Has larger interplanar spacing (0.59 nm) and can bear Na + Volume change during charging and discharging. However, due to its lower conductivity, the phenomenon of capacity fade is unavoidable. According to the research report, the SnS is reduced 2 The size of the particles is on the order of nanometers, which can allow them to withstand higher stresses. At the same time SnS 2 The volume change of the graphene in the charge-discharge process can be effectively buffered by compounding the graphene with the multilayer graphene. Meanwhile, antimony (Sb) is often used as a dopant in the field of optoelectronics to improve the conductivity of tin-based compound electrode materials. Therefore, the tin-antimony sulfide/graphene SIBs negative electrode with higher stability is hopeful to be prepared by co-introducing Sb and graphene.
Disclosure of Invention
The invention aims to solve the problems of volume expansion and active material pulverization of SIBs negative electrode materials in the charging and discharging processes. Graphene has a large specific surface area, high conductivity and mechanical properties, and is considered to be an ideal conductive substrate. Therefore, the graphene is considered to be introduced as a substrate, so that the conductivity and stability of the whole material are improved, and the preparation method for growing the tin-antimony sulfide nano small particle composite material on the surface of the graphene is provided and is applied to SIBs negative electrodes with stable structures.
Mixing tin antimony sulfide (SnSbS) x ) The graphene is loaded on the surface of graphene in the form of small nano particles (about 10 nm), so that the problems of volume expansion, active material pulverization and the like can be effectively relieved. The invention mainly adopts a two-step hydrothermal method to carry out tin antimony sulfide/graphene (SnSbS) x GNS) preparation of the composite material. The preparation process is simple and feasible, and is suitable for large-scale production. SnSbs with size of about 10nm after hydrothermal treatment x The nano particles uniformly grow on the surface of the multilayer graphene, and thermogravimetric analysis shows that the mass percentage of the ternary sulfide in the composite material is about 71%. Electrochemical tests show that the prepared material has high specific discharge capacity and good rate performance and cycling stability.
The technical scheme of the invention is as follows:
tin antimony sulfide/graphene (SbSnS) x GNS) preparation method of nano-particle composite material, comprising the following preparation steps:
(1) Firstly, preparing tin disulfide/graphene (SnS) 2 (ii)/GNS): uniformly dispersing stannic chloride, a sulfur source and graphene oxide into a solvent, uniformly mixing, carrying out one-step hydrothermal reaction at 160-180 ℃, reacting for 6-8 h, centrifugally washing, and freeze-drying to obtain stannic sulfide/graphene (SnS) 2 /GNS)。
(2) Weighing a certain amount of the product obtained in the step (1), dispersing the product in a mixed aqueous solution of tartaric acid and antimony potassium tartrate, and performing hydrothermal reaction again to obtain tin antimony sulfide/graphene SnSbS x The reaction temperature of the/GNS composite material is 110-130 ℃, the reaction time is about 6-8 h, and the final target product SbSnS is obtained after centrifugal washing and freeze drying x (ii)/GNS, wherein x =2 to 3.
In the step (1), the mass ratio of the graphene to the stannic chloride to the sulfur source is 30: 60-85: 60-120; the sulfur source is one of thioacetamide, L-cysteine or sodium sulfide; the solvent is one of water and glycol.
