CN102569762A - Preparation method of continuous nonspherical hierarchical hollow nanostructured titanium dioxide - Google Patents
Preparation method of continuous nonspherical hierarchical hollow nanostructured titanium dioxide Download PDFInfo
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- CN102569762A CN102569762A CN2012100227478A CN201210022747A CN102569762A CN 102569762 A CN102569762 A CN 102569762A CN 2012100227478 A CN2012100227478 A CN 2012100227478A CN 201210022747 A CN201210022747 A CN 201210022747A CN 102569762 A CN102569762 A CN 102569762A
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Abstract
The invention discloses a preparation method of continuous nonspherical hierarchical hollow nanostructured titanium dioxide, comprising the following steps of: adding 15-20ml of anhydrous tert-butyl alcohol into a clear transparent solution prepared from 100ml of deionized water and 3-5g of oxalic acid, carrying out magnetic stirring and heating to 60-70 DEG C, keeping warm for 2 hours, naturally cooling to room temperature to obtain a transparent mixed solution, transferring 60ml of the mixed solution into 100ml of a stainless steel reaction vessel with a teflon inner liner, placing the reaction vessel into a constant-temperature drying box, keeping warm at 150-200 DEG C for 10-15 hours, naturally cooling to room temperature to obtain a white sediment, repeatedly cleaning the obtained white sediment for 2-3 times by the use of deionized water or anhydrous ethanol, and drying in the drying box at 60-80 DEG C for 10-12 hours. The continuous nonspherical hierarchical hollow nanostructured titanium dioxide prepared in the invention has advantages of high charge/discharge specific capacity, good cycle performance and the like.
Description
Technical field
The invention belongs to nano material and lithium battery applications technical field, be specifically related to a kind of preparation method of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide, this material can be used as the lithium ion battery negative active material.
Background technology
In recent years; Abundant, the synthetic cost of material source is low because of having, environmental friendliness and titanium dioxide is as lithium cell cathode material as lithium ion battery negative material for titanium dioxide; Embed and deviate from the process of titanium dioxide lattice at lithium ion, can cause the advantage such as variation of lattice hardly and receive extensive concern.
Research shows; Nano titanium oxide (like nanocrystalline, nano wire, nanotube) relatively micron order titanium dioxide as lithium ion battery negative material have the specific surface height, with excellent performances such as electrolyte full contact and electric transmission be fast, and cause the research and development interest of academia and industrial quarters.As the ion cathode material lithium results of property, mainly there are two problems from the titanium dioxide of present report.One is that cost of manufacture is high, complex process.Be coated with carbon and nitrogen-doped titanium dioxide etc. like the titanium dioxide surface of making titania nanotube for the anodic oxidation that improves the employing of electron collection efficient and adopt for the surface conductivity that improves material; Another problem be lithium battery performance rate capability and stable aspect, still be difficult to reach industry and go up the high performance requirement of lithium battery.Along with the lithium ion battery industrial expansion, developing and develop the active material with high-energy and high power density becomes one of current problem that presses for solution.Therefore, seek a kind of high performance technologies such as conductive materials and doping that do not rely on, the titanium dioxide microstructure that can improve the uniqueness of electric transmission speed between electrode material and the current collector simultaneously again is very necessary.
Summary of the invention
It is simple that the object of the invention just provides a kind of technology, the preparation method of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide that cost is low.
Concrete steps are:
(1) 15～20 milliliters of anhydrous tertiary butanols are joined in the clear solution of 100 ml deionized water and 3～5 gram oxalic acid configurations, insulation was 2 hours after magnetic agitation was heated to 60～70 ℃, naturally cooled to room temperature and obtained transparent mixed solution;
(2) get 60 milliliters of mixed solutions that step (1) obtains and transfer to 100 milliliters having in the teflon-lined stainless steel cauldron;
(3) agitated reactor of step (2) is put into thermostatic drying chamber and be incubated 10～15 hours down, naturally cool to room temperature and obtain white depositions at 150～200 ℃;
(4) white depositions that step (3) is obtained is cleaned 2～3 times with deionized water or absolute ethyl alcohol repeatedly, in drying box, promptly makes continuous non-spherical classification micro-nano hollow-core construction titanium dioxide down in dry 10～12 hours at 60～80 ℃ then.
The continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the present invention's preparation is as the lithium ion battery negative active material, and the installation step of lithium ion battery is identical with common assembly method.The preparation method of negative plate is following; Adopt continuous non-spherical classification micro-nano hollow-core construction titanium dioxide as active material; Acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 75: 10: 15; After their abundant in proportion mixing, add a small amount of isopropyl alcohol, grind evenly, on sheet-punching machine, press the thick electrode slice of about 0.5mm then; The positive plate that presses places behind 60 ℃ the oven drying 24h subsequent use.LiPF with 1 mol
6Be dissolved in ethene carbonic acid vinegar (EC) and the carbonic acid diformazan vinegar (DMC) as electrolyte (EC and DEC volume ratio are 1: 1).The microporous membrane of processing with polytetrafluoroethylene is a barrier film, and aluminium flake is that battery case and negative plate are assembled into the buckle type lithium-ion battery.
