CN102683710A - Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof - Google Patents
Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon nanofiber load titanium dioxide thin film anode material and a preparation method thereof, and solves the technical problems that nano-scale titanium dioxide is reunited and inactivated easily during recycling of a lithium ion battery, and the conductivity is low. The carbon nanofiber load titanium dioxide thin film anode material comprises carbon nanofibers and titanium dioxide, wherein the mass of the titanium dioxide is 10 to 30 percent of the total mass of the thin film anode material. The carbon nanofiber load titanium dioxide thin film anode material which is prepared by the method and has a one-dimensional nano structure has relatively high specific capacity, high charging and discharging speed and high recycling stability and can completely use the advantages of the carbon nanofibers and the titanium dioxide.
Description
Technical field
The present invention relates to a kind of titanium deoxid film negative material and preparation method thereof, especially a kind of carried by nano carbon fiber titanium deoxid film negative material and preparation method thereof.
Background technology
Volume is little, power density is high, have extended cycle life, self discharge is little, ratio of performance to price advantages of higher because have for lithium ion battery; Occupy leading position in portable type electronic product market, be widely used in numerous mobile electronic devices fields such as mobile phone, digital camera, notebook computer.Along with the fast development of communication, medical treatment, military project, space flight industry, high-technology fields such as microelectronics industry, mini-medical apparatus, electric automobile are had higher requirement to the performance and the capacity of lithium rechargeable battery.Therefore, the high power electrode material that performance is more stable becomes the focus of current research.
Negative material is as an important component part of lithium rechargeable battery; In common negative material, titanium dioxide is cheap and easy to get, safe, environment friendly and pollution-free, is easy to realize fast charging and discharging; It is very high to insert lithium efficient, therefore becomes the focus of lithium cell cathode material research.
Utilize hydro thermal method successfully to prepare and have the nanotube-shaped of anatase phase, Type B or the two mixed crystal phase or nanometer wire titanium dioxide; Reactant, cosolvent, temperature, time through the control hydro-thermal reaction prepare the one-dimensional nano structure titanium dioxide of different-shape and crystal formation, make titanium dioxide have lower density, more open spatial channel, higher embedding lithium capacity, excellent cycle performance and doff lithium ability fast.
But the block material of titanium dioxide lacks the inner passage; Greatly reduce actual capacity and the circulation ratio of lithium ion battery when discharging and recharging; And lithium ion is in the process that embeds and deviate from, and titanium dioxide crystal lattice can produce certain distortion, and the diffusion of lithium ion has received the restriction of short and small Ti-O key; Titanium dioxide nanoparticle is prone to reunite in the battery cyclic process simultaneously, has therefore limited its application.
The main path that addresses this problem is; The material of nano titanium oxide and high power capacity is carried out such as polymer such as carbon, CNT, Graphene, metal oxide, polypyrrole, polyaniline, polyacrylonitrile compound, with collaborative both advantages of performance and remedy the deficiency of homogenous material.
Simultaneously; Improve the specific area of material; Also be the effective way that improves cycle performance,, not only can improve conductive capability to titanium dioxide as being prepared into nanotube-shaped or the nanometer wire; Also can increase material and electrolyte contact area, shorten lithium ion at the inner the evolving path of titanium dioxide, reduce the destruction of doff lithium process to material structure.
At present; The complex method of titanium dioxide and material with carbon element mainly comprises sol-gal process, precipitating load method, sputter load method, suspension load method, electrostatic spinning load method etc., and wherein method of electrostatic spinning is a kind of effective ways that prepare carried by nano carbon fiber metal or metal oxide nanoparticles relatively simply.Up to now, do not see the report that is equipped with carried by nano carbon fiber one-dimensional nano structure titanium deoxid film negative material through method of electrostatic spinning and hydro-thermal reaction legal system.
Summary of the invention
The present invention is exactly to be prone to technical problems such as reunion inactivation, conductance are low in order to solve in the lithium ion battery cyclic process Nano titanium dioxide, provides a kind of and can effectively improve the specific capacity of lithium ion battery negative material and carried by nano carbon fiber titanium deoxid film negative material of cycle performance and preparation method thereof.
