CN109698326B - Organic tin phosphide/graphite oxide composite material for negative electrode of sodium-ion battery - Google Patents
Organic tin phosphide/graphite oxide composite material for negative electrode of sodium-ion battery Download PDFInfo
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Abstract
The invention relates to an organic tin phosphide/graphite oxide composite material for a negative electrode of a sodium-ion battery. The invention realizes the preparation of the material by a simpler process. The invention has the beneficial effects that: the invention takes GO material as a precursor and SnCl2·2H2O reacts to form SnO2@ GO composite. Then triethylamine is used as an initiator of polymerization reaction to cause Hexachlorocyclotriphosphazene (HCCP) and 4, 4-dihydroxy diphenyl sulfone to generate polymerization reaction, and PZS is used for coating SnO2@ GO, carbon coating and phosphating are realized. Compared with other preparation methods of the cathode material of the sodium-ion battery, the preparation method is simple and easy to implement, and the composition of the conductive carbon material and Sn-O-P @ GN is realized simply. The sodium ion battery prepared by the invention has higher specific capacity, excellent cycling stability and rate capability.
Description
Technical Field
The invention relates to the technical field of sodium ion battery preparation, in particular to a sodium ion battery cathode material and a preparation method thereof.
Background
With the progress of science and technology and the development of society, energy and environmental problems have become one of the most important topics in the world today. Fossil fuels are still the most used energy in the world at present, however, the reserves of fossil energy are limited, and the increasing demand and unregulated exploitation of human beings inevitably lead to the exhaustion of the fossil energy. Therefore, the search for new renewable energy sources and mass storage is urgent. In many energy storage fields, electrochemical energy storage is a simple and efficient energy storage method. Among them, the lithium ion battery is an electrochemical power source widely used at present, but with the aggravation of the dependence of industries such as digital code, traffic and the like on the lithium ion battery, the limited lithium resource is bound to face the problem of shortage. The room temperature sodium ion battery has the advantages of abundant raw materials, wide distribution and low price, thereby arousing the wide research interest of people, and the research and development of the room temperature sodium ion battery can alleviate the problem of limited battery development caused by the shortage of lithium resources to a certain extent.
The current negative electrode material of the sodium-ion battery mainly comprises hard carbon, alloy and titanium-based compound. Hard carbon is a sodium ion battery cathode material which is most widely applied, but the radius of sodium ions is large, so that intercalation/deintercalation between graphite layers is difficult, and an irreversible SEI (solid electrolyte interphase) passivation layer is easily formed during first charge and discharge, so that the first coulombic efficiency is reduced, which is a main factor restricting the application of the carbon material. The metal simple substance or the alloy has serious volume expansion in the process of sodium ion embedding/removing, which causes rapid capacity attenuation and reduced electrode stability. The titanium-based oxide is used as a negative electrode material of a sodium ion battery and stores sodium through an intercalation reaction mechanism, however, the storage sites in the crystal structure of the titanium-based oxide are limited, so that the sodium storage capacity of the material is generally low.
SnO2The material is a sodium ion electrode material, but the volume expansion in the charging and discharging process is large, so that the material is crushed, and the rate capability and the cycling stability are poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a sodium ion battery negative electrode material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
(1) The negative electrode material of the sodium-ion battery is characterized by comprising the following raw material components: graphene Oxide (GO), Hexachlorocyclotriphosphazene (HCCP), 4-dihydroxy diphenyl sulfone, tin chloride, concentrated hydrochloric acid, triethylamine and a solvent.
Preferably, the solvent is methanol and ethylene glycol.
Preferably, the volume ratio of ethylene glycol to water in the raw material components is 8: 2.
(2) The preparation method of the negative electrode material of the sodium-ion battery is characterized by comprising the following steps of:
Step 2 1.25g SnCl2.2H2Dissolving O in the mixed solvent of glycol containing concentrated hydrochloric acid and water to obtain mixed solution B.
And step 3: solution B was added to solution A and stirred for 40 minutes. Putting the mixture into an autoclave and an oven, centrifuging, washing with deionized water, and freeze-drying to obtain SnO2@GO。
And 4, step 4: 0.15g SnO2@ GO is dissolved in 40ml of methanol, and ultrasonic treatment is carried out for 30min to obtain solution C.
