CN102683710B - 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, cost performance ratio because have for lithium ion battery, in portable type electronic product market share leading position, 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 Industry, performance and the capacity of high-technology field to lithium rechargeable battery such as microelectronics industry, mini-medical apparatus, electric automobile are had higher requirement.Therefore the high power electrodes 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, insert lithium efficiency very high, therefore become the focus of lithium cell cathode material research.
Utilize hydro thermal method successfully to prepare to there is Anatase, the nanotube-shaped or nanometer wire titanium dioxide of Type B or the two mixed crystal phase, prepare the one-dimensional nano structure titanium dioxide of different-shape and crystal formation by controlling reactant, cosolvent, temperature, time of hydro-thermal reaction, make titanium dioxide there is lower density, more open spatial channel, higher embedding lithium capacity, good cycle performance and doff lithium ability fast.
But the block material of titanium dioxide lacks inner passage, actual capacity and circulation ratio when greatly reducing lithium ion battery and discharging and recharging, and lithium ion is in the process embedding and deviate from, the lattice of titanium dioxide can produce certain distortion, the diffusion of lithium ion has been subject to the restriction of short and small Ti-O key, titanium dioxide nanoparticle is easily reunited in circulating battery process simultaneously, has therefore limited its application.
The main path addressing this problem is, by the material of nano titanium oxide and high power capacity such as the polymer such as carbon, carbon nano-tube, Graphene, metal oxide, polypyrrole, polyaniline, polyacrylonitrile carry out compound, to work in coordination with both advantages of performance and to make up the deficiency of homogenous material.
Simultaneously, improve the specific area of material, also be the effective way that improves cycle performance, as titanium dioxide being prepared into nanotube-shaped or nanometer wire, not only can improve conductive capability, also can increase material and electrolyte contact area, shorten lithium ion at the evolving path of titanium dioxide inside, 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 of relatively simply preparing carried by nano carbon fiber metal or metal oxide nanoparticles.Up to now, have no the report for carried by nano carbon fiber one-dimensional nano structure titanium deoxid film negative material by method of electrostatic spinning and hydro-thermal reaction legal system.
Summary of the invention
The present invention is exactly in order to solve in lithium ion battery cyclic process the Nano titanium dioxide technical problems such as inactivation, conductance are low of easily reuniting, to provide 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.
The preferred technical scheme of the present invention is that the diameter of carbon nano-fiber is 200-500nm, shape grid-gap between carbon nano-fiber, and grid-gap is of a size of 0.5-5 μ m, and voidage is 20-80%.
The further preferred technical scheme of the present invention is that titanium dioxide disperses, inlays or be coated on inside or the surface of carbon nano-fiber, or is dispersed in the interpenetrating networks space of carbon nano-fiber.
The present invention more further preferred technical scheme is that titanium dioxide forms 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 preferred 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's structural form that further preferred technical scheme is film cathode material is again nonwoven, parallel-oriented or orderly grid, and thickness is 4-50 μ m.
The present invention provides a kind of method of preparing carried by nano carbon fiber titanium deoxid film negative material simultaneously, and it comprises the following steps:
(1) precursor polymer of TiO 2 precursor solution, hydrolysis inhibitor, pore-foaming agent, carbon nano-fiber and organic solvent are made into the spinning solution of homogeneous;
(2) make the presoma/polymer nanofibre film of titanium dioxide with method of electrostatic spinning;
(3) by the presoma/polymer nanofibre film making after pre-oxidation, in protective gas atmosphere, roasting in addition, obtains the carbon nano-fiber composite film material that contains anatase titania in inside;
(4) the carbon nano-fiber composite film material making is immersed in the mixed solution of hydrothermal solution or hydrothermal solution and cosolvent, transfer in hydrothermal reaction kettle, through hydro-thermal reaction, obtain film product;
(5) by after the film product deionized water washing making, be placed in acid solution and 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.
