CN105720251B - A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof - Google Patents
A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof Download PDFInfo
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- CN105720251B CN105720251B CN201610099175.1A CN201610099175A CN105720251B CN 105720251 B CN105720251 B CN 105720251B CN 201610099175 A CN201610099175 A CN 201610099175A CN 105720251 B CN105720251 B CN 105720251B
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention discloses a kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof.The preparation method is：Antimony trisulfide is dissolved in medium, add graphene oxide solution, 1 ~ 600min of ultrasound makes its fully dispersed uniformly, mixed with sulphite and acid solution, stir 5 ~ 600min, by separation of solid and liquid, amorphous antimony trisulfide and graphene oxide composite material presoma is dried to obtain, presoma 250 ~ 550 DEG C of 1 ~ 24h of calcining under inertia or reducing atmosphere, obtain sodium-ion battery antimony trisulfide based composites.Composite material prepared by the present invention can be used for anode material of lithium-ion battery, be 2Ag in current density‑1Lower specific capacity reaches 680mAh g‑1, specific capacity conservation rate is more than 96% after 100 circulations.Compared with traditional hydro-thermal method etc., the present invention has that flow is short, process is simple, energy consumption is relatively low, production cost is small, it is easy to accomplish the advantages that large-scale production.
Description
Technical field
The present invention relates to sodium-ion battery Material Field, and in particular to a kind of sodium-ion battery antimony trisulfide based composites and
Its preparation method.
Background technology
Lithium ion battery is as high energy density cells system, in portable electronic product, electric tool and electric automobile
Field is developed rapidly., may limiting lithium ion but lithium resource reserves in the earth's crust are not abundant and expensive
Development of the battery in terms of extensive accumulation power supply.Therefore, development resource is enriched, advanced battery system of low cost, is solution
The inevitable outlet of certainly following extensive storing up electricity application.Sodium element is in same main group with lithium, has similar electronic structure and change
Performance, and sodium element rich reserves in the earth's crust are learned, it is low to refine cost so that sodium-ion battery becomes one kind development very much
One of the energy conversion of prospect and memory device.Therefore, find matched with performance of lithium ion battery, i.e., high power capacity, high magnification and
The sodium electrode material of excellent cycling performance has become the research hotspot in present battery field.
Since sodium element and lithium chemistry are close, the positive electrode of lithium ion battery can use for reference sodium ion anode material
Material, so in sodium-ion battery cathode pole material such as transition metal oxide containing sodium（Such as Na x CoO2, Na x MnO2,
NaNi0.5Mn0.5O2）With polyanionic compound（Such as Na3V2(PO4)3、NaTi2(PO4)3、NaVPO4F, Na2FePO4F）Grind
Originating party face has been achieved for very big progress.But since sodium ion has bigger than lithium ion 55% ionic radius, cause sodium
Ion can not be effectively embedded into and deviate from the graphite material interlamellar spacing with good embedding lithium performance.Therefore, high-performance, low cost are negative
The exploitation of pole material is that sodium-ion battery moves towards commercialized essential step with application.
