CN102229439B - Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material - Google Patents
Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material Download PDFInfo
- Publication number
- CN102229439B CN102229439B CN201110101600A CN201110101600A CN102229439B CN 102229439 B CN102229439 B CN 102229439B CN 201110101600 A CN201110101600 A CN 201110101600A CN 201110101600 A CN201110101600 A CN 201110101600A CN 102229439 B CN102229439 B CN 102229439B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- battery negative
- tin dioxide
- choline chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a low-temperature preparation method of a nano-crystalline tin dioxide lithium ion battery negative electrode material. The method is characterized in that SnCl2.2H2O and hydrazine hydrate used as reactants react in choline chloride based eutectic solvent type ion liquid used as a reactive solvent to produce a tin dioxide lithium ion battery negative electrode material with crystallite dimension being less than 10nm. The materials used in the method provided by the invention are easy to obtain, and the preparation process is simple; nano SnO2 powder prepared at room temperature does not need calcining at a high temperature, the requirement on equipment is low, and the preparation process is finished in a short time; the prepared nano-crystalline tin dioxide lithium ion battery negative electrode material has higher reversible capacity and cycle performance; and the method provided by the invention is not restricted by regions, has the advantages of energy-saving and environmentally-friendliness and the like, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the lithium ion battery negative material preparation field, be specifically related to a kind of low temperature preparation method of nanocrystalline structure tin dioxide lithium ion battery negative pole material.
Background technology
Lithium-ions battery is as a kind of high performance green power supply of filling; In various portable type electronic products and communication tool, be used widely in recent years; To progressively be developed as the electrical source of power of electromobile, be developed thereby promote its direction to safety, environmental protection, low cost and high-energy-density.The fast development of novel high-energy chemical power source technology is had higher requirement to battery material, and high-energy-density, high power density, low cost, environment amenable novel battery material are the present and following research emphasis.The negative material of lithium ion battery is the key factor that improves lithium ion battery reversible capacity and cycle life.At present, carbon material (comprising graphite, soft carbon and hard carbon) is the main negative material of commercial lithium ion battery.But the storage lithium ability of carbon material lower (theoretical specific capacity is 372 mAh/g) has limited the further raising of capacity of lithium ion battery.SnO
2Owing to have higher lithium storage content (781 mAh/g), be a kind of very promising lithium ion battery negative material.Yet this material volume change in charge and discharge process is bigger, and can form Li
2The irreversible reaction of O causes its relatively poor cycle performance.Research shows that the electrode materials with nanostructure has higher specific surface area, and the lithium ion insert depth is little in charge and discharge process, and has bigger space between the nanoparticle, this feasible SnO with nanostructure
2Particle can reduce the influence of volume change in charge and discharge process, thereby makes electrode be not easy fragmentation, improves the cycle performance of battery, prolongs the work-ing life of battery.
Wet chemistry method such as hydro-thermal or solvent thermal is used to prepare SnO usually
2Various nanostructures, like nano-powder, nano wire, nano-hollow ball, nanotube etc.SnO
2Nano-hollow ball and nano tube structure generally need template to assist the formation of its nanostructure, make preparation technology become loaded down with trivial details.And the precursor reagent that wet chemistry method obtains generally will be passed through comparatively high temps (>400 ° of C) calcination processing just can obtain being applied to the nanostructure SnO of lithium ion battery negative material
2Therefore, consider, seek the easy synthesis of nano crystal structure SnO of a kind of low temperature from controlling of production process and energy-conserving and environment-protective aspect
2The preparation method of lithium ion battery negative material has very big pushing effect for heavy body tinbase negative material.
Ionic liquid at room temperature be by specific organic cation and negatively charged ion constitute in room temperature or near the molten salt system that is in a liquid state under the room temperature, it has the physical and chemical performance of a series of uniquenesses, is a kind of real " green " solvent.Dark congruent melting solvent-borne type ionic liquid [A. P. Abbott, D. Boothby, G. Capper; D. L. Davies and R. K. Rasheed, J. Am. Chem. Soc., 2004; 126,9142-9147] have and synthesize peculiar advantages such as simple, cheap, that purity is high, application is easy.In addition, dark congruent melting solvent is biodegradable organism mostly.Therefore, in view of ion liquid numerous advantages, with dark congruent melting solvent-borne type ionic liquid as solvent, nano SnO
2The low-temperature fabrication of lithium ion battery negative material has wide application value.
Summary of the invention
The low temperature preparation method that the purpose of this invention is to provide a kind of nanocrystalline structure tin dioxide lithium ion battery negative pole material.