In preparation method provided by the present invention, preferred electrostatic spinning process parameter is: in 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 syringe needle internal diameter is 0.7-1.1mm, the electrostatic potential applying is 14-20kV, spinning solution flow is 0.4-0.8mL/h, and receiving range is 15-25cm, adopts single needle or Multi needle spinning.
In preparation method provided by the present invention; preferred scheme is in described step (3); first in air atmosphere, at 220-300 DEG C, carry out after pre-oxidation 4-10h; in protective gas nitrogen, argon gas or other inert gas atmosphere, carry out carbonization in 300-800 DEG C, last cooling down is to room temperature; wherein; programming rate is 1-10 DEG C/min, and cooling rate is 1-10 DEG C/min, and carbonization time is 1-10h.
In preparation method provided by the present invention, preferred scheme is in described step (4), in thermal response still, carries out hydro-thermal reaction 24-72h at 110-230 DEG C; In described step (5), be placed in acid solution and flood 12-24h; In described step (6), calcining heat is 300-600 DEG C, and calcination time is 4-12h.
In preparation method provided by the present invention, 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, 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, chloroform; Hydro-thermal reaction solution is the NaOH aqueous solution, the KOH aqueous solution, Na
2cO
3the aqueous solution, NaHCO
3the aqueous solution, K
2cO
3the aqueous solution or KHCO
3one or more combinations of the aqueous solution, concentration is 8-12mol/L; Cosolvent is one or more combinations of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, glycerol, ethylenediamine, diethanol amine, triethanolamine, monochloro methane or carbon tetrachloride; Hydro-thermal reaction solution used can also be the mixed solution of above-mentioned hydro-thermal reaction solution and above-mentioned cosolvent; Acid solution is HCl solution, HNO
3one or more combinations of solution, acetum, oxalic acid solution, concentration is 0.1-1mol/L.
In preparation method of the present invention; if select the precursor polymer of polyacrylonitrile as carbon nano-fiber; select polymethyl methacrylate as pore-foaming agent; electro spinning nanometer fiber membrane need to be carried out heat treatment in sections; carbonization is carried out in i.e. pre-oxidation in 270-300 DEG C is carried out air afterwards under protective gas atmosphere.
The condition of the hydro-thermal reaction described in preparation method of the present invention is: in the hydro-thermal reaction that does not have cosolvent to participate in, at the temperature with 120-150 DEG C, carry out after hydro-thermal reaction 24h, the metatitanic acid and the end-product titanium dioxide that in the titanate that obtains, subsequent process, occur are nanotube; At the temperature with 150-230 DEG C, carry out after hydro-thermal reaction 24-48h, the metatitanic acid and the end-product titanium dioxide that in the titanate that obtains, subsequent process, occur are nanotube, after hydro-thermal reaction 48-72h, nanotube segment self assembly is nano wire, what obtain is the mixture of nanotube and nano wire, after hydro-thermal reaction 72h, the metatitanic acid and the end-product titanium dioxide that in the titanate that obtains, subsequent process, occur are nano wire.In the time having cosolvent to exist in described hydro-thermal reaction solution, at the temperature of 120-230 DEG C, carry out after hydro-thermal reaction 48h, the metatitanic acid occurring in the titanate of gained, subsequent process and end-product titanium dioxide are nano wire.
The end-product obtaining in 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, circulate to test by the constant current charge-discharge circulation with 50mA/g and the constant current charge-discharge of zoom rate.The one-dimensional nano structure titanium dioxide polymeric film material of the carried by nano carbon fiber making is cut into the film disk that diameter is 10-20cm, in the middle of it is put in to two layers of foam nickel sheet, rear pressurization compresses, wherein, film thickness is 4-50 μ m, moulding pressure is 10-20Mpa, film contacted with nickel screen closely and be difficult for coming off under electrolyte soaks, finally drying 12h at 80-100 DEG C of vacuum drying oven.
