CN105720251A - Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material - Google Patents
Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material Download PDFInfo
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- 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
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- C12P19/00—Preparation of compounds containing saccharide radicals
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- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
The invention discloses an antimony sulfide based composite material of a sodium-ion battery and a preparation method of the antimony sulfide based composite material. The preparation method comprises the following steps of dissolving antimony sulfide in a medium, adding a graphene oxide solution, enabling the graphene oxide solution to be fully and uniformly dispersed with ultrasound for 1-600 minutes, mixing the graphene oxide solution, sulfite and an acid solution, stirring the mixed solution for 5-600 minutes, carrying out solid-liquid separation and drying to obtain a precursor of an amorphous antimony sulfide and graphene oxide composite material, and roasting the precursor for 1-24 hours at 250-550 DEG C under an inertia or reduction atmosphere to obtain the antimony sulfide based composite material of the sodium-ion battery. The composite material prepared according to the method can be used for a negative electrode material of the sodium ion battery, the specific capacity reaches 680mAh g<-1> when the current density is 2Ag<-1>, and the specific capacity retention rate is over 96% after circulation of 100 times. Compared with a traditional hydrothermal method, the preparation method has the advantages of short flow, simplicity in process, relatively low energy consumption, low production cost and the like, and is easy for mass production.
Description
Technical field
The present invention relates to sodium-ion battery Material Field, be specifically related to a kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof.
Background technology
Lithium ion battery, as high energy density cells system, is developed rapidly in portable type electronic product, electric tool and electric automobile field.But lithium resource reserves in the earth's crust are not abundant and expensive, may limiting lithium ion cell development in terms of extensive accumulation power supply.Therefore, development resource is enriched, advanced battery system with low cost, is the inevitable outlet solving following extensive storage electricity application.Sodium element and lithium are in same main group, have similar electronic structure and chemical property, and sodium element rich reserves in the earth's crust, refine low cost so that sodium-ion battery becomes one of the most promising a kind of energy conversion and memory device.Therefore, find and mate with performance of lithium ion battery, i.e. the sodium electrode material of high power capacity, high magnification and excellent cycling performance has become the study hotspot in present battery field.
Owing to sodium element and lithium chemistry are close, the positive electrode of lithium ion battery can use for reference sodium ion negative material, so at the sodium-ion battery positive pole pole material such as transition metal oxide containing sodium (such as Na x CoO 2 , Na x MnO2, NaNi0.5Mn0.5O2) and polyanionic compound (such as Na3V2(PO4)3、NaTi2(PO4)3、NaVPO4F, Na2FePO4F) research and development aspect has been achieved for the biggest progress.But owing to sodium ion has the ionic radius of big 55% than lithium ion, cause sodium ion cannot be effectively embedded in the graphite material interlamellar spacing with good embedding lithium performance and deviate from.Therefore, high-performance, exploitation and the application of low cost negative material are that sodium-ion battery moves towards business-like essential step.
Table 1
| Sb | Sb2S3 | Sb2O3 | Sb2O4 | |
| Theoretical capacity (mAh g-1) | 660 | 946 | 1109 | 1227 |
The application on anode material of lithium-ion battery of carbons material such as hard carbon, porous charcoal, carbon nano-fiber obtains in-depth study, but the efficiency first of such material is low, the highest being difficult to of capacity meets reality application.By contrast, simple substance antimony and compound (such as table 1) thereof cause the interest of researcher because of specific capacity height.In all antimony-based compounds, antimony trisulfide has more preferable specific energy density, less change in volume and more excellent cycle performance than simple substance antimony and sb oxide.In order to improve the chemical property of antimony trisulfide further, nanorize and composite graphite alkene are the effective means of the cycle life effectively alleviating material efflorescence, raising material.In document, needed for the nanometer antimony of report and compound and graphene composite material, the price of the persursor material preparation process of material that is high and that much report is complicated, and these shortcomings limit the large-scale application of antimony trisulfide/graphene composite material.The embodiment of the present invention is with business-like as primary raw material; be combined by antimony trisulfide in the aqueous solution under two-step method i.e. room temperature and graphene oxide, low-temperature sintering crystallization is prepared for that a kind of pattern is reliable, preparation method simple, raw material is easy to get, with low cost, be prone to the antimony trisulfide/graphene composite material of large-scale production.Graphene in composite provides loose structure, be conducive to the transmission of sodium ion in charge and discharge process, the Graphene being the most closely coated on antimony trisulfide surface can improve the electron conduction of whole material, and the Graphene being coated on antimony trisulfide surface can alleviate the change in volume in antimony trisulfide charge and discharge process, obtained material has higher capacity, superior high rate performance and cycle performance, is particularly suitable as the negative material of sodium ion secondary battery.
