CN103553129B - Application of sodium ion battery cathode material sodium bismuth disulfide nanoparticles - Google Patents
Application of sodium ion battery cathode material sodium bismuth disulfide nanoparticles Download PDFInfo
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- CN103553129B CN103553129B CN201310524153.1A CN201310524153A CN103553129B CN 103553129 B CN103553129 B CN 103553129B CN 201310524153 A CN201310524153 A CN 201310524153A CN 103553129 B CN103553129 B CN 103553129B
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- sodium
- bismuth
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- nabis
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses sodium ion battery cathode material sodium bismuth disulfide nanoparticles and a preparation method. The sodium bismuth disulfide nanoparticles with diameters of 100-150nm are prepared by treating carbon disulfide, bismuth nitrate and bismuth nitrate by a solvothermal method, wherein the chemical formula is NaBiS2. The process is simple, the repeatability is good, and the yield is high; the synthesis conditions are mild, and the cost is low; the prepared electrode material has a large specific capacity.
Description
Technical field
The invention belongs to cell negative electrode material preparation field, be specifically related to a kind of anode material of lithium-ion battery curing bismuth sodium nano particle and preparation method.
Background technology
Sodium-ion battery because of sodium aboundresources, distribute wide and cost is low, the operating voltage that sodium-ion battery is lower can strengthen stability and the security of electrolytic solution in non-aqueous battery, causes that people's wide model is paid close attention to.Can not reversible deintercalation sodium ion due to business-like graphite as anode material for lithium-ion battery, be not suitable as the negative material of sodium-ion battery.Therefore, find suitable anode material of lithium-ion battery and become the focus of Materials science research.
Sodium-ion battery is because the larger radius of sodium ion, conventionally cause in electrochemical reaction process sodium ion velocity of diffusion slow, difficult insertion and deintercalation are in negative material, after intercalation, crystalline structure is reset, therefore sodium-ion battery material exists, capacity is low, cyclical stability is poor, can not carry out high rate charge-discharge, the specific discharge capacity of stable circulation is 200 mAhg
-1left and right.This class battery material mainly contains Na
2ti
3o
7[P. Senguttuvan, G. Rousse, V. Seznec, J.M. Tarascon, M. R. Palac í n,
chem. Mater. 23 (2011) 4109.], carbon material: as reduced form Graphene [Y.X. Wang, S.L. Chou, H.K. Liu, S.X. Dou,
carbon, 202 (2013) 57.] and Na
3ti
2(PO
4)
3[P. Senguttuvan, G. Rousse, M.E. Arroyo y de Dompablo, H. Vezin, J.M. Tarascon, M. R. Palac í n,
j. Am. Chem. Soc. 135 (2013) 3897.] etc.Transition metal oxide, as sodium ion negative material, improves the specific discharge capacity of negative material, SnO significantly
2nanometer octahedron is at 20 mAhg
-1current density under discharge, specific discharge capacity reaches 420 mAhg
-1[D. Su, C. Wang, G. Wang, Phys.
chem. Phys. 15 (2013) 12543-50.].Up to the present, metallic antimony Sb, as negative pole, represents good cyclical stability and higher specific discharge capacity, and the specific discharge capacity that stable circulation is 160 times reaches 600 mAhg
-1, coulomb efficiency reaches 99%[A. Darwiche, C. Marino, and M.T. Sougrati, B. Fraisse, L. Stieva, L. Monconduit,
j. Am. Chem. Soc. 134 (2012) 20805.].But antimony element is poisonous, limit its application.Therefore, the anode material of lithium-ion battery of searching novel environment friendly, heavy body and stable circulation is imperative.Although curing bismuth sodium has advantages of cheapness, environmental protection and nontoxic.But few about the synthetic and application report of curing bismuth sodium, have no its report aspect battery electrode material.
Summary of the invention
The object of the present invention is to provide a kind of anode material of lithium-ion battery curing bismuth sodium nano particle and preparation method, technique is simple, reproducible, and productive rate is high; Synthesis condition gentleness, cost is low; Prepared electrode materials specific storage is high.
For achieving the above object, the present invention adopts following technical scheme:
Process dithiocarbonic anhydride, Bismuth trinitrate and sodium hydroxide by solvent-thermal method and make the curing bismuth sodium nano particle that diameter is 100-150nm, its chemical formula is: NaBiS
2.
Preparation method comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 2-200 h is reacted in sealing at 120-200 DEG C, filters, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
In the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:30-1:15.
The mol ratio of sodium hydroxide and Bismuth trinitrate is 10:1-5:1.
NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the propylene carbonate ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
Remarkable advantage of the present invention is: the present invention adopts raw material cheaply, and without the hydrothermal synthesis method of template, environmentally friendly, simple, productive rate is high, and size is even, good dispersity, and favorable reproducibility, is easy to scale operation.This curing bismuth sodium, as the negative material of sodium-ion battery, represents higher specific discharge capacity and cyclical stability, and the specific discharge capacity that stable circulation is 6 times reaches 485 mAhg
-1.There is discharge platform at low voltage 0.4V in the discharge curve of curing bismuth sodium, is the very promising anode material of lithium-ion battery of one.
Brief description of the drawings
The scanning electron microscope (SEM) photograph of the curing bismuth sodium of Fig. 1 embodiment of the present invention 1.
The XRD figure of the curing bismuth sodium of Fig. 2 embodiment of the present invention 1.
