CN103456934A - Preparation method and application of nano TiO2(B)/carbon composite fibers for lithium ion battery cathode - Google Patents
Preparation method and application of nano TiO2(B)/carbon composite fibers for lithium ion battery cathode Download PDFInfo
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Abstract
The invention relates to a preparation method and application of nano TiO2(B)/carbon composite fibers for a lithium ion battery cathode. The preparation method comprises the following steps: firstly, synthesizing tetrabutyl titanate/polyvinylpyrrolidone precursor fibers through electrostatic spinning; then, drying the precursor fibers, and carbonizing the precursor fibers at the temperature of 300-500 DEG C under the protection of nitrogen or argon; finally, carrying out hydro-thermal treatment on the carbonized product to obtain the nano TiO2(B)/carbon composite fibers. The preparation method disclosed by the invention is simple and convenient, the composition of titanium dioxide and carbon source is realized in one step, and the introduction of carbon source is not required in subsequent experiment, thus the purity of a product is ensured, the raw material is saved, and the production cost is low. The obtained nano TiO2(B)/carbon composite fibers for the lithium ion battery cathode material have good cycle performance, and can keep high capacity especially at quick charging and discharging rates, thus the cycle efficiency is high, the capacity is reduced slowly, the conductivity is improved because of the introduction of carbon, and the resistance is reduced.
Description
Technical field
The invention discloses a kind of used as negative electrode of Li-ion battery nano-TiO
2(B) preparation method and application of/carbon composite fibre, belong to electrochemistry and materials chemistry field.
Background technology
Titanium dioxide, because it has broad application prospects in fields such as photocatalysis, photodissociation water, transducer, DSSC and lithium ion batteries, has become the focus of Material Field research.Common titanium dioxide mainly comprises four kinds of crystalline phases: sharp titanium phase, Rutile Type, brookite and TiO
2(B) phase.In all crystalline phases, TiO
2(B) type titanium dioxide belongs to monoclinic system, and structure is the most loose, has larger interlamellar spacing and less density, be conducive to the embedding of lithium ion and remove, thereby the application aspect lithium ion battery has potential superior function.
To a great extent, TiO
2(B) direction of growth of size, pattern and crystal all can affect its application in lithium ion battery.Such as, nano-scale and crossover network can shorten the transmission range of lithium ion and electronics, undersized TiO
2(B) can enlarge the contact area of electrode and electrolyte, reduce current density, reduce the internal resistance of cell, improve battery performance.One dimension TiO
2(B) nanostructure is conducive to electronics along motion along the long axis, and lithium ion also can embed fast and remove on short-axis direction.Therefore, regulation and control TiO
2(B) size, pattern and the direction of growth are extremely important, can improve the performances such as discharging and recharging of lithium ion battery.
As typical one-dimensional nano structure, TiO
2(B) synthetic method of nano wire is mainly according to document (A.R.Armstrong, G.Armstrong, J.Canales, P.G.Bruce, Angew.Chem.Int.Ed.2004,43:2286.), that is: from titanium dioxide powder, in dense sodium hydroxide solution, with hydrothermal method, obtain the sodium titanate nano wire; After in certain density hydrochloric acid, carrying out the hydrogen ion exchange, the sodium titanate nano wire is converted into to the metatitanic acid nano wire; Finally the metatitanic acid nano wire is calcined and annealed, thereby the metatitanic acid nano wire is converted into to TiO
2(B) nano wire.Chinese invention patent (publication number: CN102531050A) disclose a kind of TiO of preparation
2(B) method of nano wire and the TiO that makes
2(B) purposes of nano wire, it is the method for having utilized the secondary hydro-thermal, first utilize the method for hydro-thermal or heating to obtain the nano wire of potassium titanate, then the secondary hydro-thermal is converted into TiO by Nano lines of potassium titanate
2(B) nano wire.With TiO
2(B) lithium ion battery that nano wire is negative material, still can keep larger capacity under charge-discharge velocity fast.
Yet, as a kind of semi-conducting material, TiO
2(B) lower (～10 Ω of electronic conductivity
-1cm
-1), therefore, with pure TiO
2(B) be the lithium ion battery of negative material, the inside battery energy loss is serious.One of solution is exactly as material with carbon element, with TiO by the material of electric conductivity excellence
2(B) compound, increase the importing of electronics and derive speed.For realizing material with carbon element and TiO
2(B) compound, Chinese invention patent (patent No. ZL200710050748.2) has provided the TiO that a kind of carbon coats
2the preparation method of core-shell composite nanometer powder.It utilizes the organic substance of long-chain as carbon source, and TiO
2powder has obtained TiO after uniform temperature heat treatment under vacuum condition
2/ C nano-powder.Material with carbon element is except playing the inner TiO of protection
2outside the effect of powder, the nucleocapsid TiO of formation
2/ C composite granule is easier to carry out the regulation and control of character and function.