Table 1
| Sb | Sb2S3 | Sb2O3 | Sb2O4 | |
| Theoretical capacity (mAh g-1) | 660 | 946 | 1109 | 1227 |
The application of Carbon materials such as hard carbon, porous charcoal, carbon nano-fiber on anode material of lithium-ion battery is goed deep into
Research, but the efficiency first of such material is low, capacity is not high is difficult to meet practical application.In contrast, simple substance antimony and
Its compound（Such as table 1）Because specific capacity height causes the interest of researcher.In all antimony-based compounds, antimony trisulfide than simple substance antimony and
Sb oxide has more preferable specific energy density, the volume change of smaller and more preferably cycle performance.In order to further improve sulphur
Change the chemical property of antimony, nanosizing and composite graphite alkene are effective cycle life alleviated material dusting, improve material
Effective means.The price height of persursor material needed for nanometer antimony and its compound and graphene composite material reported in the literature,
And the preparation process for the material much reported is complicated, these shortcomings limit the extensive of antimony trisulfide/graphene composite material
Using.The embodiment of the present invention with commercialized for primary raw material, by two-step method be in aqueous solution at room temperature antimony trisulfide with
Graphene oxide is compound, and low-temperature sintering crystallization is prepared for that a kind of pattern is reliable, preparation method is simple, raw material are easy to get, cost is low
Antimony trisulfide/graphene composite material that is honest and clean, being easy to large-scale production.Graphene in composite material provides loose structure, favorably
The transmission of sodium ion in charge and discharge process, whole material can be improved by being in addition closely coated on the graphene on antimony trisulfide surface
Electron conduction, and the graphene for being coated on antimony trisulfide surface can alleviate the volume change in antimony trisulfide charge and discharge process,
Obtained material has higher capacity, superior high rate performance and cycle performance, particularly suitable as the secondary electricity of sodium ion
The negative material in pond.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of sodium-ion battery antimony trisulfide based composites and its preparation
Method, the composition of the composite material is Sb2S3/ graphene.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of sodium-ion battery antimony trisulfide based composites, comprises the following steps：
(1) antimony trisulfide stirring and dissolving is formed into solution in media as well;
(2) toward 0.1 ~ 30 mg ml of addition in step (1) resulting solution-1Graphene oxide solution, ultrasound 1 ~ 600
Min, until being uniformly dispersed；
(3) step (2) resulting solution and sulphite and sour mixed solution are sufficiently mixed, stir 1 ~ 600 min, led to
Cross separation of solid and liquid, drying solid obtains amorphous antimony trisulfide and graphene oxide composite material presoma；
(4) composite material precursor is calcined into 1 ~ 24 h for 250 ~ 550 DEG C under inertia or reducing atmosphere, that is, obtains sodium
Ion battery antimony trisulfide based composites.
Further, step（1）The medium is the one or more in vulcanized sodium, potassium sulfide and ammonium sulfide solution,
Concentration is 0.1 ~ 5 mol L-1, antimony trisulfide occurs to chemically react with medium forms [SbS3]3-And dissolve.
Further, step（1）The antimony trisulfide addition and the molar ratio of sulphurizing salt in medium are（0.001~3）：1.
Further, step（2）Graphene oxide in the graphene oxide solution is with antimony trisulfide mass ratio
（0.001~0.5）：1.
Further, step（3）The sulphite for ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite,
One or more in potassium bisulfite and sodium hydrogensulfite；The molar ratio of sulphurizing salt is in the addition and medium of sulphite
（0.5~5）：1.
Further, step（3）The acid be hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid in one kind or
It is several；The molar ratio of sulphurizing salt is in the addition and medium of acid（0.5~3）：1；The concentration of acid is less than 5 mol L-1。
Step（3）Sulphite and acid be precipitating reagent, the purpose for adding precipitating reagent is to consume the S in solution2-From
Son, makes antimony trisulfide and sulphur be deposited in surface of graphene oxide, the reaction of generation is as follows：4[SbS3]3- + 3SO3 2- + 18H+ →
6S + 9H2O + 2Sb2S3。
Further, step（3）The mixing time is 5 ~ 600 min.
Further, step（3）The drying is the one or more in freeze-drying, vacuum drying and forced air drying.
Further, step（4）Either reducing atmosphere is nitrogen, argon gas, hydrogen or their gaseous mixture to the inertia.
A kind of sodium-ion battery antimony trisulfide based composites as made from above-mentioned preparation method, the composite material is by antimony trisulfide
It is combined with the graphene of sulfur doping.
Compared with prior art, the invention has the advantages that and technique effect：
1）It is that antimony trisulfide and graphene oxide are compound in aqueous solution at room temperature the present invention provides two-step method, low temperature burning
Junction crystalline substance is prepared for the sodium that a kind of morphology controllable, preparation method are simple, raw material are easy to get, are of low cost, being easy to large-scale production
Ion battery antimony trisulfide based composites.