Summary of the invention
The technical problem to be solved is to provide a kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof, and the composition of described composite is Sb2S3/ Graphene.
The purpose of the present invention is achieved through the following technical solutions.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites, comprises the following steps:
(1) antimony trisulfide stirring and dissolving is formed solution in media as well;
(2) in step (1) gained solution, 0.1 ~ 30 is added
mg ml-1Graphene oxide solution, ultrasonic 1 ~ 600 min, until be uniformly dispersed；
(3) step (2) gained solution is sufficiently mixed with sulphite and acid mixed solution, stirs 1 ~ 600
Min, obtains amorphous antimony trisulfide and graphene oxide composite material presoma by solid-liquid separation, drying solid；
(4) by composite material precursor 250 ~ 550 DEG C of calcining 1 ~ 24 h under inertia or reducing atmosphere, sodium-ion battery antimony trisulfide based composites is i.e. obtained.
Further, step (1) described medium is one or more in sodium sulfide, Potassium monosulfide. and ammonium sulfide solution, and concentration is 0.1 ~ 5
mol L-1, antimony trisulfide forms [SbS with medium generation chemical reaction3]3-And dissolve.
Further, step (1) described antimony trisulfide addition is (0.001 ~ 3) with the mol ratio of sulphurizing salt in medium: 1.
Further, the graphene oxide in the graphene oxide solution described in step (2) and antimony trisulfide mass ratio are (0.001 ~ 0.5): 1.
Further, step (3) described sulphite is one or more in ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite, Potassium acid sulfite and sodium sulfite；The addition of sulphite is (0.5 ~ 5) with the mol ratio of sulphurizing salt in medium: 1.
Further, the acid described in step (3) is one or more in hydrochloric acid, sulphuric acid, nitric acid, acetic acid, oxalic acid and citric acid；The addition of acid is (0.5 ~ 3) with the mol ratio of sulphurizing salt in medium: 1；The concentration of acid is less than 5 mol L-1。
The sulphite of step (3) and acid are precipitant, and the purpose adding precipitant is the S in order to consume in solution2-Ion, makes antimony trisulfide and sulfur be deposited in surface of graphene oxide, and the reaction of generation is as follows: 4 [SbS3]3- + 3SO3 2-
+ 18H+ → 6S + 9H2O
+ 2Sb2S3。
Further, step (3) described mixing time is 5 ~ 600 min.
Further, step (3) is described is dried as one or more in lyophilization, vacuum drying and forced air drying.
Further, step (4) described inertia or reducing atmosphere are nitrogen, argon, hydrogen or their gaseous mixture.
A kind of sodium-ion battery antimony trisulfide based composites prepared by above-mentioned preparation method, this composite is composited by the Graphene of antimony trisulfide with sulfur doping.
Compared with prior art, the invention have the advantages that and technique effect:
1) the invention provides antimony trisulfide and graphene oxide in the aqueous solution under two-step method i.e. room temperature to be combined, low-temperature sintering crystallization be prepared for a kind of morphology controllable, preparation method is simple, raw material is easy to get, with low cost, be prone to the sodium-ion battery antimony trisulfide based composites of large-scale production.
2) Graphene in the composite of the present invention provides loose structure, be conducive to the transmission of sodium ion in charge and discharge process, the Graphene being the most closely coated on antimony trisulfide surface can improve the electron conduction of whole material, and the Graphene being coated on antimony trisulfide surface can alleviate the change in volume in antimony trisulfide charge and discharge process, obtained material has higher capacity, superior high rate performance and cycle performance.