Its step of the low temperature preparation method of nanocrystalline structure tin dioxide lithium ion battery negative pole material of the present invention is following:
(1) with SnCl
22H
2O is dissolved in the dark congruent melting solvent of choline chloride 60 base, stirs, and is mixed with the reaction soln that concentration is 10.0 ~ 50.0 g/L;
(2) stir down; Speed with 0.5 ~ 3 ml/min in above-mentioned every liter of reaction soln adds 20 ~ 60 ml Hydrazine Hydrate 80s; Under the room temperature, methyl alcohol and washed with de-ionized water precipitated product are used in spinning behind reaction 1 ~ 3 h successively; Dry under 40 ~ 100 ° of C then, obtain the nanocrystalline structure tin dioxide lithium ion battery negative pole material.
Further, the dark congruent melting solvent of the choline chloride 60 base in the above-mentioned steps (1) is a choline chloride 60 and terepthaloyl moietie 1:2 mixed solution in molar ratio, or choline chloride 60 and urea 1:2 mixed solution in molar ratio.
Adopt the dark congruent melting solvent-borne type of choline chloride 60 base ionic liquid as reaction solvent among the present invention, SnCl
22H
2O is as Xi Yuan, Hydrazine Hydrate 80 (N
2H
4H
2O) as reductive agent.Its reaction mechanism is N
2H
4H
2Sn in the O reduction reaction system
2+, in solution, at first form nano metal Sn particle because nanometer Sn grain-size is minimum, have high reaction activity and high, will be spontaneous change SnO into
2
The invention has the advantages that:
Raw materials used common being easy to get of the inventive method, preparation technology is easy should to go.Reaction system composition of the present invention is simple, and preparation is convenient, does not contain corrosives.Friendly with the dark congruent melting solvent of choline chloride 60 base as solvent environment.The nano SnO for preparing under the room temperature
2Powder grain size is less than 10 nm, and good uniformity need not high-temperature calcination and handles, and is low for equipment requirements, consuming time few.The tindioxide that the present invention obtains has high specific surface area, when using as lithium ion battery negative material, has higher reversible capacity and cycle performance.The nanocrystalline structure tindioxide that the present invention obtains also can be used as support of the catalyst, air-sensitive and humidity-sensitive material and uses; The low temperature preparation method of nanocrystalline structure tin dioxide lithium ion battery negative pole material disclosed by the invention is not limited by the region; Have advantages such as energy-conserving and environment-protective, be fit to large-scale commercial prodn.
Description of drawings
Fig. 1 is the nanocrystalline SnO that obtains of embodiment 1
2Transmission electron micrograph.
Fig. 2 is the nanocrystalline SnO that obtains of embodiment 2
2Transmission electron micrograph.
Fig. 3 is nanocrystalline SnO
2The charge and discharge cycles curve of lithium ion battery negative material, the current density of constant current charge-discharge are respectively 50 mA/g and 100 mA/g.
Embodiment
Embodiment 1:
Choline chloride 60 and terepthaloyl moietie are mixed under 75 ° of C according to mol ratio 1:2, obtain the dark congruent melting solvent of choline chloride 60 base.With 15.00 g SnCl
22H
2O is dissolved in 1 liter of dark congruent melting solvent of choline chloride 60 base, at this moment SnCl in the reaction soln
22H
2The concentration of O is 15g/L, and magnetic agitation is even.Under the room temperature, in above-mentioned 1 liter of reaction soln, with the slow 40 ml Hydrazine Hydrate 80 (N that add of the rate of addition of 1 ml/min
2H
4H
2O), in the dropping process, reaction soln keeps high-speed stirring, reacts 2 h then.Precipitated product adopts spinning, uses washed with methanol then three times, and is with washed with de-ionized water once dry under 60 ° of C at last, promptly obtains nanocrystalline SnO
2Lithium ion battery negative material, its transmission electron micrograph is as shown in Figure 1.Can find out SnO by Fig. 1
2Nanocrystalline perfect crystalline, grain size is evenly distributed, and average grain size is 4 nm.
Embodiment 2:
Choline chloride 60 and urea are mixed under 75 ° of C according to mol ratio 1:2, obtain the dark congruent melting solvent of choline chloride 60 base.With 30.00 g SnCl
22H
2O is dissolved in 1 liter of dark congruent melting solvent of choline chloride 60 base, at this moment SnCl in the reaction soln
22H
2The concentration of O is 30 g/L.Under the room temperature, in above-mentioned 1 liter of reaction soln, with the slow 40 ml Hydrazine Hydrate 80 (N that add of the rate of addition of 0.5 ml/min
2H
4H
2O), in the dropping process, reaction soln keeps high-speed stirring, reacts 3 h then.Precipitated product adopts spinning, uses washed with methanol then three times, and is with washed with de-ionized water once dry under 40 ° of C at last, promptly obtains nanocrystalline SnO
2Lithium ion battery negative material, its transmission electron micrograph is as shown in Figure 2.Can find out SnO by Fig. 2
2Nanocrystalline perfect crystalline, grain size is evenly distributed, and average grain size is 7 nm.