And 5: 300mg of HCCP and 400mg of 4, 4-dihydroxydiphenyl sulfone were dissolved in 10ml of methanol, respectively, and added to solution C, followed by stirring for 5min, addition of triethylamine, and stirring for 24 hours. When the reaction time is up, centrifuging the gray precipitate, washing the gray precipitate for 3 times by using methanol, and drying the gray precipitate in vacuum to obtain PZS @ SnO2@GO。
Step 6: mixing PZS @ SnO2@ GO is calcined to obtain C @ Sn-O-P @ GN.
Preferably, in step 1, the volume ratio of the ethylene glycol to the water is 8: 2.
Preferably, in the step 2, the volume ratio of the ethylene glycol to the water is 8: 2; the amount of the concentrated hydrochloric acid contained was 0.5 ml.
Preferably, in step 3, the temperature of the oven is 140 ℃, and the hydrothermal time is 5 hours or more.
Preferably, in step 5, the solution is added dropwise; the amount of the added triethylamine is 1.5 ml; the stirring temperature was 35 ℃.
Preferably, in step 6, during the calcination: the calcining temperature is 800 ℃, the calcining time is 2h, and the calcining protective atmosphere is argon. The heating rate and the cooling rate in the calcination are both 2 ℃/min.
According to the electrochemical performance test of the sodium ion battery negative electrode material, a negative electrode active substance is used as a negative electrode pole piece, Super P and PVDF (dissolved in NMP) are uniformly mixed into slurry according to the mass ratio of 80:10:10 and then coated on copper foil. In a vacuum oven 100oC, after drying for 12h, cutting the electrode slice into a circular slice with the diameter of 12mm, wherein the loading capacity of the electrode slice is 1.1-1.5mg/cm2Half-cell testing was performed using CR2032 button cells assembled in a glove box with water and oxygen partial pressures less than 0.1 ppm. The half cell uses sodium as a counter electrode, glass fiber as a separator, NaClO4Dissolving in a solvent with the volume ratio of 1: DEC,5% FEC solution as electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes GO material as a precursor and coats SnCl with the precursor2.2H2O, forming SnO2@ GO. Using ethylene diamine as initiator of polymerization reaction to make Hexachlorocyclotriphosphazene (HCCP) and 4, 4-dihydroxy diphenyl sulfone produce polymerization reaction to obtain PZS (poly (cyclotriphosphazene-co-4,4' -sulforyldiol)), then making PZS coat SnO2@ GO, carbon coating and phosphating are realized. Compared with other preparation methods of the cathode material of the sodium-ion battery, the preparation method is simple and easy to implement, and the composition of the conductive carbon material and Sn-O-P @ GN is realized simply. The sodium ion battery prepared by the preparation method provided by the invention has the advantages of higher specific capacity, excellent cycling stability and excellent rate capability.
The electrochemical performance test of the cathode material of the sodium ion battery is characterized in that the sodium ion battery is assembled by a carbon-coated phosphorus-doped composite material.
Drawings
The invention has the following drawings:
FIG. 1 is a scheme showing the synthesis of C @ Sn-O-P @ GN;
FIG. 2 is C @ Sn-O-P @ GN; Sn-O-P glass @ GN; an XRD pattern of PZS @ GN, C @ Sn-O-P glass, C @ Sn @ GN;
FIG. 3 is a Raman spectrum of C @ Sn-O-P @ GN;
FIG. 4 shows C @ Sn @ GN and SnO2Thermogravimetric plot of @ GN;
FIG. 5 is a C @ Sn-O-P glass @ GN scanning electron microscope and transmission electron microscope test chart;
FIG. 6 is a graph showing electrochemical performance tests.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Dissolving 200mg of GO in a mixed solvent of ethylene glycol and water (volume ratio is 8: 2), carrying out ultrasonic treatment for 30min, and uniformly stirring to obtain a mixed solution A. Then weigh 1.25g SnCl2.2H2O in concentrated hydrochloric acid (0.5 ml)>5M) of ethanol and water (the volume ratio is 8: 2) to obtain a mixed solution B. Solution B was added to solution A and stirred for 40 minutes. Placed in an autoclave and transferred to an oven, 140oC, 5h, centrifuging, washing with deionized water, and freeze-drying to obtain SnO2@ GO. 0.15g SnO was weighed2@ GO is dissolved in 40ml of methanol, and ultrasonic treatment is carried out for 30min to obtain solution C. Weighing 300mg HCCP and 400mg 4, 4-dihydroxy diphenyl sulfone, respectively dissolving in 10ml methanol, dropwise adding into solution C, stirring for 5min, adding 1.5ml triethylamine, 35oC, stirring for 24 hours. When the reaction time was up, the grey precipitate was centrifuged and washed 3 times with methanol, 30 timesoC vacuum drying for more than 12h to obtain PZS @ SnO2@ GO. Mixing PZS @ SnO2@GO 800oCalcining the C for 2h (protection under argon atmosphere) to obtain C @ Sn-O-P @ GN.