Accompanying drawing explanation
Fig. 1 is business Sb in embodiment 12S3And Sb2S3/ graphene material XRD figure is composed；
Fig. 2 is the Sb of preparation in embodiment 12S3/ graphene material SEM schemes；
Fig. 3 is the Sb of preparation in embodiment 12S3/ graphene material current density is 100 mAh g-1Time first charge-discharge curve chart；
Fig. 4 is business Sb in embodiment 22S3, Graphene and the Sb of preparation2S3/ graphene material Raman schemes；
Fig. 5 is the Sb of preparation in embodiment 22S3/ graphene material TEM schemes；
Fig. 6 is business Sb in embodiment 22S3Sb with preparation2S3/ graphene material is 2 A g in electric current density-1Time cycle performance figure；
Fig. 7 is the Sb of preparation in embodiment 32S3The high rate performance figure of/graphene material；
Fig. 8 is business Sb in embodiment 32S3Sb with preparation2S3/ graphene material SEM figure after 100 circulations.
Detailed description of the invention
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.Following example are intended to illustrate rather than limitation of the invention further.
Embodiment 1:
By 0.1 mmol commercialization Sb2S3Stirring and dissolving is 1000
Ml concentration is 0.1 mol L-1Sodium sulfide solution in (mol ratio of antimony trisulfide and sodium sulfide is 0.001:1), in above-mentioned solution, add 0.1 mg ml-1Graphene oxide solution, making graphene oxide in graphene oxide solution and antimony trisulfide mass ratio is 0.001:1, and supersound process 1 minute.Sodium sulfite and concentration that solution after supersound process joins 50 mmol are 5 mol L-1Sulphuric acid mixed solution in (mol ratio making sodium sulfite and sodium sulfide is 0.5:1, and sulphuric acid is 0.5:1 with the mol ratio of sodium sulfide), stir 5 minutes, is centrifuged, lyophilization precipitate obtains presoma.By this presoma at nitrogen atmosphere 250oC sinters 24 hours, obtains Sb2S3/ graphene material.Sb2S3The physical and chemical performance of/graphene material characterizes sees Fig. 1 and Fig. 2.XRD shows the Sb that the method synthesizes2S3/ graphene material and raw material be thing phase, the purest phase antimony trisulfide material.SEM shows that composite is loose porous, and antimony trisulfide granule is the most tiny, compound with Graphene uniform.Products therefrom is assembled into button cell and surveys its charge/discharge capacity, in the range of 0.01-2.5V, carry out discharge and recharge.Being illustrated in figure 3 electric current density is 100 mAh g-1Time first charge-discharge curve, charging and discharging curve does not has the charge and discharge platform of Graphene, illustrates that clad is not involved in deintercalation sodium.Meanwhile, the capacity of composite reaches 792.8
mAh g-1。
Embodiment 2:
By 30 mmol commercialization Sb2S3Stirring and dissolving is 5 mol L in 2 ml concentration-1Potassium sulfide solution in (mol ratio of antimony trisulfide and Potassium monosulfide. is 3:1), in above-mentioned solution, add 30 mg ml-1Graphene oxide solution, making graphene oxide in graphene oxide solution and antimony trisulfide mass ratio is 0.5:1, and supersound process 600 minutes.Solution after supersound process is joined the ammonium sulfite of 50 mmol, potassium sulfite mixture (ammonium sulfite and potassium sulfite mol ratio 1:1) and 0.01 mol L-1Nitric acid and (making sulphite is 5:1 with the mol ratio of Potassium monosulfide., and acid is 3:1 with the mol ratio of Potassium monosulfide .) in the mixed solution (nitric acid and acetic acid mol ratio 1:3) of acetic acid, stir 10 hours, the presoma that vacuum filtration, forced air drying filtering residue obtain.By this presoma in argon gas atmosphere 550oC sinters 1 hour, obtains Sb2S3/ graphene material.Sb2S3The physical and chemical performance of/graphene material characterizes sees Fig. 4, Fig. 5 and Fig. 6.In Fig. 4, Raman display Graphene success is combined with antimony trisulfide.In Fig. 5, TEM result also indicates that antimony trisulfide and Graphene are compound uniformly.It will be appreciated from fig. 6 that the cyclical stability of composite is increased dramatically, after 200 circulations, capability retention is 96.3%.