Dried combination electrode is as battery cathode, using metal lithium sheet as electrode being formed to 2025 type button batteries, the organic electrolyte using is LiPF6/EC: DEC (1: 1, Vol), work electrode and to adopting Celgard (PP/PE/PP) barrier film between electrode.Whole process is assembled (O2 < 1ppm in the glove box that is full of protective atmosphere (Ar); H2O < 1ppm); charge-discharge test carries out having on programme controlled electro-chemical test equipment; the electric current of circulating battery is 50mA/g, and 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 as follows: the present invention makes carried by nano carbon fiber anatase titanium dioxide laminated film by method of electrostatic spinning, and through hydro-thermal reaction, ion-exchange and roasting finally obtain one-dimensional nano structure titanium dioxide/carbon nano-fiber laminated film negative material, and by regulating the reaction temperature of hydro-thermal reaction, time and cosolvent, obtain having different one-dimentional structures (nanotube-shaped, nanometer wire or both mixed structures) and different crystal phase structure (Detitanium-ore-type, Type B or both mixed structures) titanium dioxide and laminated film negative material thereof, successfully realize the object of regulation and control product pattern and crystal formation.This material has excellent reversible capability of charging and discharging and cyclical stability, can be used for lithium ion battery, polymer battery, particularly film-type battery.Method technique 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 is not higher than the titanium dioxide class negative material in current Study on Li-ion batteries using (application at present appears in the newspapers), can be widely used in, in lithium ion battery production, greatly improving the performance of battery.
Brief description of the drawings
Fig. 1 is the SEM figure of embodiment 1, comparative example 1, embodiment 3 and embodiment 5, wherein (a) is comparative example 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 example 1, embodiment 1, embodiment 3 and embodiment 5, wherein (a) is comparative example 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 example 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 example 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 different current densities.
Embodiment
Below in conjunction with example, the invention will be further described.In following comparative example and embodiment, the manufacturer of material used and model are referring to table 1.
Comparative example 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, for electrostatic spinning.
In electrostatic spinning process, select No. 12 syringe needles (internal diameter is 1.1mm), the electrostatic potential applying is 18kV, spinning solution flow is 0.6ml/h, receiving range between metal roller and 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 at 280 DEG C to constant strain pre-oxidation 5h; then be placed in retort roasting 2h under the protection of 600 DEG C and high pure nitrogen; programming rate is 3 DEG C/min, can obtain carbon nano-fiber internal load titania nanoparticles laminated film with the cooling taking-up of cooling rate of 5 DEG C/min.The crystal formation of titania nanoparticles is Detitanium-ore-type, is about 10wt% in the load capacity of carbon nano-fiber inside, 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, for electrostatic spinning.
In electrostatic spinning process, select No. 12 syringe needles (internal diameter is 1.1mm), the electrostatic potential applying is 18kV, spinning solution flow is 0.6ml/h, receiving range between metal roller and 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 at 280 DEG C to constant strain pre-oxidation 5h; then be placed in retort roasting 2h under the protection of 600 DEG C and high pure nitrogen; programming rate is 3 DEG C/min, can obtain carried by nano carbon fiber titania nanoparticles laminated film with the cooling taking-up of cooling rate of 5 DEG C/min.
Composite film material is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in teflon-lined hydrothermal reaction kettle, obtain carried by nano carbon fiber sodium titanate nanotubes be incubated 20h at 120 DEG C in vacuum drying oven after.
Take out fiber membrane and clean to pH=7 with deionized water, then immerse in the aqueous hydrochloric acid solution of pH=2, place 24h and obtain carried by nano carbon fiber titanate radical nanopipe under normal temperature, form and the size of nanotube remain unchanged.
Finally in retort, under high pure nitrogen, with the temperature roasting 4h of 400 DEG C, finally obtain carried by nano carbon fiber titania nanotube, form and the size of titania nanotube remain unchanged substantially, the crystalline phase of nanotube-shaped titanium dioxide is Detitanium-ore-type, and titanium dioxide is about 10wt% in the load capacity on carbon nano-fiber surface, tube wall has 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, for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference example 1 of carried by nano carbon fiber titania nanoparticles laminated film.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in teflon-lined hydrothermal reaction kettle, obtain carried by nano carbon fiber sodium titanate nanotubes be incubated 12h at 230 DEG C in vacuum drying oven after.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, place 24h and obtain carried by nano carbon fiber titanate radical nanopipe under normal temperature, form and the size of nanotube remain unchanged.