Analytical characterisation
Analysis and characterization the samples were subjected to structural, phase analysis using X-ray diffractometer type MPD X' Pert PRO (XRD, CuK α, λ =0.15406 nm) in the netherlands, and the carbon content of the samples was tested using a german STA 409 PC Luxx thermogravimetric analyzer (TGA) in an air atmosphere. The morphology and structure of the samples were observed by Scanning Electron Microscopy (SEM) of the Hitachi model S-4800 and Transmission Electron Microscopy (TEM) of the JEM-2100UHR model. The elements contained in the sample were analyzed by Thermo Scientific ESCALab250Xi multifunctional photoelectron spectroscopy (XPS, AlK α). The analysis and study of graphene in the composite material and the surface of the composite material were carried out using a JobinYvon HR800 Raman spectrometer (Raman).
Results and analysis:
FIG. 1 illustrates a synthetic scheme of C @ Sn-O-P @ Graphene material. Firstly, oxidizing graphite to obtain graphene oxide, and then carrying out SnCl2.2H2Dissolving O in a mixed solvent of ethylene glycol containing concentrated hydrochloric acid and water (volume ratio of 8: 2), and mixing with graphene oxide to obtain SnO2@ GO. Polymerizing HCCP with 4, 4-dihydroxy diphenyl sulfone under the action of ethylenediamine, adding the product into SnO dissolved in methanol2@ GO to obtain PZS @ SnO2@ GO is calcined at high temperature to obtain C @ Sn-O-P @ GN.
To determine the crystal structure of Sn, we performed XRD analysis on the product. FIG. 2 is an XRD spectrum of C @ Sn-O-P glass @ GN, PZS @ GN, C @ Sn-O-P glass, and C @ Sn @ GN. Several organic tin phosphide-based carbon materials (C @ Sn-O-P glass @ GN, Sn-O-P glass @ GN and C @ Sn-O-P glass) synthesized in FIG. 2 belong to amorphous glass structures, no obvious lattice structure is detected, and graphene-loaded SnO2And 4, 4-dihydroxy diphenyl sulfone, can be matched with simple substance Sn because graphite carbon can be SnO when the temperature is higher than 700 DEG C2Reducing the Sn into a simple substance. Two characteristic diffraction peaks of PZS @ GN at 25.5 ° and 43 ° correspond to the (002) and (100) crystal planes of graphite, respectively. The peak at 25.5 ° is relatively sharp, indicating a higher degree of reduction of graphene.
In order to study the graphitization degree of the tin organophosphate-based carbon material after high-temperature calcination, raman spectroscopy is performed on the material, and the test result is shown in fig. 3. As shown in FIG. 3, two distinct peaks are at 1343 cm each-1(D band) and 1585 cm-1The ratio of (G band) G band to I band was 0.957, indicating that the sample was highly reduced, exhibited a highly disordered structure, and had good conductivity.
In order to explore the content of metallic tin in the tin-based carbon material of organic phosphoric acid, thermogravimetric curve analysis is carried out on the material, and the content of tin in C @ Sn-O-P glass @ GN is 58% as shown in FIG. 4.