In the step (2), the antimony potassium tartrate and the tartaric acid are respectively dissolved in 30mL of distilled water serving as a mixed aqueous solution, wherein the mass ratio of the distilled water to the antimony potassium tartrate to the tartaric acid is 375: 1: 4-4.5; snS before hydrothermal reaction 2 The concentration of the/GNS in the mixed aqueous solution is 1-2 mg/mL -1 。
The invention also provides an application of the tin antimony sulfide/graphene composite material in a sodium ion battery cathode, and the method comprises the following steps:
(3) Assembling the sodium-ion battery: the final target product SnSbS x The preparation method comprises the following steps of uniformly mixing/GNS, conductive carbon black (super P) and polyvinylidene fluoride binder (PVDF) according to the mass ratio of 7: 2: 1 or 8: 1, transferring the mixture into a refiner, and infiltrating the refiner with N-methyl pyrrolidone (NMP). After the electrode paste is prepared into uniform electrode paste, uniformly coating the electrode paste on the surface of copper foil by using a wet film preparation device, wherein the coating thickness is 50 to100 μm. After coating, the coating was dried in a vacuum oven at 100 ℃ for 12h. And finally, making the electrode into a disk electrode with the diameter of 14mm by using a puncher, and forming a two-electrode system with sodium metal in a glove box, wherein the battery assembly model is a CR2032 button battery.
The invention has the advantages and beneficial effects that:
the preparation method has simple preparation steps, adopts common distilled water as a reaction solvent, and has low cost; meanwhile, the reaction condition is mild, the control is easy, and the repeatability is high. The addition of the graphene plays a role in dispersing the prepared tin-antimony sulfide, and the agglomeration of the material is avoided to a great extent. The size of tin antimony sulfide grown on the surface of the graphene is about 5-10 nm, and the integral composite material has a multilayer structure, so that the structure is beneficial to rapid de-intercalation and intercalation of sodium ions in the charge and discharge process, and the problem of volume expansion in the charge and discharge process can be buffered. In addition, the excellent conductivity and stability of the graphene can be complementary with the high-capacity advantage of the tin-antimony sulfide, and the sodium storage performance of the tin-antimony sulfide is comprehensively improved.
Drawings
FIG. 1 shows the prepared SnS 2 GNS and Sbsns x XRD spectrum of/GNS.
FIG. 2 shows the preparation of SbSnS x SEM and Mapping elemental distribution diagram of/GNS, (a) low magnification SEM picture of SbsnSx/GNS; (b) high power SEM image of SbsSnSx/GNS; (c) An element map, wherein (c 1) is a Sn element distribution map; (c 2) is a Sb element diagram; (C3) is an S element distribution diagram (C4) is a C element distribution diagram.
FIG. 3 shows the preparation of SbSnS x TEM topography of/GNS.
FIG. 4 shows the preparation of SbSnS x And Sbsns x TGA test of/GNS.
FIG. 5 shows the preparation of SbSnS x The multiplying power performance diagram of/GNS, wherein (a) is the multiplying power diagram of two electrode materials, and (b) is SbSnS x Constant current charge and discharge curves at different current densities for the GNS.
FIG. 6 shows preparation of SbSnS x Cycle life performance plot of/GNS.
Detailed Description
Example 1: in the preparation of SnS 2 In the/GNS step, the sheet diameter of the graphene can be 100 nm-5 μm, and the thickness can be 0.6 nm-10 nm. After adding SnCl 4 Before thioacetamide, the concentration of graphene may be 1mg/mL -1 . The inventors have found that 1mg/mL is used in comparison with other concentrations -1 The concentration of (2) enables the dispersion to be more uniform and stable.
(1) Tin disulfide/graphene (SnS) 2 Preparation of/GNS): the preparation of SnS 2 The hydrothermal reaction temperature of/GNS is 180 ℃, the reaction time is 6h, and after centrifugal washing and freeze drying, the tin disulfide/graphene (SnS) is obtained 2 /GNS). Compared with other temperatures, the temperature interval ensures SnS 2 The graphene can have better crystallinity and can grow on the surface of graphene in a uniform shape. Meanwhile, the volume filling amount of the reaction kettle is 70%. The mass of graphene, tin tetrachloride and thioacetamide was 30mg, 85mg and 70mg, respectively.