A kind of carried by nano carbon fiber titanium deoxid film negative material provided by the invention, it contains carbon nano-fiber and titanium dioxide, and the quality of titanium dioxide accounts for the 10-30% of film cathode material gross mass.
Optimized technical scheme of the present invention is that the diameter of carbon nano-fiber is 200-500nm, shape grid space between the carbon nano-fiber, and the grid void size is 0.5-5 μ m, voidage is 20-80%.
The further optimized technical scheme of the present invention is inside or the surface that titanium dioxide disperses, inlays or be coated on carbon nano-fiber, perhaps is dispersed in the interpenetrating networks space of carbon nano-fiber.
The further again optimized technical scheme of the present invention is that titanium dioxide forms the nanometer wire, and the diameter of nanometer wire titanium dioxide is 10-200nm, and length is 0.1-50 μ m.
The present invention more another optimized technical scheme to be that titanium dioxide forms nanotube-shaped, the internal diameter of nanotube-shaped titanium dioxide is that 3-6nm, external diameter are 8-11nm, length is 100-200nm.
The present invention more further optimized technical scheme be that the structural form of film cathode material is nonwoven, parallel-oriented or orderly grid, thickness is 4-50 μ m.
The present invention provides a kind of method for preparing carried by nano carbon fiber titanium deoxid film negative material simultaneously, and it may further comprise the steps:
(1) spinning solution that the precursor polymer and the organic solvent of TiO 2 precursor solution, hydrolysis inhibitor, pore-foaming agent, carbon nano-fiber is made into homogeneous;
(2) make the presoma/polymer nanofibre film of titanium dioxide with method of electrostatic spinning;
(3) with the presoma that makes/polymer nanofibre film through after the pre-oxidation, in addition roasting obtains the carbon nano-fiber composite film material that anatase titania is contained in inside in protective gas atmosphere;
(4) the carbon nano-fiber composite film material that makes is immersed in the mixed solution of hydrothermal solution or hydrothermal solution and cosolvent, transfer in the hydrothermal reaction kettle,, obtain the film product through hydro-thermal reaction;
(5) with the film product that makes with deionized water wash after, place acid solution to carry out ion-exchange reactions, obtain intermediate hydrogen metatitanic acid/carbon nano-fiber film;
(6) gained hydrogen metatitanic acid/carbon nano-fiber film is calcined in carbide furnace, obtained the carbon nano-fiber of carried titanium dioxide.
Among the preparation method provided by the present invention, preferred electrostatic spinning process parameter is: in the spinning solution, the mass concentration of polymer is 7-15%; The mass concentration of pore-foaming agent is 2-5%, and the molar concentration of TiO 2 precursor and hydrolysis inhibitor is 0.1-1mol/L, and the syringe needle internal diameter is 0.7-1.1mm; The electrostatic potential that applies is 14-20kV; The spinning solution flow is 0.4-0.8mL/h, and receiving range is 15-25cm, adopts single needle head or the spinning of spininess head.
Among the preparation method provided by the present invention, preferred scheme is in the said step (3), elder generation carries out pre-oxidation 4-10h under 220-300 ℃ in air atmosphere after; In protective gas nitrogen, argon gas or other inert gas atmosphere, carry out carbonization in 300-800 ℃, cooling at last is cooled to room temperature; Wherein, Programming rate is 1-10 ℃/min, and cooling rate is 1-10 ℃/min, and carbonization time is 1-10h.
Among the preparation method provided by the present invention, preferred scheme is in the said step (4), in the thermal response still, under 110-230 ℃, carries out hydro-thermal reaction 24-72h; In the said step (5), place acid solution to flood 12-24h; In the said step (6), calcining heat is 300-600 ℃, and calcination time is 4-12h.