2）Graphene in the composite material of the present invention provides loose structure, is conducive to the biography of sodium ion in charge and discharge process
Defeated, the electron conduction of whole material can be improved by being in addition closely coated on the graphene on antimony trisulfide surface, and be coated on sulphur
The graphene on change antimony surface can alleviate the volume change in antimony trisulfide charge and discharge process, and obtained material has higher appearance
Amount, superior high rate performance and cycle performance.
Brief description of the drawings
Fig. 1 is business Sb in embodiment 12S3And Sb2S3/ graphene material XRD spectrums；
Fig. 2 is the Sb prepared in embodiment 12S3/ graphene materials SEM schemes；
Fig. 3 is the Sb prepared in embodiment 12S3/ graphene material currents density is 100 mAh g-1When fill first
Discharge curve；
Fig. 4 is business Sb in embodiment 22S3, graphene and preparation Sb2S3/ graphene materials Raman schemes；
Fig. 5 is the Sb prepared in embodiment 22S3/ graphene materials TEM schemes；
Fig. 6 is business Sb in embodiment 22S3With the Sb of preparation2S3/ graphene materials are 2 A g in current density-1When
Cycle performance figure；
Fig. 7 is the Sb prepared in embodiment 32S3The high rate performance figure of/graphene materials；
Fig. 8 is business Sb in embodiment 32S3With the Sb of preparation2S3The SEM figure of/graphene materials after 100 circulations.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.Following embodiments are intended to illustrate hair
Bright rather than limitation of the invention further.
Embodiment 1：
0.1 mmol is commercialized Sb2S3Stirring and dissolving is 0.1 mol L in 1000 ml concentration-1Sodium sulfide solution in
（The molar ratio of antimony trisulfide and vulcanized sodium is 0.001：1）, 0.1 mg ml are added into above-mentioned solution-1Graphene oxide solution,
It is 0.001 to make the graphene oxide in graphene oxide solution and antimony trisulfide mass ratio：1, and be ultrasonically treated 1 minute.By ultrasound
Solution after processing is added to the sodium sulfite of 50 mmol and concentration is 5 mol L-1Sulfuric acid mixed solution in（Make sulfurous
The molar ratio of sour sodium and vulcanized sodium is 0.5：1, the molar ratio of sulfuric acid and vulcanized sodium is 0.5：1）, stir 5 minutes, centrifugation, freezing
Dry sediment obtains presoma.By the presoma in nitrogen atmosphere 250oWhen C sintering 24 is small, Sb is obtained2S3/ graphene materials
Material.Sb2S3The physical and chemical performance characterization of/graphene materials is shown in Fig. 1 and Fig. 2.XRD shows the Sb of this method synthesis2S3/
Graphene materials are the same thing phase, i.e. pure phase antimony trisulfide material with raw material.SEM shows that composite material is loose porous, and
It is very tiny to vulcanize antimony particle, it is compound uniformly with graphene.Products therefrom is assembled into button cell and surveys its charge/discharge capacity,
Discharge and recharge is carried out in the range of 0.01-2.5V.It is 100 mAh g to be illustrated in figure 3 current density-1When first charge-discharge curve,
Charging and discharging curve does not have the charge and discharge platform of graphene, illustrates that clad is not involved in deintercalation sodium.Meanwhile the capacity of composite material reaches
To 792.8 mAh g-1。
Embodiment 2：
30 mmol are commercialized Sb2S3Stirring and dissolving is 5 mol L in 2 ml concentration-1Potassium sulfide solution in（Antimony trisulfide
Molar ratio with potassium sulfide is 3：1）, 30 mg ml are added into above-mentioned solution-1Graphene oxide solution, make graphene oxide
Graphene oxide and antimony trisulfide mass ratio in solution are 0.5：1, and be ultrasonically treated 600 minutes.By the solution after supersound process
It is added to ammonium sulfite, the potassium sulfite mixture of 50 mmol（Ammonium sulfite and potassium sulfite molar ratio 1:1）With 0.01 mol
L-1The mixed solution of nitric acid and acetic acid（Nitric acid and acetic acid molar ratio 1:3）In（It is 5 to make the molar ratio of sulphite and potassium sulfide：
1, sour and potassium sulfide molar ratio is 3：1）, when stirring 10 is small, it is filtered by vacuum, the presoma that forced air drying filter residue obtains.Should
Presoma is in argon gas atmosphere 550oWhen C sintering 1 is small, Sb is obtained2S3/ graphene materials.Sb2S3The materialization of/graphene materials
Performance characterization is shown in Fig. 4, Fig. 5 and Fig. 6.Raman shows that graphene success is compound with antimony trisulfide in Fig. 4.TEM results also table in Fig. 5
Bright antimony trisulfide is compound uniformly with graphene.It will be appreciated from fig. 6 that the cyclical stability of composite material is increased dramatically, 200 circulations
Capacity retention ratio is 96.3% afterwards.