Embodiment 3:
By 30 mmol commercialization Sb2S3Stirring and dissolving is 2.5 mol L in 8 ml concentration-1Ammonium sulfide and sodium sulfide mixed solution (ammonium sulfide and sodium sulfide mol ratio 1:3) in (antimony trisulfide is 1.5:1 with the mol ratio of sulphurizing salt), in above-mentioned solution, add 15 mg ml-1Graphene oxide solution, making graphene oxide in graphene oxide solution and antimony trisulfide mass ratio is 0.25:1, and supersound process 300 minutes.By 55 mmol ammonium bisulfites and 35 mmol nitric acid, (making sulphite is 2.75:1 with the mol ratio of sulphurizing salt, acid and the mol ratio of sulphurizing salt are 1.75:1) mixed liquor be poured in above-mentioned solution, stirring 8 hours, centrifugal, vacuum drying precipitate obtains presoma.By this presoma 3%
vol. H2/N2Atmosphere 300oC sinters 5 hours, obtains Sb2S3/ graphene material.Products therefrom is assembled into button cell and surveys its charge/discharge capacity, in the range of 0.01-2.5V, carry out high rate performance test test with cycle life.It is illustrated in figure 7 Sb2S3/ graphene material capacity under different electric current densities.It can be seen that composite has superior high rate performance, such as 5 A g-1During electric current density, Sb2S3/ graphene material capacity is 589.8 mAh g-1.Fig. 8 is business Sb2S3And Sb2S3/ graphene material is 1 A g in electric current density-1Active substance SEM figure on electrode after Shi Xunhuan 200 times.As seen from the figure, business Sb2S3Material efflorescence is serious (a, b as in Fig. 8), and the pattern of composite is well protected (c, d as in Fig. 8).
Claims (9)
1. the preparation method of a sodium-ion battery antimony trisulfide based composites, it is characterised in that comprise the following steps:
(1) antimony trisulfide stirring and dissolving is formed solution in media as well;
(2) in step (1) gained solution, 0.1 ~ 30 is added
mg ml-1Graphene oxide solution, ultrasonic 1 ~ 600 min, until be uniformly dispersed；
(3) step (2) gained solution is sufficiently mixed with sulphite and acid mixed solution, stirs 5 ~ 600 min, obtain amorphous antimony trisulfide and graphene oxide composite material presoma by solid-liquid separation, drying solid；
(4) by composite material precursor 250 ~ 550 DEG C of calcining 1 ~ 24 h under inertia or reducing atmosphere, sodium-ion battery antimony trisulfide based composites is i.e. obtained.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: step (1) described medium is one or more in sodium sulfide, Potassium monosulfide. and ammonium sulfide solution, and concentration is 0.1 ~ 5 mol L-1。
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: step (1) described antimony trisulfide addition is (0.001 ~ 3) with the mol ratio of sulphurizing salt in medium: 1.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: the graphene oxide in graphene oxide solution described in step (2) and antimony trisulfide mass ratio are (0.001 ~ 0.5): 1.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: step (3) described sulphite is one or more in ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite, Potassium acid sulfite and sodium sulfite；The addition of sulphite is (0.5 ~ 5) with the mol ratio of sulphurizing salt in medium: 1.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: the acid described in step (3) is one or more in hydrochloric acid, sulphuric acid, nitric acid, acetic acid, oxalic acid and citric acid；The addition of acid is (0.5 ~ 3) with the mol ratio of sulphurizing salt in medium: 1；The concentration of acid is less than 5 mol L-1。
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that: step (3) is described to be dried as one or more in lyophilization, vacuum drying and forced air drying.
The preparation method of a kind of sodium-ion battery antimony trisulfide based composites the most according to claim 1, it is characterised in that step (4) described inertia or reducing atmosphere are nitrogen, argon, hydrogen or their gaseous mixture.
9. a kind of sodium-ion battery antimony trisulfide based composites prepared by preparation method described in any one of claim 1 ~ 8, it is characterised in that this composite is composited by the Graphene of antimony trisulfide with sulfur doping.
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| CN106654192A (en) * | 2016-08-13 | 2017-05-10 | 华南理工大学 | Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof |
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| CN105720251B (en) | 2018-05-15 |
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