To study the microstructure and morphology of the composite material, we performed scanning electron microscopy and transmission electron microscopy tests on the material (shown in fig. 5). FIGS. 5 (a) and 5 (b) are scanning electron micrographs of C @ Sn-O-P glass @ GN, which shows that C @ Sn-O-P glass @ GN is composed of a crimped carbon material having rugose pores and no tin nanoparticles are visible on the surface. FIGS. 5 (c) and 5 (d) are transmission electron micrographs thereof. The figure shows nanoparticles around 10nm, but since the material exhibits an amorphous structure, no crystallographic fringes can be detected, which is consistent with XRD. This indicates that, in the presence of phosphorus and an oxygen-containing carbon-based material, after high-temperature calcination, tin coordinates with phosphorus and oxygen to form a Sn-O-P glassy substance.
C @ Sn-O-P glass @ GN, PZS @ GN, C @ Sn-O-P glass and Sn @ GN are respectively coated on copper foil and assembled into a button cell in a glove box, and the electrochemical performance of the material is tested. FIG. 6 (a) is a cyclic voltammogram of C @ Sn-O-P glass @ GN, as shown in the figure, the reduction peak at 1.93V corresponds to the formation of SEI film in the first cycle, and disappears during the subsequent cycles, the peaks at 1.55V, 1.20V, 1.91V are due to sodium treatment of P, and the peaks at 0.367V, 0.01V are alloying reactions of Sn and Na. The oxidation peaks at 0.1V and 0.6V are due to the dealloying reaction of Sn. The oxidation peaks at 1.59V, 1.68V, 2.18V are due to the gradual sodium depletion of P. The higher the repetition of the curves of the second and third circles, the higher the reversibility of the electrochemical reaction. FIG. 6 (b) is a constant current charge and discharge curve of C @ Sn-O-P glass @ GN, the first discharge specific volume is 873.9mAh g-1The specific volume of charging is 366.2mAh g-1The coulombic efficiency was 42%, which was attributed to the formation of SEI film and high carbon content. FIG. 6 (C) is a graph of C @ Sn-O-P glass @ GN, PZS @ GN, C @ Sn-O-P glass at 100mA g-1For the next 100 cycles, the specific volume of C @ Sn-O-P glass @ GN after 100 cycles is 364.2mAh g-1The capacity retention was 99.3%. The specific volume of Sn @ GN and Sn-O-P glass @ GN after 100 cycles is 151 mAh g-1And 277.4 mAh g-1The capacity retention amounts were 16.6% and 66.9%, respectively, which are caused by Sn being crushed after many cycles due to large volume expansion of Sn during charge and discharge and thin carbon coating layer. The PZS @ GN and GN show good cycling stability, and the first discharge specific capacities are 484.2 mAh g respectively-1And 884.5 mAh g-1The first charging specific capacity is 177.2 mAh g respectively-1And 165.4 mAh g-1The coulombic efficiencies are 36.6% and 18.9% respectively, which shows that phosphorus doping can expand the interlayer spacing of graphene, improve the conductivity, enable sodium ions to be rapidly inserted into/out of a graphene layer, and further improve the storage capacity and the first coulombic efficiency. FIG. 6 (d) C @ Sn-O-P glass @ GN, Sn @ GN, PZS @ GN, C @ Sn-O-P glass at different current densities (from 100mA g)-1To 300mA g-1) Specific capacity of the electrode, C @ Sn-O-P glass @ GN electrode is 100mA g-1、200mA g-1、500mA g-1、1000mA g-1、2000mA g-1、3000mA g-1The specific discharge capacity is 400mAh g respectively-1、332mAh g-1、288.6mAh g-1、284.6mAh g-1、204.2mAh g-1When the current density is recovered to 100mA g-1And the specific volume is still 366.8 mAh g after 30 times of circulation-1. When the current density is recovered to 100mA/g and the specific volume is still 366.8 mAh g after 30 times of circulation-1. The rate capability of C @ Sn-O-P glass is equivalent to that of C @ Sn-O-P glass @ GN, but when the current is recovered to 100mA g-1After 30 times of circulation, the specific volume is reduced to 271.7 mAh g-1At the same time, PZS @ GN and GN also have good multiplying power performance, especially at 100mA g-1、200mA g-1、500mA g-1、1000mA g-1、2000mA g-1、3000mA g-1The specific discharge capacity is 182.8mAh g-1、160.2mAh g-1、134.7mAh g-1、115.8mAh g-1、97mAh g-1When the current is restored to 100mA g-1After 30 times of circulation, the specific volume is stabilized at 180mAh g-1. Sn @ GN shows poor rate characteristics at 100mA g-1、200mA g-1、500mA g-1、1000mA g-1、2000mA g-1、3000mA g-1The specific discharge capacity is 373.2mAh g-1、240mAh g-1、156mAh g-1、110.2mAh g-1、71mAh g-1When the current is restored to 100mA g-1After 30 times of circulation, the specific volume is stabilized at 173.7mAh g-1. FIG. 6 (e) shows C @ Sn-O-P glass @ GN at 500mA g-1And 1A g -11500 long cycles below. Specific volume of first charge is 306.3m Ah g-1And 289.2Ah g-1The specific volumes after 1500 times of circulation are 237.1mAh g respectively-1And 195.2mAh g-1The corresponding capacity reserves were 77.4% and 67.5%, respectively.