Embodiment 3:
Choline chloride 60 and terepthaloyl moietie are mixed under 75 ° of C according to mol ratio 1:2, obtain the dark congruent melting solvent of choline chloride 60 base.With 15.00 g SnCl
22H
2O is dissolved in 1 liter of dark congruent melting solvent of choline chloride 60 base, at this moment SnCl in the reaction soln
22H
2The concentration of O is 15g/L, and magnetic agitation is even.Under the room temperature, in above-mentioned 1 liter of reaction soln, with the slow 60 ml Hydrazine Hydrate 80 (N that add of the rate of addition of 3 ml/min
2H
4H
2O), in the dropping process, reaction soln keeps high-speed stirring, reacts 3 h then.Precipitated product adopts spinning, uses washed with methanol then three times, and is with washed with de-ionized water once dry under 90 ° of C at last, promptly obtains nanocrystalline SnO
2Lithium ion battery negative material.Its crystal morphology and Fig. 1 are similar, SnO
2Nanocrystalline perfect crystalline, grain size is evenly distributed, and average grain size is 5 nm.
With embodiment 1, the nanocrystalline SnO of embodiment 2 and embodiment 3
2Powder as follows, is assembled into battery as lithium ion battery negative material.
With embodiment 1, the nanocrystalline SnO of embodiment 2 and embodiment 3
2As electrode active material and tackiness agent PVDF (PVDF) and the black mixed of pressing 80:5:15 of conductive acetylene; Add 1-Methyl-2-Pyrrolidone (NMP) and be stirred into slurry; Evenly be coated in copper foil surface, then pole piece dried 12 h down at 85 ℃.After the roll squeezer compacting, place vacuum drying oven again electrode slice, divide the negative plate that cuts into lithium ion battery in 90 ℃ of drying 8 h.
The electrode slice of processing is assembled into the lithium ion half-cell carries out Performance Detection, metal Li sheet is as SnO
2Counter electrode.Electrolytic solution is to contain 1 mol/L LiPF
6DEC+EC (volume ratio DEC:EC=7:3), barrier film is used Vestolen PP 7052 Celgard2300.The battery assembling process is accomplished in relative humidity is lower than 1% dry glove box.The battery that assembles carries out the constant current charge-discharge test after placing 12 h; Charging/discharging voltage is 0.02 V ~ 3.0 V; In 25 ℃ ± 2 ℃ environment,, measure the nanocrystalline SnO of the present invention respectively 50 mA/g and 100 mA/g constant current charge-discharge loop tests (rate of charge is identical with corresponding discharge-rate)
2The reversible capacity of lithium ion battery negative and charge-discharge performance.Embodiment 1 obtains SnO
2Nanocrystalline test result is as shown in Figure 3, and hence one can see that, the nanocrystalline SnO of the present invention
2Lithium ion battery negative has higher reversible capacity and cycle performance.
Claims (1)
1. the low temperature preparation method of nanocrystalline structure tin dioxide lithium ion battery negative pole material, its step is following:
(1) with SnCl
22H
2O is dissolved in the dark congruent melting solvent of choline chloride 60 base, stirs, and is mixed with the reaction soln that concentration is 10.0 ~ 50.0g/L; The dark congruent melting solvent of said choline chloride 60 base is a choline chloride 60 and terepthaloyl moietie 1:2 mixed solution in molar ratio, or choline chloride 60 and urea 1:2 mixed solution in molar ratio;
(2) stir down; Speed with 0.5 ~ 3mL/min in above-mentioned every liter of reaction soln adds 20 ~ 60mL Hydrazine Hydrate 80; Under the room temperature, methyl alcohol and washed with de-ionized water precipitated product are used in spinning behind reaction 1 ~ 3h successively; Dry under 40 ~ 100 ° of C then, obtain the nanocrystalline structure tin dioxide lithium ion battery negative pole material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110101600A CN102229439B (en) | 2011-04-22 | 2011-04-22 | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110101600A CN102229439B (en) | 2011-04-22 | 2011-04-22 | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229439A CN102229439A (en) | 2011-11-02 |
| CN102229439B true CN102229439B (en) | 2012-10-03 |
Family
ID=44842062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110101600A Active CN102229439B (en) | 2011-04-22 | 2011-04-22 | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229439B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613123B (en) * | 2013-12-13 | 2015-02-18 | 青岛大学 | Method for preparing monodisperse stannic oxide nanocrystalline particles |
| CN103803640B (en) * | 2014-01-26 | 2015-07-22 | 柳州豪祥特科技有限公司 | Method for preparing nanometer ITO (indium tin oxide) powder by virtue of coprecipitation method |