Among the preparation method provided by the present invention, the titanium precursor body comprises one or more combinations of butyl titanate, isopropyl titanate, titanium tetrachloride, titanium sulfate, titanyl sulfate; Hydrolysis inhibitor comprises one or more combinations of anhydrous acetic acid, acrylic acid, neck benzenediol, acetoacetic acid allyl ester, acetylacetone,2,4-pentanedione and hydrochloric acid, sulfuric acid, phosphoric acid; Polymer is one or both combinations in polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, the polyvinyl butyral resin; Pore-foaming agent is one or more combinations of polymethyl methacrylate, PLA, polyvinylpyrrolidone, polyethylene glycol, methylcellulose, Sodium Polyacrylate, polyacrylamide; Organic solvent is one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform; Hydro-thermal reaction solution is one or more combinations of the NaOH aqueous solution, the KOH aqueous solution, the Na2CO3 aqueous solution, the NaHCO3 aqueous solution, the K2CO3 aqueous solution or the KHCO3 aqueous solution, and concentration is 8-12mol/L; Cosolvent is one or more combinations of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, glycerine, ethylenediamine, diethanol amine, triethanolamine, monochloro methane or carbon tetrachloride; The hydro-thermal reaction solutions employed can also be the mixed solution of above-mentioned hydro-thermal reaction solution and above-mentioned cosolvent; Acid solution is one or more combinations of HCl solution, HNO3 solution, acetum, oxalic acid solution, and concentration is 0.1-1mol/L.
Among the preparation method of the present invention; If select the precursor polymer of polyacrylonitrile for use as carbon nano-fiber; Select for use polymethyl methacrylate as pore-foaming agent; Need electro spinning nanometer fiber membrane be carried out heat treatment in sections, promptly carry out pre-oxidation in the air, under protective gas atmosphere, carry out carbonization afterwards at 270-300 ℃.
The condition of the hydro-thermal reaction described in the preparation method of the present invention is: in the hydro-thermal reaction that does not have cosolvent to participate in; After carrying out hydro-thermal reaction 24h under with 120-150 ℃ temperature, metatitanic acid that occurs in the titanate that obtains, the subsequent process and end-product titanium dioxide are nanotube; After carrying out hydro-thermal reaction 24-48h under with 150-230 ℃ temperature; Metatitanic acid that occurs in the titanate that obtains, the subsequent process and end-product titanium dioxide are nanotube; Behind hydro-thermal reaction 48-72h, the nanotube segment self assembly is a nano wire, and what obtain is the mixture of nanotube and nano wire; Behind hydro-thermal reaction 72h, metatitanic acid that occurs in the titanate that obtains, the subsequent process and end-product titanium dioxide are nano wire.When having cosolvent to exist in the described hydro-thermal reaction solution, after carrying out hydro-thermal reaction 48h under 120-230 ℃ the temperature, metatitanic acid that occurs in the titanate of gained, the subsequent process and end-product titanium dioxide are nano wire.
The end-product that obtains among the preparation method of the present invention comprises pure Type B nanometer wire titanium dioxide/carbon nano-fiber composite material film, anatase-phase nano tubulose titanium dioxide/carbon nano-fiber composite material film and anatase-phase nano tubulose titanium dioxide mixing Type B nanometer wire titanium dioxide/carbon nano-fiber composite material film.
In order to study the chemical property of lithium ion battery laminated film negative material of the present invention, test through circulating with the constant current charge-discharge circulation of 50mA/g and the constant current charge-discharge that becomes multiplying power.Be cut into the film disk that diameter is 10-20cm to the one-dimensional nano structure titanium dioxide polymeric film material of the carried by nano carbon fiber that makes; It is put in the middle back of two layers of foam nickel sheet compresses; Wherein, film thickness is 4-50 μ m, and moulding pressure is 10-20Mpa; Film is contacted with nickel screen closely and be difficult for soaking down and come off, dry 12h at 80-100 ℃ of vacuum drying oven at last at electrolyte.
Dried combination electrode is as GND, with metal lithium sheet as electrode being formed 2025 type button batteries, the organic electrolyte that uses be LiPF6/EC: DEC (1: 1, Vol), work electrode and to adopting Celgard (PP/PE/PP) barrier film between the electrode.Whole process in the glove box that is full of protective atmosphere (Ar), assemble (O2＜1ppm, H2O＜1ppm), charge-discharge test carry out having on programme controlled electro-chemical test equipment, the electric current of battery circulation is 50mA/g, the voltage of battery charging and discharging is 3.0V.
