CN106629837B - A kind of preparation method of the titanic oxide material rich in titanous defect - Google Patents
A kind of preparation method of the titanic oxide material rich in titanous defect Download PDFInfo
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- CN106629837B CN106629837B CN201610817168.0A CN201610817168A CN106629837B CN 106629837 B CN106629837 B CN 106629837B CN 201610817168 A CN201610817168 A CN 201610817168A CN 106629837 B CN106629837 B CN 106629837B
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- C01—INORGANIC CHEMISTRY
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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Abstract
The present invention relates to a kind of preparation methods of titanium dioxide sheet layer material rich in titanous defect.Use normal propyl alcohol, butyl titanate, hydrofluoric acid and graphene oxide as raw material, is synthesized by solvent-thermal method.In synthesis process, hydrofluoric acid is surfactant, can promote the formation of titanous defect and lamellar structure；Graphene oxide is additive, improves the electric conductivity of material prepared, has also further promoted the formation of titanous defect；Meanwhile we carry out the drying of material using Freeze Drying Technique, and original structure can be kept not collapse, short texture, specific surface area is than big.Therefore, the material is used for negative electrode of lithium ion battery, compared to commercial titanium dioxide P25, our material is in sheet and is rich in titanous defect, with biggish specific surface area, it not only contributes to improve electron-transport speed, also helps the quick deintercalation for promoting lithium ion, improve the high rate performance and reversible capacity of lithium ion battery.
Description
Technical field
The invention belongs to technical field of nano material, in particular to a kind of nano titania material rich in titanous defect
The preparation method of material, the material can be used as lithium ion battery negative material.
Background technique
TiO2As lithium ion battery negative material, theoretical capacity is suitable with conventional graphite electrodes, reacts the body of front and back
Product changes unobvious (about 3%), and lithium ion battery safety performance and cycle life can be improved；Again, TiO2It is with higher embedding
Lithium current potential (1.7V vs. Li+/ Li), it can avoid the consumption of active material and electrolyte when because of the formation of SEI film, reducing can not
Inverse capacitance loss；Finally, TiO2Chemical property is very stable, nontoxic, non-environmental-pollution.But TiO2Electric conductivity it is poor so that
Interface resistance between active material and electrolyte is larger.In order to promote its electric conductivity, we joined centainly during the preparation process
For the hydrofluoric acid of amount as surfactant and a small amount of graphene oxide as additive, the titanium dioxide prepared is rich in three
The ultrathin nanometer lamella black titanium dioxide of valence titanium defect.Titanium dioxide of the preparation containing titanous defect reported at present
Method mainly has chemical vapor deposition, superlaser, electronics or argon ion bombardment.These methods generally all high energy consumption, multi-step,
Synthesis condition is harsh or equipment is expensive, and the solvent-thermal method that we use is relatively easy and easily controllable.Patent 1
(CN105126796A, date of publication on December 9th, 2015) is also disclosed and is contained the two of titanous defect using solvent structure
The preparation method of titanium oxide, still, the maximum advantage of the preparation method disclosed in us are that we used graphene oxides
As additive, finally obtained advantageous effects are to significantly improve the content of titanous defect, simultaneous oxidation graphene conduct
Nucleation site shortens generated time；Moreover, we used Freeze Drying Techniques compared to patent 1, material is both ensured
Structure will not collapse because of dry, and make material loose porous, be more advantageous to the quick deintercalation of lithium ion.