Embodiment 3：
30 mmol are commercialized Sb2S3Stirring and dissolving is 2.5 mol L in 8 ml concentration-1Ammonium sulfide mixed with vulcanized sodium
Close solution（Ammonium sulfide and vulcanized sodium molar ratio 1:3）In（The molar ratio of antimony trisulfide and sulphurizing salt is 1.5：1）, into above-mentioned solution
Add 15 mg ml-1Graphene oxide solution, make the graphene oxide in graphene oxide solution be with antimony trisulfide mass ratio
0.25：1, and be ultrasonically treated 300 minutes.By 55 mmol ammonium bisulfites and 35 mmol nitric acid（Make sulphite and sulphurizing salt
Molar ratio be 2.75：1, sour and sulphurizing salt molar ratio is 1.75：1）Mixed liquor be poured into above-mentioned solution, stirring is 8 small
When, centrifugation, vacuum drying sediment obtain presoma.By the presoma in 3% vol. H2/N2Atmosphere 300oWhen C sintering 5 is small,
Obtain Sb2S3/ graphene materials.Products therefrom is assembled into button cell and surveys its charge/discharge capacity, in 0.01-2.5V scopes
Interior progress high rate performance test is tested with cycle life.It is illustrated in figure 7 Sb2S3/ graphene materials are under different current densities
Capacity.It can be seen from the figure that composite material has superior high rate performance, such as 5 A g-1During current density, Sb2S3/
Graphene material capacities are 589.8 mAh g-1.Fig. 8 is business Sb2S3And Sb2S3/ graphene materials are 1 in current density
A g-1Active material SEM figures on electrode after Shi Xunhuan 200 times.As seen from the figure, business Sb2S3Material dusting is serious（Such as
A, b in Fig. 8）, the pattern of composite material protected well（Such as c, d in Fig. 8）.
Claims (7)
1. a kind of preparation method of sodium-ion battery antimony trisulfide based composites, it is characterised in that comprise the following steps：
(1) antimony trisulfide stirring and dissolving is formed into solution in media as well;
(2) toward 0.1 ~ 30 mg ml of addition in step (1) resulting solution-1Graphene oxide solution, 1 ~ 600 min of ultrasound, directly
To being uniformly dispersed；Graphene oxide in the graphene oxide solution is with antimony trisulfide mass ratio（0.001~0.5）：1；
(3) step (2) resulting solution and sulphite and sour mixed solution are sufficiently mixed, stir 5 ~ 600 min, by solid
Liquid separation, drying solid obtain amorphous antimony trisulfide and graphene oxide composite material presoma；
(4) composite material precursor is calcined into 1 ~ 24 h for 250 ~ 550 DEG C under non-oxidizing atmosphere, that is, obtains sodium-ion battery
Antimony trisulfide based composites；The non-oxidizing atmosphere is nitrogen, argon gas, hydrogen or their gaseous mixture.