The beneficial effect of lithium ion battery laminated film negative material provided by the present invention and preparation method thereof is following: the present invention makes carried by nano carbon fiber anatase titanium dioxide laminated film through method of electrostatic spinning; And process hydro-thermal reaction, ion-exchange and roasting finally obtain one-dimensional nano structure titanium dioxide/carbon nano-fiber laminated film negative material; And through regulating reaction temperature, time and the cosolvent of hydro-thermal reaction; Obtain having different one-dimentional structures (nanotube-shaped, nanometer wire or both mixed structures) and different crystal phase structures (Detitanium-ore-type, Type B or both mixed structures) titanium dioxide and laminated film negative material thereof successfully realized the purpose of regulation and control product pattern and crystal formation.This material has excellent charging and discharging reversible capacity and cyclical stability, can be used for lithium ion battery, polymer battery, particularly the film-type battery.Method technology of the present invention is simple, controllability is strong, with low cost, environmental friendliness; The specific capacity of the composite negative pole material of preparing and cycle life are higher than the titanium dioxide class negative material (application does not at present appear in the newspapers) in the present Study on Li-ion batteries using; Can be widely used in greatly improving the performance of battery in the lithium ion battery production.
Description of drawings
Fig. 1 is the SEM figure of embodiment 1, Comparative Examples 1, embodiment 3 and embodiment 5; Wherein (a) is Comparative Examples 1 titania nanoparticles/carbon nano-fiber; (b) be embodiment 1 titania nanotube/carbon nano-fiber; (c) be embodiment 3 titania nanotube nano wire mixing/carbon nano-fibers, (d) be embodiment 5 titanium dioxide nano threads/carbon nano-fiber;
Fig. 2 is the TEM figure of Comparative Examples 1, embodiment 1, embodiment 3 and embodiment 5; Wherein (a) is Comparative Examples 1 titania nanoparticles/carbon nano-fiber; (b) be embodiment 1 titania nanotube/carbon nano-fiber; (c) be embodiment 3 titania nanotube nano wire mixing/carbon nano-fibers, (d) be embodiment 5 titanium dioxide nano threads/carbon nano-fiber;
Fig. 3 is the XRD figure of Comparative Examples 1, embodiment 1, embodiment 3 and embodiment 5;
Fig. 4 be embodiment 3 and embodiment 5 first, secondary charging and discharging curve figure;
Fig. 5 is Comparative Examples 1, embodiment 3 and embodiment 5 50 cycle life curve charts under same current density;
Fig. 6 is embodiment 3 and the cycle life curve chart of embodiment 5 under the different electric current density.
Embodiment
Below in conjunction with instance the present invention is described further.The manufacturer of used material and model are referring to table 1 among following Comparative Examples and the embodiment.
Comparative Examples 1:
3ml tetra-n-butyl titanate and 2ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.
In the electrostatic spinning process; Select No. 12 syringe needles (internal diameter is 1.1mm) for use; The electrostatic potential that applies is 18kV, and the spinning solution flow is 0.6ml/h, and the receiving range between metal roller and the syringe needle is 20cm; Cylinder external diameter linear velocity is 8m/s, obtains the nano fibrous membrane of certain thickness partial parallel orientation through the spinning of 5h.
The electro spinning nanometer fiber membrane of gained is carried out constant strain pre-oxidation 5h under 280 ℃; Place retort roasting 2h under 600 ℃ of protections with high pure nitrogen then; Programming rate is 3 ℃/min, takes out with the cooling rate cooling of 5 ℃/min and then can obtain carbon nano-fiber internal load titania nanoparticles laminated film.The crystal formation of titania nanoparticles is a Detitanium-ore-type, and the load capacity inner at carbon nano-fiber is about 10wt%, and the particle diameter of titanium dioxide granule is about 10-300nm.
Embodiment 1:
3ml tetra-n-butyl titanate and 2ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.
In the electrostatic spinning process; Select No. 12 syringe needles (internal diameter is 1.1mm) for use; The electrostatic potential that applies is 18kV, and the spinning solution flow is 0.6ml/h, and the receiving range between metal roller and the syringe needle is 20cm; Cylinder external diameter linear velocity is 8m/s, obtains the nano fibrous membrane of certain thickness partial parallel orientation through the spinning of 5h.