Summary of the invention
The purpose of the present invention is preparing a kind of titanium dioxide sheet layer material rich in titanous defect, which can be applied
In negative electrode of lithium ion battery.Method provided by the invention is that the mixed solution of preparation is put into high pressure using a step solvent-thermal method
Reaction preparation is rich in the titanium dioxide sheet layer material of titanous defect in reaction kettle.Specific preparation method includes the following steps:
(1) 25 ~ 30 ml normal propyl alcohols are weighed with graduated cylinder to be added in the beaker with magneton, sequentially adds 2 ~ 3 with liquid-transfering gun
Obtained mixed solution magnetic agitation at room temperature is used liquid relief in whipping process by ml butyl titanate and 0.8 ~ 1ml hydrofluoric acid
The graphene oxide colloidal sol of 1 ~ 1.5 ml, 5 ~ 15 min of magnetic agitation is added in rifle；
(2) mixed solution is put into reaction kettle, 6 ~ 24 h is reacted at 180 ~ 200 DEG C；
(3) obtained precipitating deionized water and ethyl alcohol will be reacted with certain revolving speed centrifuge washing 3 ~ 5 times；
(4) 18 ~ 24 are freeze-dried to the material after centrifugation at -40 ~ -50 DEG C, 30 ~ 40 Pa using freeze drier
H can obtain the titanium dioxide sheet layer material rich in titanous.
The beneficial effects of the invention are as follows mixed solution is prepared, using solvent structure composite material, preparation method is simple
Easy to operate, energy consumption is relatively low, and carries out in closed container, pollutes small.Utilize method provided by the present invention preparation
Titanic oxide material is a kind of sheet material, and has more titanous defect.When for lithium ion battery negative material
When, the advantages of introducing titanous, has in titanium dioxide: the electron-transport speed of titanium dioxide is improved, to improve coulomb
Efficiency；More Lacking oxygens are produced in raw material, to produce more storage lithium sites.Titanium dioxide is prepared into super
After thin nanoscale twins, the diffusion path of electronics and lithium ion is become shorter, so the diffusion of electronics and lithium ion is easier, in turn
The high rate performance of battery is improved, meanwhile, nano material also has the characteristics that large specific surface area, therefore electrode material and electrolyte
Contact resistance is small.In conclusion the titanium dioxide for using us to prepare is applied to lithium-ion electric as negative electrode material compared to P25
Pond has the characteristics that coulombic efficiency is higher, storage lithium site is more, high rate performance is more excellent, internal resistance is smaller.Scanning electron microscope (SEM) photograph (Fig. 1)
It has been shown that, the titanic oxide material prepared by us is sheet, and size is about 200nm；Electron paramagnetic resonance figure (Fig. 2) display,
Relative to business titanium dioxide P25, the titanic oxide material prepared by us has titanous abundant；Lithium ion battery times
Rate performance map (Fig. 3) display, compared to business titanium dioxide P25, the titanic oxide material prepared by us has more excellent
Lithium electricity high rate performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the titanic oxide material synthesized in present example 1.
Fig. 2 is that the titanic oxide material synthesized in present example 1 and business are total with the electron paramagnetic of titanium dioxide P25
Shake comparison diagram.
Fig. 3 is that the titanic oxide material synthesized in present example 1 and business are forthright again with the lithium electricity of titanium dioxide P25
It can comparison diagram.
Specific embodiment
A kind of preparation method of titanium dioxide sheet layer material rich in titanous defect proposed by the present invention can be by as follows
Method implement, specific preparation method includes the following steps:
Embodiment 1
(1) 25 ml normal propyl alcohols are weighed with graduated cylinder to be added in the beaker with magneton, sequentially adds 2 ml titaniums with liquid-transfering gun
Obtained mixed solution magnetic agitation at room temperature is used liquid-transfering gun by sour four butyl esters and 0.8 ml hydrofluoric acid in whipping process
The graphene oxide colloidal sol of 1 ml, 10 min of magnetic agitation is added；
(2) mixed solution is put into reaction kettle, 12 h is reacted at 180 DEG C；
(3) after obtained precipitating deionized water and ethyl alcohol will be reacted with certain revolving speed centrifuge washing, freezing is used
Drying machine is freeze-dried 24 h to the material after centrifugation under conditions of -50 DEG C, 40 Pa and can obtain being rich in the two of titanous
Titanium oxide sheet layer material.
Embodiment 2
(1) 30 ml normal propyl alcohols are weighed with graduated cylinder to be added in the beaker with magneton, sequentially adds 2.5ml with liquid-transfering gun
Obtained mixed solution magnetic agitation at room temperature is used liquid-transfering gun by butyl titanate and 1 ml hydrofluoric acid in whipping process
The graphene oxide colloidal sol of 1 ml, 10 min of magnetic agitation is added；
(2) mixed solution is put into reaction kettle, 24 h is reacted at 180 DEG C；
(3) after obtained precipitating deionized water and ethyl alcohol will be reacted with certain revolving speed centrifuge washing, freezing is used
Drying machine is freeze-dried 18 h to the material after centrifugation under conditions of -40 DEG C, 50 Pa and can obtain being rich in the two of titanous
Titanium oxide sheet layer material.
Claims (3)
1. a kind of preparation method of the titanic oxide material rich in titanous defect, it is characterised in that:
(1) dosage of butyl titanate is 2 ~ 3 ml, and the dosage of normal propyl alcohol is 25 ~ 30 ml, and the dosage of hydrofluoric acid is 0.8 ~ 1
Ml, the dosage of graphene oxide colloidal sol are 1 ~ 1.5 ml, the final quality and oxygen for requiring butyl titanate in prepared reactant
The mass ratio of graphite alkene remains 120: 1 to 150: 1；
(2) when being synthesized using solvent-thermal method, reaction temperature is 180 ~ 200 DEG C, and the reaction time is 6 ~ 24 h.
2. being rich in the titanic oxide material of titanous defect as prepared by claim 1, characterized in that be sheet, length and width
For 100 ~ 300 nm, thickness is 20 ~ 60 nm.
3. being rich in the titanic oxide material of titanous defect as prepared by claim 1, characterized in that be rich in titanous.
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| CN107824173A (en) * | 2017-11-01 | 2018-03-23 | 南通纺织丝绸产业技术研究院 | A kind of titanous auto-dope titania nanoparticles partial reduction stannic oxide/graphene nano piece composite and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657624A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Gray nano titanium dioxide material and preparation method and application thereof |
| CN104724755A (en) * | 2015-03-06 | 2015-06-24 | 华北电力大学 | Preparation method of micron-sized lamellar titanium dioxide nano material |
| CN105126796A (en) * | 2015-07-13 | 2015-12-09 | 华北电力大学 | Preparation method of fluorine-doped lamellar black titanium dioxide nano material |
| CN105772037A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Material for removing bromate in water through ultraviolet photocatalysis and preparation method thereof |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657624A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Gray nano titanium dioxide material and preparation method and application thereof |
| CN104724755A (en) * | 2015-03-06 | 2015-06-24 | 华北电力大学 | Preparation method of micron-sized lamellar titanium dioxide nano material |
| CN105126796A (en) * | 2015-07-13 | 2015-12-09 | 华北电力大学 | Preparation method of fluorine-doped lamellar black titanium dioxide nano material |
| CN105772037A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Material for removing bromate in water through ultraviolet photocatalysis and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Anatase TiO2 nanocrystals with exposed {001} facets on graphene sheets via molecular grafting for enhanced photocatalytic activity;Lei Sun et al.;《Nanoscale》;20111207;全文 |
| Graphene Oxide-Assisted Synthesis of Microsized Ultrathin Single-Crystalline Anatase TiO2 Nanosheets and Their Application in Dye-Sensitized Solar Cells;Biao Chen et al.;《Appl. Mater. Interfaces》;20160108;全文 |
| One-Step Preparation of Graphene-Supported Anatase TiO2 with Exposed {001} Facets and Mechanism of Enhanced Photocatalytic Properties;Liuan Gu et al.;《 Appl. Mater. Interfaces》;20130325;第3086页实验部分以及第3087页右栏第一行和图2 |
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