C @ Sn-O-P glass @ GN has good electrochemical properties due to:
(1) the Sn particles are loaded on the reduced graphene, so that the conductivity of the composite material is improved on one hand, the transfer of electrons is facilitated, and the volume expansion of Sn can be buffered on the other hand; (2) polymerization of hexachlorocyclotriphosphazene and 4, 4-dihydroxydiphenylsulfone can not only coat Sn particles and provide a carbon-based buffer layer, but also realize that phosphorus doping provides extra specific capacity and reacts with Sn to form an amorphous Sn-O-P stable chemical structure; (3) the electrochemical performance of the material is further improved through the synergistic effect among the graphene buffer layer, the carbon coating layer and the phosphorus doping.
Although the present invention has been described in detail in the specification with reference to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention, such as changes in the mixture ratio of reactants, changes in the drying temperature, reaction time, and the like. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (2)
1. An organic tin phosphide/graphite oxide composite material for a negative electrode of a sodium-ion battery, which is characterized in that: dissolving 200mg of GO in a mixed solvent of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 8:2, carrying out ultrasonic treatment for 30min, and stirringStirring to obtain mixed solution A, and weighing 1.25g SnCl2 ·2H2O is dissolved in a mixed solvent of ethylene glycol and water containing 0.5ml of concentrated hydrochloric acid having a concentration>5M, wherein the volume ratio of the glycol to the water is 8:2, so as to obtain a mixed solution B, adding the solution B into the solution A, stirring for 40 minutes, putting into an autoclave, transferring into an oven, and carrying out 140 DEG CoC, 5h, centrifuging, washing with deionized water, and freeze-drying to obtain SnO2@GO；
0.15g SnO2Dissolving @ GO in 40ml of methanol, performing ultrasonic treatment for 30min to obtain a solution C, weighing 300mg of HCCP and 400mg of 4, 4-dihydroxy diphenyl sulfone, respectively dissolving in 10ml of methanol, dropwise adding into the solution C, stirring for 5min, adding 1.5ml of triethylamine for initiation, and performing 35 minoStirring for 24h, centrifuging the grey precipitate when the reaction time is up, washing with methanol for 3 times, 30 timesoC vacuum drying for more than 12h to obtain PZS @ SnO2@ GO, followed by PZS @ SnO2@GO 800oAnd C, calcining for 2h, and protecting in an argon atmosphere to obtain the organic tin phosphide/graphite oxide composite material C @ Sn-O-P @ GN.
2. The organic tin phosphide/graphite oxide composite material for sodium-ion battery negative electrode as set forth in claim 1, wherein: the preparation method of the sodium ion battery cathode comprises the steps of weighing the organic tin phosphide/graphite oxide composite material C @ Sn-O-P @ GN, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 1, and uniformly mixing the three materials to form slurry; and uniformly coating the slurry on a copper foil, drying the copper foil in a vacuum drying oven at 100 ℃ for 12 hours, and then compacting the electrode plate.
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