(2) Tin antimony sulfide/graphene (SnSbS) x Preparation of/GNS) composites
In the preparation of SnSbs x In the step of/GNS (x =2 to 3), the tartaric acid is added to the solution to promote the dissolution of antimony potassium tartrate, so that the solution before the reaction is more uniform and stable. 80mg of antimony potassium tartrate was first added to 30mL of distilled water, and the amount of tartaric acid added may be 320mg.
In the preparation of SnSbs x SnS adopted in the hydrothermal step of the/GNS composite material in order to prevent the problem of graphene agglomeration caused by secondary hydrothermal 2 The concentration of/GNS in the solution prepared above may be 1.5 mg/mL -1 . The hydrothermal temperature can be 120 ℃, the reaction time is 6h, and the volume filling amount of the reaction kettle is 70 percent.
Example 2
(1)SnS 2 Preparation of/GNS: first, 180mg of graphene is uniformly dispersed in 100mL of distilled water, and 360mg of SnCl is added 4 And 720mg of L-cysteine, stirred for 2h. The preparation of SnS 2 The hydrothermal reaction temperature of the/GNS can be 180 ℃, the reaction time is 8h, and SnS is obtained after centrifugal washing and freeze drying 2 /GNS。
(2) Preparation of SnSbS x /GNS (x =2 to 3): firstly, the SnS is processed 2 the/GNS product was dispersed in 30mL of distilled water at a concentration of 1mg/mL, and after uniform dispersion, 320mg of tartaric acid and 80mg of antimony potassium tartrate were added, respectively. After stirring for 1h, the hydrothermal temperature is 120 ℃ and the reaction time is 6h. The filling amount of the hydrothermal reaction kettle is 70%.
Example 3
(1)SnS 2 Preparation of/GNS: first, 30mL of ethylene glycol was taken and 40mg of graphene was ultrasonically dispersed therein. After the dispersion was homogeneous, 110mg of SnCl was added 4 And 98mg of sodium sulfide, after stirring for 2h. The preparation of SnS 2 The hydrothermal reaction temperature of/GNS can be 180 ℃, the reaction time is 8h, and SnS is obtained after centrifugal washing by distilled water and freeze drying 2 /GNS。
(2) Preparation of SnSbS x (x =2 to 3): firstly, the SnS is processed 2 the/GNS product was dispersed in 30mL of distilled water at a concentration of 1mg/mL, and after uniform dispersion, 320mg of tartaric acid and 80mg of antimony potassium tartrate were added, respectively. After stirring for 1h, hydrothermal at 120 ℃ for 6h. The filling amount of the hydrothermal reaction kettle is 70%.
Assembly of a battery
Example 4:
(1) Preparing electrode paste, snSbS x The mass ratio of the/GNS active material, the conductive carbon black (super P) and the polyvinylidene fluoride binder (PVDF) is 7: 2: 1. After being wetted with an appropriate amount of N-methylpyrrolidone (NMP) and sufficiently and uniformly mixed in a homogenizer, the mixed electrode slurry was coated on a copper foil with a wet film maker, and the coating thickness may be 100 μm.
(2) The electrolyte solvent was 2.5mL of Ethylene Carbonate (EC) and 2.5mL of Propylene Carbonate (PC), 0.25mL of fluoroethylene carbonate (FEC) was added, and after mixing well, 5mmol of NaClO was added 4 . Glass fiber with a diameter of 16mm was used as a separator, and a metal sodium sheet with a diameter of 14mm was used as a counter electrode. The whole assembly process of the CR2032 button cell battery is carried out in a glove box in an argon atmosphere, and the voltage test range is 0.01-3.0V.
FIG. 1 shows SnS 2 (iv) GNS and SnSbs x /GThe XRD spectrogram of NS shows that the two materials can perfectly correspond to the standard card JCPDS No.23-0677 of tin disulfide and the standard card JCPDS No.50-0927 of carbon at the same time, and obvious miscellaneous peaks are found in test data, so that the prepared material is proved to have better purity. By comparison, there was no significant change in the characteristic diffraction peaks of the XRD data for the two materials, since the atomic radii of Sn and Sb are closer and the content of Sb is smaller, so that the characteristic diffraction peaks associated with antimony sulfide did not appear.