The electro spinning nanometer fiber membrane of gained is carried out constant strain pre-oxidation 5h under 280 ℃; Place retort roasting 2h under 600 ℃ of protections with high pure nitrogen then; Programming rate is 3 ℃/min, takes out with the cooling rate cooling of 5 ℃/min and then can obtain carried by nano carbon fiber titania nanoparticles laminated film.
Composite film material is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in the teflon-lined hydrothermal reaction kettle, 120 ℃ obtain the carried by nano carbon fiber sodium titanate nanotubes behind the insulation 20h down in vacuum drying oven.
Take out fiber membrane and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2 again, normal temperature held 24h obtains the carried by nano carbon fiber titanate radical nanopipe, and the form and the size of nanotube remain unchanged.
At last in retort, under the high pure nitrogen, with 400 ℃ temperature roasting 4h; Finally obtain the carried by nano carbon fiber titania nanotube, the form and the size of titania nanotube remain unchanged basically, and the crystalline phase of nanotube-shaped titanium dioxide is a Detitanium-ore-type; And titanium dioxide is about 10wt% in the load capacity on carbon nano-fiber surface, and tube wall has the 1-4 layer, and the external diameter of nanotube is 8-11nm; Internal diameter is 3-6nm, and length is 100-200nm.The diameter of carbon nano-fiber is 250-400nm.
Embodiment 2:
6ml tetra-n-butyl titanate and 4ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference implementation of carried by nano carbon fiber titania nanoparticles laminated film example 1.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in the teflon-lined hydrothermal reaction kettle, 230 ℃ obtain the carried by nano carbon fiber sodium titanate nanotubes behind the insulation 12h down in vacuum drying oven.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, normal temperature held 24h obtains the carried by nano carbon fiber titanate radical nanopipe, and the form and the size of nanotube remain unchanged.
At last in retort, under the high pure nitrogen, with 400 ℃ temperature roasting 4h; Finally obtain the carried by nano carbon fiber titania nanotube, the form and the size of titania nanotube remain unchanged, and the tube wall of nanotube has the 1-4 layer; The external diameter of nanotube is 8-11nm, and internal diameter is 3-6nm, and length is 100-200nm; The crystalline phase of titanium dioxide is a Detitanium-ore-type, and the load capacity of titanium dioxide on carbon nano-fiber surface be about 20wt%, and the diameter of carbon nano-fiber is 250-400nm.
Embodiment 3:
6ml tetra-n-butyl titanate and 4ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference implementation of carried by nano carbon fiber titania nanoparticles laminated film example 1.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in the teflon-lined hydrothermal reaction kettle, in vacuum drying oven, obtain the nanotube and the nano wire mixture of carried by nano carbon fiber sodium titanate under 230 ℃ behind the insulation 50h.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, normal temperature held 24h obtains nanotube, the nano wire mixture of carried by nano carbon fiber metatitanic acid, and the form and the size of nanotube and nano wire remain unchanged.
At last in retort, under the high pure nitrogen, with 400 ℃ temperature roasting 4h; Finally obtain carried by nano carbon fiber titania nanotube and nano wire mixture, the form and the size of titania nanotube and nano wire remain unchanged, and the tube wall of nanotube has the 1-4 layer; The external diameter of nanotube is 8-11nm, and internal diameter is 3-6nm, and length is 100-200nm; The diameter of nano wire is 80-120nm, and length is 1.5-2 μ m, and the crystalline phase of nanotube titanium dioxide is a Detitanium-ore-type; The crystalline phase of nano wire titanium dioxide is a Type B, and titanium dioxide is about 20wt% in the load capacity on carbon nano-fiber surface, and the diameter of carbon nano-fiber is 250-400nm.
Embodiment 4:
6ml tetra-n-butyl titanate and 4ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference implementation of carried by nano carbon fiber titania nanoparticles laminated film example 1.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in the teflon-lined hydrothermal reaction kettle, 230 ℃ obtain carried by nano carbon fiber sodium titanate nano wire behind the insulation 72h down in vacuum drying oven.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, normal temperature held 24h obtains carried by nano carbon fiber metatitanic acid nano wire, and the form and the size of nano wire remain unchanged.