Electrostatic spinning is a kind of good method for preparing one-dimensional nano structure material, and extensively, simple process, can realize the controlled of material component structure in research.The present invention adopts the method for electrostatic spinning first to prepare butyl titanate (TBT)/polyvinylpyrrolidone (PVP) precursor fibre, then, through Overheating Treatment, can obtain TiO
2(B) composite fibre of/C.In the material preparation, do not need to introduce again carbon source, but, when electrospinning prepares nanofiber, a step has realized the compound of titanium dioxide and carbon source, only experience once heat treated transformation of crystal process in preparation process.So the present invention had both simplified the preparation technology of composite material, improved the purity of product, also saved carbon source.The TiO obtained
2(B) composite material of/C, have height ratio capacity and high cyclical stability, is a kind of well behaved lithium ion battery negative material.This preparation method there is not yet document and patent report.
Summary of the invention
The object of the present invention is to provide a kind of used as negative electrode of Li-ion battery TiO
2(B) preparation method of/carbon composite fibre, first adopt electrospinning process to prepare butyl titanate (TBT)/polyvinylpyrrolidone (PVP) precursor fibre, then pass through high temperature cabonization, and hydrothermal treatment consists is synthesized TiO
2(B)/C composite fibre.Products therefrom is by TiO
2(B) and the composite fibre that forms of two kinds of components of carbon (C), can realize TiO
2(B) type and material with carbon element is closely compound, and resulting composite material has height ratio capacity and cyclical stability.Concrete technical scheme is as follows:
A kind of used as negative electrode of Li-ion battery nano-TiO
2(B) preparation method of/carbon composite fibre, at first, adopt the synthetic butyl titanate (TBT) of electrostatic spinning/polyvinylpyrrolidone (PVP) precursor fibre; Then, after being dried, described precursor fibre under nitrogen or argon shield, in 300～500 ℃ (optimum 500 ℃), descends carbonization 3～6h; Finally, the product after carbonization is carried out to hydrothermal treatment consists and obtain described nano-TiO
2(B)/carbon composite fibre;
The method of the synthetic TBT/PVP precursor fibre of described electrostatic spinning is as follows: under the magnetic agitation condition, by the optimum 1.0g of 0.8～1.2g() butyl titanate, the optimum 0.3g of 0.3～0.5g() polyvinylpyrrolidone (PVP), be dissolved in the optimum 7mL of 4～7mL() ethanol, the optimum 2mL of 1～3mL() acetic acid and the optimum 1.8mL of 0.5～2mL() N, in the mixed solution of dinethylformamide (DMF), mixing and stirring; Get the aforementioned solution stirred at the optimum 12kV of 9～12kV() electrospinning under voltage, obtain described butyl titanate/polyvinylpyrrolidone precursor fibre;
The method of described hydrothermal treatment consists is as follows: the product after carbonization is dissolved in to the optimum 9mol/L of 8～11mol/L() sodium hydroxide solution; obtain suspension; react 12～24h with 180～210 ℃ (optimum 200 ℃) in airtight water heating kettle; it is neutral that the precipitated product of gained is washed to the acid-base value of cleaning solution with diluted acid and deionized water; calcine 3～6h under 400～500 ℃ (optimum 500 ℃) after drying under nitrogen or argon shield, obtain described nano-TiO
2(B)/carbon composite fibre.
The nano-TiO that described preparation method obtains
2(B) application of/carbon composite fibre, by described nano-TiO
2(B)/carbon composite fibre is as the work electrode of lithium ion battery, and the lithium sheet is auxiliary and reference electrode, and electrolyte is (as 1M LiPF
6the volume ratio of/DMC and EC is 1:1), be assembled into cover tube model battery, with the current density of 50mA/g, discharge and recharge, first discharge capacity 353～364mAh/g.
This preparation method's advantage is: 1, electrostatic spinning prepares the one-dimensional nano structure fiber, and component structure is controlled, technology maturation, and simple process, be the solid technical support that provides of controlled preparation TBT/PVP precursor fibre; When 2, electrostatic spinning prepares the TBT/PVP precursor fibre, a step has realized the compound of titanium dioxide and carbon source, does not need to introduce carbon source in subsequent experimental again.Simplify preparation technology, guaranteed the purity of product, and saved raw material; 3, the TiO that the method obtains
2(B)/C composite fibre has one-dimentional structure and short b axle and c-axis (Fig. 1); 4, raw material is easy to get, and the preparation method is simple, and production cost is lower.
The nano-TiO that this preparation method obtains
2(B)/carbon composite fibre is for the advantage of lithium ion battery negative material: 1, because composite fibre has good one-dimentional structure, less particle diameter, high specific area, and the characteristics such as short b axle and c-axis, showed good cycle performance, especially under fast charging and discharging speed, still can keep higher capacity, as discharge capacity first even can reach 364mAh/g, for lithium ion battery negative, in current all titanium-oxygen system, be that effect is best; 2, cycle efficieny is high, and capacity loss is slow; 3, introduce carbon, increased conductivity, reduced resistance.
The accompanying drawing explanation
Fig. 1 is the product TiO of embodiment 1
2(B) TiO
2the TEM photo of/C composite fibre I;
Fig. 2 is the product TiO of embodiment 1
2(B) TiO
2the charging and discharging curve of/C composite fibre I;
Fig. 3 is the product TiO of embodiment 1
2(B) TiO
2the cyclical stability figure of/C composite fibre I.
Embodiment
Be below embodiments of the invention, provided detailed execution mode and concrete operating process, its purpose is only being understood content of the present invention better.Therefore protection scope of the present invention is not subject to the restriction of illustrated embodiment.
Embodiment 1 preparation TiO
2(B)/C composite fibre I
Under the magnetic agitation condition, by 0.8g butyl titanate, 0.4g PVP, be dissolved in the mixed solution of 6mL ethanol, 2mL acetic acid and 1mL DMF mixing and stirring.Get solution 10mL with syringe, spinning head the place ahead is the copper mesh gathering-device, and voltage is 10kV, and flow velocity is 1.0mL/h.Spinning obtains the TBT/PVP precursor fibre after finishing, and carefully takes off tunica fibrosa, 60 ℃ of vacuum dryings.Then under nitrogen protection, be warming up to 300 ℃ with 2 ℃/min speed and calcined, be incubated 120 minutes.
Sample after calcining is got to 0.35g and be dissolved in 10M NaOH solution, obtain suspension.In airtight 50mL water heating kettle, with 200 ℃, react 24 hours; after stopping reaction; by 0.1M hydrochloric acid and deionized water washing for the precipitated product of gained; until the acid-base value of cleaning solution is neutral; after drying, under nitrogen protection, with 2 ℃/min speed, be warming up to 500 ℃; insulation 300min, further carbonization.Obtain TiO
2(B)/C composite fibre I.The TEM photo of product as shown in Figure 1.
The test condition of this electrode material is: the current density with 50mA/g discharges and recharges, and temperature is 25 ℃; Owing to sealing, so pressure and humidity do not affect.Test result as shown in Figure 2, shows: the discharge capacity first of material is 364mAh/g, and the charging capacity after 100 circulations is 268mAh/g, cycle performance excellent (as shown in Figure 3).
Embodiment 2 preparation TiO
2(B)/C composite fibre II
Under the magnetic agitation condition, by 0.8g butyl titanate, 0.4g PVP, be dissolved in the mixed solution of 5mL ethanol, 2mL acetic acid and 1mL DMF.Mixing and stirring.Get solution 10mL with syringe, spinning head the place ahead is the copper mesh gathering-device, and voltage is 11kV, and flow velocity is 1.0mL/h.Spinning obtains the TBT/PVP precursor fibre after finishing, and carefully takes off tunica fibrosa, 60 ℃ of vacuum dryings.Then under nitrogen protection, be warming up to 500 ℃ with 2 ℃/min speed and calcined, be incubated 120 minutes.
Sample after calcining is got to 0.4g and be dissolved in 10M NaOH solution; obtain suspension, react 24 hours with 180 ℃ in airtight 50mL water heating kettle, after stopping reaction; by 0.1M hydrochloric acid and deionized water washing for the precipitated product of gained; until the acid-base value of cleaning solution is neutral, after drying, under nitrogen protection; be warming up to 400 ℃ with 2 ℃/min speed; insulation 300min, further carbonization, obtain TiO
2(B)/C composite fibre II.
The test condition of this electrode material as described in Example 1, discharges and recharges with the current density of 50mA/g.Test result shows: the initial charge capacity of material is 353mAh/g, and the charging capacity after 100 circulations is 260mAh/g, the cycle performance excellence.
Claims (5)
1. a used as negative electrode of Li-ion battery nano-TiO
2(B) preparation method of/carbon composite fibre, is characterized in that, at first, adopts the synthetic butyl titanate of electrostatic spinning/polyvinylpyrrolidone precursor fibre; Then, described precursor fibre is dried after under nitrogen or argon shield, in 300～500 ℃ of lower carburizing reagent 3～6h; Finally, the product after carbonization is carried out to hydrothermal treatment consists and obtain described nano-TiO
2(B)/carbon composite fibre;
The method that described electrostatic spinning synthesizes butyl titanate/polyvinylpyrrolidone precursor fibre is as follows: under the magnetic agitation condition, by 0.8～1.2g butyl titanate, 0.3～0.5g polyvinylpyrrolidone, be dissolved in 4～7mL ethanol, 1～3mL acetic acid and 0.5～2mL N, in the mixed solution of dinethylformamide, mixing and stirring; Get the aforementioned solution stirred electrospinning under 9～12kV voltage, obtain described butyl titanate/polyvinylpyrrolidone precursor fibre;
The method of described hydrothermal treatment consists is as follows: the sodium hydroxide solution that the product after carbonization is dissolved in to 8～11mol/L; obtain suspension; react 12～24h with 180～210 ℃ in airtight water heating kettle; it is neutral that the precipitated product of gained is washed to the acid-base value of cleaning solution with diluted acid and deionized water; calcine 3～6h under 400～500 ℃ after drying under nitrogen or argon shield, obtain described nano-TiO
2(B)/carbon composite fibre.
2. preparation method according to claim 1, is characterized in that, described butyl titanate is 1.0g, and described polyvinylpyrrolidone is 0.3g.
3. preparation method according to claim 1, is characterized in that, the voltage of described electrospinning is 12kV.
4. preparation method according to claim 1, is characterized in that, the temperature of described water heating kettle is 200 ℃.
5. the nano-TiO obtained according to the arbitrary described preparation method of claim 1 to 4
2(B) application of/carbon composite fibre, is characterized in that, by described nano-TiO
2(B)/carbon composite fibre is as the work electrode of lithium ion battery, the lithium sheet is auxiliary and reference electrode, and electrolyte is assembled into cover tube model battery, with the current density of 50mA/g, discharges and recharges, discharge capacity 353～364mAh/g first, the charging capacity after 100 circulations is 268mAh/g.
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| CN105462550A (en) * | 2015-11-16 | 2016-04-06 | 安徽理工大学 | Flexible film with super hydrophobicity high adhesion and preparation method thereof |
| CN107394159A (en) * | 2017-07-24 | 2017-11-24 | 江苏大学 | A kind of composite fibre negative material and preparation method thereof |
| CN107785565A (en) * | 2017-10-31 | 2018-03-09 | 湘潭大学 | A kind of Sn TiO2The electrostatic spinning preparation method of C nano fiber |
| CN107785563A (en) * | 2017-09-13 | 2018-03-09 | 天津大学 | Nano-TiO2The preparation method of electrode material |
| CN107799756A (en) * | 2017-10-31 | 2018-03-13 | 湘潭大学 | A kind of Na2Ti3O7The preparation method of C nano fiber |
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| CN109306551A (en) * | 2018-07-18 | 2019-02-05 | 湘潭大学 | A kind of boron doped titanic oxide nanofiber and preparation method thereof and application as lithium ion battery negative material |
| CN110124648A (en) * | 2019-05-08 | 2019-08-16 | 陕西科技大学 | A kind of surface Lacking oxygen TiO2The preparation method of/carbon composite nanotube |
| CN110718681A (en) * | 2019-10-23 | 2020-01-21 | 陕西科技大学 | Preparation method of phosphorus-doped titanium dioxide/carbon nanofiber negative electrode material |
| CN111646473A (en) * | 2020-06-04 | 2020-09-11 | 松山湖材料实验室 | Si-TiO2Preparation method of-C composite nanowire, product and application thereof |
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| CN107394159B (en) * | 2017-07-24 | 2020-09-25 | 江苏大学 | Composite fiber negative electrode material and preparation method thereof |
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