A kind of 2. preparation method of sodium-ion battery antimony trisulfide based composites according to claim 1, it is characterised in that：
Step（1）The medium is the one or more in vulcanized sodium, potassium sulfide and ammonium sulfide solution, and concentration is 0.1 ~ 5 mol L-1。
A kind of 3. preparation method of sodium-ion battery antimony trisulfide based composites according to claim 1, it is characterised in that：
Step（1）The antimony trisulfide addition and the molar ratio of sulphurizing salt in medium are（0.001~3）：1.
A kind of 4. preparation method of sodium-ion battery antimony trisulfide based composites according to claim 1, it is characterised in that：
Step（3）The sulphite is ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite and sulfurous acid
One or more in hydrogen sodium；The molar ratio of sulphurizing salt is in the addition and medium of sulphite（0.5~5）：1.
A kind of 5. preparation method of sodium-ion battery antimony trisulfide based composites according to claim 1, it is characterised in that：
Step（3）The acid is the one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid；Acid addition with
The molar ratio of sulphurizing salt is in medium（0.5~3）：1；The concentration of acid is less than 5 mol L-1。
A kind of 6. preparation method of sodium-ion battery antimony trisulfide based composites according to claim 1, it is characterised in that：
Step（3）The drying is the one or more in freeze-drying, vacuum drying and forced air drying.
7. a kind of sodium-ion battery antimony trisulfide based composites as made from any one of claim 1 ~ 6 preparation method, its
It is characterized in that, which is combined by the graphene of antimony trisulfide and sulfur doping.
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| CN106654192B (en) * | 2016-08-13 | 2020-02-18 | 华南理工大学 | Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof |
| CN107195877A (en) * | 2017-05-04 | 2017-09-22 | 大连理工大学 | A kind of sodium-ion battery graphene/Sb2S3The preparation method of/carbon composite |
| CN107331842A (en) * | 2017-06-30 | 2017-11-07 | 华南理工大学 | It is a kind of with the antimony trisulfide base negative material of high reversible capacity and its preparation and application |
| CN108400298B (en) * | 2018-02-08 | 2020-11-17 | 陕西科技大学 | Method for preparing graphene-loaded antimony nanotube negative electrode material for sodium ion battery and application of graphene-loaded antimony nanotube negative electrode material |
| CN108624634B (en) * | 2018-04-19 | 2021-09-21 | 华南理工大学 | Method for preparing sugar ester derivative with antibacterial function by enzyme method |
| CN110776006B (en) | 2018-07-27 | 2023-07-21 | 香港科技大学 | Preparation method of ultrathin antimony sulfide nanosheets serving as lithium/sodium ion battery anode materials |
| CN110364706B (en) * | 2019-06-27 | 2021-07-20 | 华南理工大学 | Antimony oxide-based negative electrode material with high reversible capacity and preparation method thereof |
| CN110444738A (en) * | 2019-08-22 | 2019-11-12 | 中南大学 | A method of preparing lithium ion battery micropore carbon adsorption stibnite composite negative pole |
| CN111129489B (en) * | 2019-11-29 | 2022-02-11 | 上海应用技术大学 | Graphene-based antimony sulfide negative electrode material and preparation method and application thereof |
| CN111554886B (en) * | 2020-04-02 | 2021-05-18 | 中南林业科技大学 | Lamellar Sb @ Sb-In-S @ rGO sodium ion battery anode material and preparation method thereof |
| CN111410702A (en) * | 2020-05-06 | 2020-07-14 | 扬州日兴生物科技股份有限公司 | Modified chitosan and preparation method thereof |
| CN111933900B (en) * | 2020-06-23 | 2022-05-10 | 南京农业大学 | Antimony sulfide/graphene composite nano material and preparation method and application thereof |
| CN112072088B (en) * | 2020-08-26 | 2022-03-29 | 西安建筑科技大学 | Nano nitrogen-doped stibnite composite material, preparation method and application thereof |
| CN112072107B (en) * | 2020-08-28 | 2022-07-05 | 中南大学 | Antimony sulfide-based composite material and preparation method and application thereof |
| CN113540457A (en) * | 2021-06-11 | 2021-10-22 | 南京理工大学 | Graphene composite amorphous metal-based sulfide electrode material and preparation method thereof |
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