| CN104192810B (en) * | 2014-08-15 | 2015-10-28 | 浙江大学 | A kind of preparation method of layered double-hydroxide of large interlamellar spacing |
| TWI570989B (en) | 2015-08-21 | 2017-02-11 | 財團法人工業技術研究院 | Electrolyte composition, and sodium secondary battery |
| CN108550842A (en) * | 2018-05-18 | 2018-09-18 | 天津师范大学 | A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and preparation method thereof |
| CN108899542A (en) * | 2018-05-25 | 2018-11-27 | 浙江众泰汽车制造有限公司 | A kind of hard carbon cathode material, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428847A (en) * | 2008-12-15 | 2009-05-13 | 吉林大学 | Process for producing nanostructured tin dioxide lithium ion battery negative pole material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010195657A (en) * | 2009-02-26 | 2010-09-09 | Mitsubishi Materials Corp | Method for producing ultrafine particle tin oxide powder |
-
2011
- 2011-04-22 CN CN201110101600A patent/CN102229439B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428847A (en) * | 2008-12-15 | 2009-05-13 | 吉林大学 | Process for producing nanostructured tin dioxide lithium ion battery negative pole material |
Non-Patent Citations (3)
| Title |
|---|
| Andrew P. Abbott et al..Solubility of Metal Oxides in Deep Eutectic Solvents Based on Choline Chloride.《Journal of Chemical and Engineering Data》.2006,第51卷(第4期),1280-1282. * |
| JP特开2010-195657A 2010.09.09 |
| Kang-Min Kim et al..Preparation of SnO Nanosheets and SnO2 Fine Powders by Hydrazine Method.《稀有金属材料与工程》.2006,第35卷43-46. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229439A (en) | 2011-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104538595B (en) | Embedded nano metal load type carbon nano-sheet lithium ion battery negative material and its preparation method and application | |
| Wang et al. | Excellent stability of spinel LiMn2O4-based cathode materials for lithium-ion batteries | |
| CN100530780C (en) | Composite lithium titanate electrode material and preparation method thereof | |
| CN102214816B (en) | Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN102229439B (en) | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material | |
| CN103531758B (en) | Nano metal tin and composite cathode material of silicon/carbon/graphite and preparation method thereof | |
| Ma et al. | Synthesis of amorphous ZnSnO3 double-shell hollow microcubes as advanced anode materials for lithium ion batteries | |
| CN107069001B (en) | Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof | |
| CN103219168A (en) | Li4Ti5O12/ grapheme composite electrode material and preparation method thereof | |
| CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| Chang et al. | Ultrathin SnO2 nanosheets anchored on graphene with improved electrochemical kinetics for reversible lithium and sodium storage | |
| Wang et al. | Hydrothermal synthesis of flower-like Zn2SnO4 composites and their performance as anode materials for lithium-ion batteries | |
| Vujković et al. | Hydrothermal synthesis of Li4Ti5O12/C nanostructured composites: morphology and electrochemical performance | |
| CN105489874A (en) | Stannic oxide nanoparticles with high electrical property and preparation method therefor | |
| Wang et al. | Enhanced cyclic performance of Cu2V2O7/reduced Graphene Oxide mesoporous microspheres assembled by nanoparticles as anode for Li-ion battery | |
| CN112290022B (en) | Lithium ion battery anode lithium supplement additive and preparation method and application thereof | |
| CN105226273A (en) | A kind of iron manganese phosphate for lithium and preparation method thereof and application | |
| Liu et al. | A green and facile hydrothermal synthesis of γ-MnOOH nanowires as a prospective anode material for high power Li-ion batteries | |
| Liu et al. | Comparative study of the cathode and anode performance of Li2MnSiO4 for lithium-ion batteries | |
| Wen et al. | Ultra-thin N-doped carbon coated SnO2 nanotubes as anode material for high performance lithium-ion batteries | |
| Li et al. | Synthesis and electrochemical performance of Li4Ti5O12/Ag composite prepared by electroless plating | |
| Song et al. | Recent advances in LiV3O8 as anode material for aqueous lithium-ion batteries: Syntheses, modifications, and perspectives | |
| Jiang et al. | Facile synthesis and lithium storage mechanism study of directly usable tin-based metal organic framework | |
| CN108598405B (en) | Preparation method of three-dimensional graphene tin oxide carbon composite negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |