CN104037390A - Preparation method for silicon/carbon nanowire-loaded titanium dioxide negative material for lithium battery - Google Patents
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- CN104037390A CN104037390A CN201410285934.4A CN201410285934A CN104037390A CN 104037390 A CN104037390 A CN 104037390A CN 201410285934 A CN201410285934 A CN 201410285934A CN 104037390 A CN104037390 A CN 104037390A
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention relates to a preparation method for silicon/carbon nanowire-loaded titanium dioxide negative material for a lithium battery. The preparation method is characterized by comprising the following specific preparation steps: (1) mixing an organic high-molecular polymer with certain weight and a solvent with certain weight, fully stirring for dissolving, dropwise adding a hydrolysis inhibitor with certain weight into a solution, stirring uniformly, adding a titanium source and nano-silica powder, stirring continuously, and finally obtaining a mixed electrospinning solution; performing electrospinning by using the mixed electrospinning solution to obtain protofilament; (2) in a certain atmosphere, heating the electrospinning protofilament to a specific temperature, cooling the electrospinning protofilament after the temperature is kept for a period of time to obtain a preprocessed material, later, reheating the preprocessed material to a specific temperature, cooling the preprocessed material to room temperature after the temperature is kept for a period of time, and finally, grinding the preprocessed material to obtain the silicon/carbon nanowire and titanium dioxide composite negative material. The negative material has high specific capacity and high cycling performance; the advantages of a silicon/carbon nano-material and titanium dioxide serving as the negative material of a lithium ion battery can be exerted at the same time.
Description
Technical field
The preparation method who the present invention relates to a kind of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material, belongs to battery material technical field.
Background technology
Due to fast development and the extensive use of various portable electric appts and electric automobile, demand high for energy, the lithium ion battery that has extended cycle life is very urgent.Silicon is as lithium ion battery negative material, and its theoretical specific capacity can reach 4200mAh/g.But silicon materials, under the condition of high level removal lithium embedded, exist serious bulk effect, easily cause the structural breakdown of material and coming off of active material, thereby the cyclical stability of electrode is declined greatly.For fear of the above-mentioned deficiency of silicon, use the incomplete same material of another kind of current potential to become as its buffering skeleton the research direction that silicon is battery material.
Carbonaceous negative material has good stability and conductivity, and comparatively approaching with the embedding lithium current potential of silicon, is the extraordinary basis material disperseing as silicon grain.The method of preparing silicon/carbon composite has mechanical ball-milling method, high temperature pyrolytic cracking (HTP), vapour deposition process and spray pyrolysis, wherein comparatively easily product nucleus shell structure of high-temperature decomposition, and the combination of silicon grain and carbon is tight, even structure.Very high level improves the structural stability of silicon materials.But carbonaceous material also exists very serious defect, that is exactly that carbon potential too approaches lithium metal, and separating out of Li dendrite easily occurs in charge and discharge process, and the change in volume that its removal lithium embedded causes is in addition larger, and its cycle performance is declined.By contrast, it is little that the octahedral structure of anatase titanium dioxide makes it discharge and recharge change in volume, and with respect to the voltage of lithium at 1.7V, be not easy to form lithium metal Zhi Jing.Therefore carried titanium dioxide in carbonaceous material, can effectively improve fail safe and the stability of material.
This patent provides a kind of electrostatic spinning to prepare the method for silicon/carbon nanocoils carried titanium dioxide lithium ion battery negative material.The method is using organic high molecular polymer as carbon source, and nano silica fume and facile hydrolysis titanium source and carbon source are blended in solvent, forms electrostatic spinning solution, heats decomposition after electrospinning, finally generates silicon/carbon carried titanium dioxide negative material.
Through patent retrieval, there are domestic many sections of patents (CN102157731A, CN102185128A, CN102394288A etc.) to adopt pyrolysismethod to prepare silicon/carbon negative pole material, different from this patent method.Other one section of patent (CN102157732) is used titanate radical nanopipe and glucose synthesis of titanium dioxide/carbon composite nanotube.Different from this patent test method.Other two sections of patents (CN101937985A, CN102683710A) are used respectively Graphene and carbon nano-fiber and titanium dioxide to process Formed and composite titania material, different from this patent method.
Summary of the invention
The object of this invention is to provide a kind of preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material, the lithium ion battery negative material consistent appearance that it is prepared, and there is higher specific capacity and cycle performance, can give play to silicon/carbon nanomaterial and the titanium dioxide advantage as lithium ion battery negative material simultaneously.
Technical scheme of the present invention is achieved in that a kind of preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material, it is characterized in that concrete synthetic method is as follows:
(1) electrostatic spinning process:
The organic high molecular polymer of certain mass is mixed with the solvent phase of certain mass, fully stirring and dissolving, in solution, drip afterwards the hydrolysis inhibitor of certain mass, after stirring, add titanium source and nano silica fume to continue to stir, finally obtain electrostatic spinning mixed solution; Electrostatic spinning mixed solution is carried out to electrostatic spinning, obtain precursor;
(2) heat treatment step:
Under certain atmosphere, electrostatic spinning precursor is heated to specified temp, cooling after insulation a period of time, obtain material previously treated.Afterwards, material previously treated is heated to a certain specified temp again, after insulation a period of time, is cooled to room temperature, can obtain silicon/carbon nanocoils composite titanium dioxide negative material finally by crossing to grind;
In electrostatic spinning process, organic high molecular polymer is that polytetrafluoroethylene, polypropylene are fine, poly(ethylene oxide); Solvent can be selected mixed solvent, the water of ethanol, DMF and ethanol; Hydrolysis inhibitor can be selected glacial acetic acid, acetylacetone,2,4-pentanedione, hydrochloric acid; Tetrabutyl titanate, metatitanic acid four isopropyl esters, titanium tetrachloride can be selected in titanium source; The concentration of high molecular polymer in solvent is 8wt% ~ 12wt%; Silica flour is 1:8 ~ 1:6 with polymer quality ratio; Titanium source and high molecular polymer mass ratio are 1:5 ~ 1:2; The mol ratio of titanium source and hydrolysis inhibitor is 1:5 ~ 1:2.
In heat treatment step, preliminary treatment first can be at O
2under atmosphere or under air atmosphere, carry out, heating-up temperature is between 250 ~ 450 DEG C, and temperature retention time is between 30 ~ 120 minutes; The heating of carbonization is for the second time to carry out under argon gas or blanket of nitrogen, and heating-up temperature is at 500 ~ 650 DEG C, and heating time is between 4 ~ 8 hours.
Good effect of the present invention is to have higher specific capacity and cycle performance, can give play to silicon/carbon nanomaterial and the titanium dioxide advantage as lithium ion battery negative material simultaneously.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram spectrum of silicon/carried by nano carbon fiber titanium dioxide in example 1 of the present invention.
Fig. 2 is the power spectrum test curve of silicon/carried by nano carbon fiber titanium dioxide in example 2 of the present invention.
Fig. 3 is the scanning electron microscope diagram spectrum of silicon/carried by nano carbon fiber titanium dioxide in example 3 of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described:
embodiment 1
As shown in Figure 1, by 2.4g polytetrafluoroethylene (PVP) and 24g ethanol mix and blend, be configured to the PVP solution of 10wt%; Add afterwards 0.5g glacial acetic acid, after stirring, adding tetrabutyl titanate 1.2g and silica flour 0.4g(is that titanium source and high molecular polymer mass ratio are 1:2, and the mol ratio of titanium source and glacial acetic acid is 1:2, and polymer quality and silica flour mass ratio are 6:1).Through carrying out electrostatic spinning after last whipping step, obtain electrostatic spinning precursor.
Electrostatic spinning precursor is inserted in Muffle furnace, under air atmosphere, temperature is increased to 300 DEG C with 10 DEG C of programming rates per minute, be incubated cooling after 30 minutes.Again obtained material previously treated is put into atmosphere furnace, under argon shield atmosphere, be warming up to 600 DEG C, heat 4 hours, obtain carbon fiber/composite titania material after cooling.
embodiment 2
As shown in Figure 2, by fine 1.92g polypropylene (PAN) and 21.6g DMF (NMP) and 2.4g ethanol mix and blend, be configured to the PAN solution of 8wt%; Add afterwards 0.68g acetylacetone,2,4-pentanedione, after stirring, adding tetrabutyl titanate 0.4g and silica flour 0.3g(is that titanium source and high molecular polymer mass ratio are 1:5, and the mol ratio of titanium source and acetylacetone,2,4-pentanedione is 1:5, and polymer quality and silica flour mass ratio are 8:1).Through carrying out electrostatic spinning after last whipping step, obtain electrostatic spinning precursor.
Electrostatic spinning precursor is inserted in atmosphere furnace, under oxygen atmosphere, temperature is increased to 250 DEG C with 5 DEG C of programming rates per minute, be incubated cooling after 30 minutes.Under nitrogen protection atmosphere, be warming up to 500 DEG C again, heat 8 hours, obtain carbon fiber/composite titania material after cooling.
embodiment 3
As shown in Figure 3, by 2.88g poly(ethylene oxide) (PEO) and 24g deionized water water mix and blend, be configured to the PEO aqueous solution of 12wt%; Add afterwards 2.91g, 38% concentrated hydrochloric acid, after stirring, adding titanium tetrachloride 1.44g and silica flour 0.57g(is that titanium source and high molecular polymer mass ratio are 1:2, the mol ratio of titanium source and hydrogen chloride is 1:4, polymer quality and silica flour mass ratio are 5:1).Through carrying out electrostatic spinning after last whipping step, obtain electrostatic spinning precursor.
Electrostatic spinning precursor is inserted in Muffle furnace, under air atmosphere, temperature is increased to 450 DEG C with 5 DEG C of programming rates per minute, be incubated cooling after 120 minutes.In nitrogen protection atmosphere stove, be warming up to 650 DEG C again, heat 4 hours, obtain carbon fiber/composite titania material after cooling.
Claims (4)
1. the preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material
It is characterized in that concrete preparation process is as follows:
(1) electrostatic spinning process:
The organic high molecular polymer of certain mass is mixed with the solvent phase of certain mass, fully stirring and dissolving, in solution, drip afterwards the hydrolysis inhibitor of certain mass, after stirring, add titanium source and nano silica fume to continue to stir, finally obtain electrostatic spinning mixed solution; Electrostatic spinning mixed solution is carried out to electrostatic spinning, obtain precursor;
(2) heat treatment step:
Under certain atmosphere, electrostatic spinning precursor is heated to specified temp, cooling after insulation a period of time, obtain material previously treated; Afterwards, material previously treated is heated to a certain specified temp again, after insulation a period of time, is cooled to room temperature, can obtain silicon/carbon nanocoils composite titanium dioxide negative material finally by crossing to grind.
2. a kind of preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material according to claim 1, is characterized in that the organic high molecular polymer in described electrostatic spinning process is that polytetrafluoroethylene, polypropylene are fine, poly(ethylene oxide); Solvent can be selected mixed solvent, the water of ethanol, DMF and ethanol; Hydrolysis inhibitor can be selected glacial acetic acid, acetylacetone,2,4-pentanedione, hydrochloric acid; Tetrabutyl titanate, metatitanic acid four isopropyl esters, titanium tetrachloride can be selected in titanium source.
3. a kind of preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material according to claim 1, is characterized in that high molecular polymer in the described electrostatic spinning process concentration in solvent is 8wt% ~ 12wt%; Silica flour is 1:8 ~ 1:6 with polymer quality ratio; Titanium source and high molecular polymer mass ratio are 1:5 ~ 1:2; The mol ratio of titanium source and hydrolysis inhibitor is 1:5 ~ 1:2.
4. a kind of preparation method of silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material according to claim 1, is characterized in that the preliminary treatment first in described heat treatment step can be at O
2under atmosphere or under air atmosphere, carry out, heating-up temperature is between 250 ~ 450 DEG C, and temperature retention time is between 30 ~ 120 minutes; The heating of carbonization is for the second time to carry out under argon gas or blanket of nitrogen, and heating-up temperature is at 500 ~ 650 DEG C, and heating time is between 4 ~ 8 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550827A (en) * | 2018-05-08 | 2018-09-18 | 广东迈纳科技有限公司 | A kind of preparation method of three-dimensional porous shape silicon-carbon cathode material and application |
| CN108598416A (en) * | 2018-04-24 | 2018-09-28 | 华南理工大学 | A kind of silicon/titanium dioxide/carbon composite and preparation method thereof for negative electrode of lithium ion battery |
| CN109837610A (en) * | 2019-02-26 | 2019-06-04 | 湘潭大学 | A kind of Na2TiSiO5The electrostatic spinning preparation method of C nano fiber |
| CN110391400A (en) * | 2019-07-26 | 2019-10-29 | 南通大学 | A kind of preparation method of flexible self-supporting silicon/super long titanium dioxide nanotube electrode |
| CN112086629A (en) * | 2020-09-08 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material |
| CN114284479A (en) * | 2021-12-22 | 2022-04-05 | 博路天成新能源科技有限公司 | Preparation method of novel carbon-silicon negative electrode material |
| CN115132959A (en) * | 2022-07-26 | 2022-09-30 | 北方民族大学 | Lithium ion battery cathode material with self-supporting structure and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598416A (en) * | 2018-04-24 | 2018-09-28 | 华南理工大学 | A kind of silicon/titanium dioxide/carbon composite and preparation method thereof for negative electrode of lithium ion battery |
| CN108550827A (en) * | 2018-05-08 | 2018-09-18 | 广东迈纳科技有限公司 | A kind of preparation method of three-dimensional porous shape silicon-carbon cathode material and application |
| CN109837610A (en) * | 2019-02-26 | 2019-06-04 | 湘潭大学 | A kind of Na2TiSiO5The electrostatic spinning preparation method of C nano fiber |
| CN110391400A (en) * | 2019-07-26 | 2019-10-29 | 南通大学 | A kind of preparation method of flexible self-supporting silicon/super long titanium dioxide nanotube electrode |
| CN110391400B (en) * | 2019-07-26 | 2022-04-15 | 南通大学 | Preparation method of flexible self-supporting silicon/ultra-long titanium dioxide nanotube electrode |
| CN112086629A (en) * | 2020-09-08 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material |
| CN114284479A (en) * | 2021-12-22 | 2022-04-05 | 博路天成新能源科技有限公司 | Preparation method of novel carbon-silicon negative electrode material |
| CN115132959A (en) * | 2022-07-26 | 2022-09-30 | 北方民族大学 | Lithium ion battery cathode material with self-supporting structure and preparation method and application thereof |
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Application publication date: 20140910 |