The charging and discharging curve (a) and the cycle performance figure (b) that circulate for the second time and for the third time of the curing bismuth sodium nano particle of Fig. 3 embodiment of the present invention 1.
The scanning electron microscope (SEM) photograph of the curing bismuth sodium of Fig. 4 embodiment of the present invention 2.
The scanning electron microscope (SEM) photograph of the curing bismuth sodium of Fig. 5 embodiment of the present invention 3.
Embodiment
Process dithiocarbonic anhydride, Bismuth trinitrate and sodium hydroxide by solvent-thermal method and make the curing bismuth sodium nano particle that diameter is 100-150nm, its chemical formula is: NaBiS
2.
Preparation method comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 2-200 h is reacted in sealing at 120-200 DEG C, filters, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
In the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:30-1:15.
The mol ratio of sodium hydroxide and Bismuth trinitrate is 10:1-5:1.
NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the propylene carbonate ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
Embodiment 1
The preparation method of curing bismuth sodium nano particle comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 200 h are reacted in sealing at 120 DEG C, filter, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
In the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:30.
The mol ratio of sodium hydroxide and Bismuth trinitrate is 10:1.
NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the propylene carbonate ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
Embodiment 2
The preparation method of curing bismuth sodium nano particle comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 2 h are reacted in sealing at 200 DEG C, filter, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
In the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:15.
The mol ratio of sodium hydroxide and Bismuth trinitrate is 5:1.
NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the propylene carbonate ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
Embodiment 3
The preparation method of curing bismuth sodium nano particle comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 100 h are reacted in sealing at 160 DEG C, filter, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
In the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:15.
The mol ratio of sodium hydroxide and Bismuth trinitrate is 10:1.
NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the propylene carbonate ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. an application for curing bismuth sodium nano particle, is characterized in that: process dithiocarbonic anhydride, Bismuth trinitrate and sodium hydroxide by solvent-thermal method and make the curing bismuth sodium nano particle that diameter is 100-150nm, its chemical formula is: NaBiS
2; By NaBiS
2nano particle is as the active ingredient of the negative material of sodium-ion battery, and conductive agent is ultrapure carbon, and binding agent is polyvinylidene difluoride (PVDF), and three's mass ratio is 7:2:1; Ionogen is the carbonic allyl ester solution of 1 M sodium perchlorate; Battery case is CR2025 model, and collector is copper sheet, and barrier film is glass fibre membrane; Sodium Metal 99.5 sheet is as positive pole, and battery has been assembled under argon shield.
2. the application of curing bismuth sodium nano particle according to claim 1, is characterized in that: NaBiS
2the preparation method of nano particle comprises the following steps:
(1) sodium hydroxide is dissolved in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol;
(2) under magnetic agitation, Bismuth trinitrate is joined in the mixing solutions of step (1), continue to stir 2 hours;
(3) solution of step (2) is moved in reactor, 2-200 h is reacted in sealing at 120-200 DEG C, filters, and with after a large amount of deionized waters and absolute ethanol washing, 60 DEG C of dry 12 h, obtain NaBiS
2nano particle.
3. the application of curing bismuth sodium nano particle according to claim 2, is characterized in that: in the mixed solvent of dithiocarbonic anhydride and dehydrated alcohol, the volume ratio of dithiocarbonic anhydride and dehydrated alcohol is 1:30-1:15.
4. the application of curing bismuth sodium nano particle according to claim 1, is characterized in that: the mol ratio of sodium hydroxide and Bismuth trinitrate is 10:1-5:1.
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| CN201310524153.1A CN103553129B (en) | 2013-10-31 | 2013-10-31 | Application of sodium ion battery cathode material sodium bismuth disulfide nanoparticles |
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| CN105668624A (en) * | 2015-12-31 | 2016-06-15 | 上海应用技术学院 | Method for preparing microcrystalline Bi-S based semiconductor material through strong alkali hydrothermal technology |
| CN106450247B (en) * | 2016-10-28 | 2020-02-21 | 南开大学 | Metal bismuth negative electrode and ether-based electrolyte for sodium/potassium ion secondary battery |
| CN116031404B (en) * | 2022-12-21 | 2024-09-27 | 昆明理工大学 | Method for constructing surface electron migration channel of bismuth-based anode material |
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Non-Patent Citations (6)
| Title |
|---|
| Largle-Scale Synthesis of Ultralong Bi2S3 Nanoribbons via a Solvothermal Process;Zhaoping Liu et al.;《Advanced Materials》;20030605;第15卷(第11期);936-940 * |
| Synthesis and Growth Mechanism of Bi2S3 Nanoribbons;Zhaoping Liu et al.;《Chem. Eur. J.》;20040202;第10卷;634-640 * |
| Zhaoping Liu et al..Largle-Scale Synthesis of Ultralong Bi2S3 Nanoribbons via a Solvothermal Process.《Advanced Materials》.2003,第15卷(第11期),936-940. * |
| Zhaoping Liu et al..Synthesis and Growth Mechanism of Bi2S3 Nanoribbons.《Chem. Eur. J.》.2004,第10卷634-640. * |
| 张小敏等.硫化铋纳米管的制备及性能研究.《人工晶体学报》.2013,第42卷(第6期),1070-1076. * |
| 硫化铋纳米管的制备及性能研究;张小敏等;《人工晶体学报》;20130630;第42卷(第6期);1070-1076 * |
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