At last in retort, under the high pure nitrogen, with 400 ℃ temperature roasting 4h; Finally obtain the carried by nano carbon fiber titanium dioxide nano thread, the form and the size of titanium dioxide nano thread remain unchanged, and the diameter of nano wire is 80-120nm; Length is 1.5-2 μ m; The crystalline phase of nano wire titanium dioxide is a Type B, and titanium dioxide is about 20wt% in the load capacity on carbon nano-fiber surface, and the diameter of carbon nano-fiber is 250-400nm.
Embodiment 5:
9ml tetra-n-butyl titanate and 6ml anhydrous acetic acid and mixed solution are joined in the dimethyl formamide solution of 60ml polyacrylonitrile (concentration is 9wt%) and polymethyl methacrylate (concentration is 3wt%), form the solution of homogeneous, be used for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference implementation of carried by nano carbon fiber titania nanoparticles laminated film example 1.
Laminated film is immersed in 1: 1 mixed solution of sodium hydrate aqueous solution and absolute ethyl alcohol volume ratio of 10mol/L; Be transferred in the teflon-lined hydrothermal reaction kettle; 170 ℃ obtain carried by nano carbon fiber sodium titanate nano wire behind the insulation 48h down in vacuum drying oven; The diameter of nano wire is 80-120nm, and length is 1.5-2 μ m.
Take out fiber membrane and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, normal temperature held 24h obtains carried by nano carbon fiber metatitanic acid nano wire, and the form and the size of nano wire remain unchanged.
At last in retort, under the high pure nitrogen, with 400 ℃ temperature roasting 4h; Finally obtain the carried by nano carbon fiber titanium dioxide nano thread, the form and the size of titanium dioxide nano thread remain unchanged, and the diameter of nano wire is 80-120nm; Length is 1.5-2 μ m; The crystalline phase of titanium dioxide shows as Type B, and the load capacity of titanium dioxide on carbon nano-fiber surface be about 30wt%, and the diameter of carbon nano-fiber is 250-400nm.
Table 1
Employed hydrothermal reaction kettle is customized forming among the present invention, and its structure and general hydrothermal reaction kettle structure are basic identical, and promptly shell is processed by stainless steel precision, in polytetrafluoroethylene bushing is arranged, polytetrafluoroethyllining lining is a cylinder, at the bottom of comprising glass and bowl cover.The internal diameter of liner is 60mm, and the degree of depth is 70.77mm, and volume is 200ml.Adopt double shielding, can be acidproof, alkali etc.Safe temperature: 100-250 ℃, maximum pressure 3MPaG.
Among the present invention, after carrying out hydrothermal treatment consists, titanium dioxide exists with the form of nanotube and nano wire, and capacity and cycle performance improve a lot.
As shown in Figure 5, the first discharge specific capacity that compares ratio 1 is 789.2mAh/g, and the specific discharge capacity after 50 circulations is 210mAh/g; The first discharge specific capacity of embodiment 3 and embodiment 5 is respectively 1292.4mAh/g and 948.9mAh/g, is greatly improved, and after through 50 circulations, specific discharge capacity still can remain on about 610mAh/g and 430mAh/g.
Claims (9)
1. a carried by nano carbon fiber titanium deoxid film negative material is characterized in that containing carbon nano-fiber and titanium dioxide, and the quality of titanium dioxide accounts for the 10-30% of film cathode material gross mass.
2. ask 1 described carried by nano carbon fiber titanium deoxid film negative material according to right; The diameter that it is characterized in that said carbon nano-fiber is 200-500nm; Shape grid space between the said carbon nano-fiber, said grid void size are 0.5-5 μ m, and voidage is 20-80%.
3. ask 1 or 2 described carried by nano carbon fiber titanium deoxid film negative materials according to right; It is characterized in that inside or surface that said titanium dioxide disperses, inlays or be coated on said carbon nano-fiber, perhaps be dispersed in the interpenetrating networks space of said carbon nano-fiber.