FIG. 2 shows prepared SnSbs x SEM and Mapping elemental analysis chart of/GNS, and SnSbS can be known from the chart x No significant agglomeration occurred during growth on the surface of the graphene platelet. Through the Mapping test of fig. 2C, four elements of Sn (C1 in fig. 2), sb (C2 in fig. 2), S (C3 in fig. 2) and C (C4 in fig. 2) contained in the composite material can be proved.
FIG. 3 is a SnSbS x TEM morphology of/GNS, and SnSbs can be seen x The nano-small particles grow very uniformly on the surface of graphene and have a size of about 10nm.
FIG. 4 is SnSbs x TGA test of/GNS, and SnSbs can be calculated according to the test result x In SnSbs x The mass fraction in the/GNS is 71%.
FIG. 5 is SnSbs x The multiplying power performance tested by the battery assembled by the GNS and the metallic sodium shows that the current density is 50 mA-g -1 The reversible capacity can reach 1372mAh g -1 (ii) a When the current density increased to 10A g -1 The reversible capacity can still be maintained at about 650mAh g -1 (a in FIG. 5). In fig. 5, b is a constant current charge and discharge curve chart of the assembled sodium-ion battery under different current densities.
FIG. 6 is a SnSbs prepared x The current density of the/GNS is 1000 mA-g -1 The prepared electrode material shows better circulation stability, namely the coulombic efficiency is more stable after 500-week circulation, and the capacity can be maintained at about 750 mAh.g -1 。
Claims (3)
1. A preparation method of a tin-antimony sulfide/graphene composite material, wherein the tin-antimony sulfide/graphene composite material is applied to a sodium ion battery cathode, and comprises the following preparation steps:
(1) Firstly, preparing tin disulfide/graphene SnS 2 The ratio of/GNS: uniformly dispersing tin tetrachloride, a sulfur source and graphene oxide in a solvent, uniformly mixing, carrying out one-step hydrothermal reaction at 160-180 ℃, wherein the reaction time is 6-8 h, carrying out centrifugal washing, and carrying out freeze drying to obtain tin disulfide/graphene SnS 2 /GNS；
(2) Dispersing the product obtained in the step (1) in a mixed aqueous solution of tartaric acid and antimony potassium tartrate, carrying out hydrothermal reaction again at the reaction temperature of 120 ℃ for 6 hours, wherein the volume filling amount of a reaction kettle is 70%, carrying out centrifugal washing, and carrying out freeze drying to obtain the tin-antimony sulfide/graphene composite material, wherein the general formula of the tin-antimony sulfide/graphene composite material is SnSbS x (ii)/GNS, wherein x =2 to 3; prepared SnSbs x The nano small particles uniformly grow on the surface of the graphene, and the size of the nano small particles is 10nm; snSbs x In SnSbs x The mass fraction in the/GNS is 71%, and the whole composite material has a multilayer structure.
2. The method for preparing the tin antimony sulfide/graphene composite material as claimed in claim 1, wherein in the step (1), the mass ratio of the graphene to the tin tetrachloride to the sulfur source is 30: 60 to 85: 60 to 120; the sulfur source is one of thioacetamide, L-cysteine or sodium sulfide; the solvent is one of water and glycol.
3. The preparation method of the tin antimony sulfide/graphene composite material according to claim 1, wherein in the step (2), the mixed aqueous solution is prepared into a mixed solution of tartaric acid and antimony potassium tartrate in 30mL of distilled water, wherein the mass ratio of the distilled water to the antimony potassium tartrate to the tartaric acid is 375: 1: 4 to 4.5; snS before hydrothermal reaction 2 The concentration of the/GNS in the mixed aqueous solution is 1 to 2 mg/mL -1 。
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