After the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide that adopts among the present invention was formed battery as negative electrode active material and metal lithium sheet, its first discharge specific capacity reached 427mAh/g; Circulate the specific discharge capacity of material after 100 times still up to 170mAh/g.Above-mentioned performance shows that continuous non-spherical classification micro-nano hollow-core construction titanium dioxide has advantages such as charging and discharging capacity height, good cycle, is a kind of lithium cell cathode material with development potentiality.
The structure of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide is confirmed by x-ray diffractometer among the present invention.The X-ray diffracting spectrum of the nano composite material of being synthesized has Detitanium-ore-type TiO
2With a small amount of rutile TiO
2Characteristic diffraction peak.The field emission scanning electron microscope test shows, the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of Hydrothermal Preparation all is communicated with.Transmissioning electric mirror test shows that the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide layer shell that is synthesized is formed by 20-30 is nanocrystalline.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the embodiment of the invention 1.
Fig. 2 is the field emission scan figure of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the embodiment of the invention 1.
Fig. 3 is the transmission electron microscope picture of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the embodiment of the invention 1.
Fig. 4 is the curve chart of impulse electricity first of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the embodiment of the invention 1.
Fig. 5 is the cycle performance curve chart of the continuous non-spherical classification micro-nano hollow-core construction titanium dioxide of the embodiment of the invention 1.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
(1) 18 milliliters of anhydrous tertiary butanols are joined in the clear solution of 100 ml deionized water and 5 gram oxalic acid configurations, insulation was 2 hours after magnetic agitation was heated to 70 ℃, naturally cooled to room temperature and obtained transparent mixed solution;
(2) 60 milliliters of mixed solutions getting above-mentioned acquisition are transferred to 100 milliliters having in the teflon-lined agitated reactor;
(3) agitated reactor of step (2) is put into thermostatic drying chamber and be incubated 10 hours down, naturally cool to room temperature and obtain white depositions at 160 ℃;
(4) white depositions that step (3) is obtained is cleaned 2 times with deionized water or absolute ethyl alcohol repeatedly, in drying box, promptly makes continuous non-spherical classification micro-nano hollow-core construction titanium dioxide down in dry 10 hours at 60 ℃ then.
The XRD of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide sees Fig. 1; The FESEM of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide sees Fig. 2; The TEM of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide sees Fig. 3; The curve of cycle charge-discharge first of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide is seen Fig. 4, and the cycle performance curve of continuous non-spherical classification micro-nano hollow-core construction titanium dioxide is seen Fig. 5.
Embodiment 2:
(1) 20 milliliters of anhydrous tertiary butanols are joined in the clear solution of 100 ml deionized water and 3 gram oxalic acid configurations, insulation was 2 hours after magnetic agitation was heated to 60 ℃, naturally cooled to room temperature and obtained transparent mixed solution;
(2) 60 milliliters of mixed solutions getting above-mentioned acquisition are transferred to 100 milliliters having in the teflon-lined agitated reactor;
(3) agitated reactor of step (2) is put into thermostatic drying chamber and be incubated 15 hours down, naturally cool to room temperature and obtain white depositions at 200 ℃;
(4) white depositions that step (3) is obtained is cleaned 3 times with deionized water or absolute ethyl alcohol repeatedly, in drying box, promptly makes continuous non-spherical classification micro-nano hollow-core construction titanium dioxide down in dry 12 hours at 80 ℃ then.
Claims (1)
1. the preparation method of a titanium dioxide is characterized in that concrete steps are:
(1) 15～20 milliliters of anhydrous tertiary butanols are joined in the clear solution of 100 ml deionized water and 3～5 gram oxalic acid configurations, insulation was 2 hours after magnetic agitation was heated to 60～70 ℃, naturally cooled to room temperature and obtained transparent mixed solution;
(2) get 60 milliliters of mixed solutions that step (1) obtains and transfer to 100 milliliters having in the teflon-lined stainless steel cauldron;
(3) agitated reactor of step (2) is put into thermostatic drying chamber and be incubated 10～15 hours down, naturally cool to room temperature and obtain white depositions at 150～200 ℃;
(4) white depositions that step (3) is obtained is cleaned 2～3 times with deionized water or absolute ethyl alcohol repeatedly, in drying box, promptly makes titanium dioxide down in dry 10～12 hours at 60～80 ℃ then.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109671920A (en) * | 2018-10-31 | 2019-04-23 | 吉林大学 | Nano diamond and titanium dioxide hollow ball combination electrode material and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109671920A (en) * | 2018-10-31 | 2019-04-23 | 吉林大学 | Nano diamond and titanium dioxide hollow ball combination electrode material and preparation method |
| CN109671920B (en) * | 2018-10-31 | 2021-12-31 | 吉林大学 | Nano-diamond and titanium dioxide hollow sphere composite electrode material and preparation method thereof |
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Application publication date: 20120711 |