4. ask 3 described carried by nano carbon fiber titanium deoxid film negative materials according to right, it is characterized in that said titanium dioxide forms the nanometer wire, the diameter of said nanometer wire titanium dioxide is 10-200nm, and length is 0.1-50 μ m.
5. ask 3 described carried by nano carbon fiber titanium deoxid film negative materials according to right, it is nanotube-shaped to it is characterized in that said titanium dioxide forms, and the internal diameter of said nanotube-shaped titanium dioxide is that 3-6nm, external diameter are 8-11nm, and length is 100-200nm.
6. ask 5 described carried by nano carbon fiber titanium deoxid film negative materials according to right, the structural form that it is characterized in that said film cathode material is nonwoven, parallel-oriented or orderly grid, and thickness is 4-50 μ m.
7. method for preparing carried by nano carbon fiber titanium deoxid film negative material as claimed in claim 1 is characterized in that may further comprise the steps:
(1) spinning solution that the precursor polymer and the organic solvent of TiO 2 precursor solution, hydrolysis inhibitor, pore-foaming agent, carbon nano-fiber is made into homogeneous;
(2) make the presoma/polymer nanofibre film of titanium dioxide with method of electrostatic spinning;
(3) with the presoma that makes/polymer nanofibre film through after the pre-oxidation, in addition roasting obtains the carbon nano-fiber composite film material that anatase titania is contained in inside in protective gas atmosphere;
(4) the carbon nano-fiber composite film material that makes is immersed in the mixed solution of hydrothermal solution or hydrothermal solution and cosolvent, transfer in the hydrothermal reaction kettle,, obtain the film product through hydro-thermal reaction;
(5) with the film product that makes with deionized water wash after, place acid solution to carry out ion-exchange reactions, obtain intermediate hydrogen metatitanic acid/carbon nano-fiber film;
(6) gained hydrogen metatitanic acid/carbon nano-fiber film is calcined in carbide furnace, obtained the carbon nano-fiber of carried titanium dioxide.
8. the method for preparing carried by nano carbon fiber titanium deoxid film negative material according to claim 7 is characterized in that in the said step (4), in the thermal response still, under 120-230 ℃, carries out hydro-thermal reaction 24-72h.
9. according to claim 7 or the 8 described methods that prepare carried by nano carbon fiber titanium deoxid film negative material, it is characterized in that said titanium precursor body comprises one or more combinations of butyl titanate, isopropyl titanate, titanium tetrachloride, titanium sulfate, titanyl sulfate; Said hydrolysis inhibitor comprises one or more combinations of anhydrous acetic acid, acrylic acid, neck benzenediol, acetoacetic acid allyl ester, acetylacetone,2,4-pentanedione and hydrochloric acid, sulfuric acid, phosphoric acid; Said polymer is one or both combinations in polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, the polyvinyl butyral resin; Said pore-foaming agent is one or more combinations of polymethyl methacrylate, PLA, polyvinylpyrrolidone, polyethylene glycol, methylcellulose, Sodium Polyacrylate, polyacrylamide; Said organic solvent is one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform; Said hydro-thermal reaction solution is one or more combinations of the NaOH aqueous solution, the KOH aqueous solution, the Na2CO3 aqueous solution, the NaHCO3 aqueous solution, the K2CO3 aqueous solution or the KHCO3 aqueous solution, and concentration is 8-12mol/L; Said cosolvent is one or more combinations of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, glycerine, ethylenediamine, diethanol amine, triethanolamine, monochloro methane or carbon tetrachloride; Said hydro-thermal reaction solutions employed can also be the mixed solution of above-mentioned hydro-thermal reaction solution and above-mentioned cosolvent; Described acid solution is one or more combinations of HCl solution, HNO3 solution, acetum, oxalic acid solution, and concentration is 0.1-1mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210159566.XA CN102683710B (en) | 2012-05-21 | 2012-05-21 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
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| CN201210159566.XA CN102683710B (en) | 2012-05-21 | 2012-05-21 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
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| CN102683710A true CN102683710A (en) | 2012-09-19 |
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