Finally in retort, under high pure nitrogen, with the temperature roasting 4h of 400 DEG C, finally obtain carried by nano carbon fiber titania nanotube, form and the size of titania nanotube remain unchanged, the tube wall of nanotube has 1-4 layer, and the external diameter of nanotube is 8-11nm, and internal diameter is 3-6nm, length is 100-200nm, the crystalline phase of titanium dioxide is Detitanium-ore-type, 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 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, for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference example 1 of carried by nano carbon fiber titania nanoparticles laminated film.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in teflon-lined hydrothermal reaction kettle, in vacuum drying oven, at 230 DEG C, be incubated the nanotube and the nano wire mixture that obtain carried by nano carbon fiber sodium titanate after 50h.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, place nanotube, nano wire mixture that 24h obtains carried by nano carbon fiber metatitanic acid under normal temperature, form and the size of nanotube and nano wire remain unchanged.
Finally in retort, under high pure nitrogen, with the temperature roasting 4h of 400 DEG C, finally obtain carried by nano carbon fiber titania nanotube and nano wire mixture, form and the size of titania nanotube and nano wire remain unchanged, the tube wall of nanotube has 1-4 layer, the external diameter of nanotube is 8-11nm, internal diameter is 3-6nm, length is 100-200nm, the diameter of nano wire is 80-120nm, length is 1.5-2 μ m, the crystalline phase of nanotube titanium dioxide is Detitanium-ore-type, the crystalline phase of nano wire titanium dioxide is Type B, titanium dioxide is about 20wt% in the load capacity on carbon nano-fiber surface, 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, for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference example 1 of carried by nano carbon fiber titania nanoparticles laminated film.
Laminated film is immersed in the sodium hydrate aqueous solution of 10mol/L, be transferred in teflon-lined hydrothermal reaction kettle, obtain carried by nano carbon fiber sodium titanate nano wire be incubated 72h at 230 DEG C in vacuum drying oven after.
Take out laminated film and clean to pH=7 with deionized water, immerse in the aqueous hydrochloric acid solution of pH=2, place 24h and obtain carried by nano carbon fiber metatitanic acid nano wire under normal temperature, form and the size of nano wire remain unchanged.
Finally in retort, under high pure nitrogen, with the temperature roasting 4h of 400 DEG C, finally obtain carried by nano carbon fiber titanium dioxide nano thread, 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 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, for electrostatic spinning.Through electrostatic spinning, pre-oxidation and carbonization, the preparation reference example 1 of carried by nano carbon fiber titania nanoparticles laminated film.
Laminated film is immersed in the sodium hydrate aqueous solution and 1: 1 mixed solution of absolute ethyl alcohol volume ratio of 10mol/L, be transferred in teflon-lined hydrothermal reaction kettle, be incubated 48h at 170 DEG C in vacuum drying oven after, obtain carried by nano carbon fiber sodium titanate nano wire, 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, place 24h and obtain carried by nano carbon fiber metatitanic acid nano wire under normal temperature, form and the size of nano wire remain unchanged.
Finally in retort, under high pure nitrogen, with the temperature roasting 4h of 400 DEG C, finally obtain carried by nano carbon fiber titanium dioxide nano thread, 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 titanium dioxide is about 30wt% in the load capacity on carbon nano-fiber surface, and the diameter of carbon nano-fiber is 250-400nm.
Table 1
The hydrothermal reaction kettle using in the present invention is customized forming, and its structure and general hydrothermal reaction kettle structure are basic identical, and shell is processed by stainless steel precision, inside has polytetrafluoroethylene bushing, and polytetrafluoroethyllining lining is 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 DEG C, maximum pressure 3MPaG.
In the present invention, carrying out after 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 50 circulations, specific discharge capacity still can remain on 610mAh/g and 430mAh/g left and right.
Claims (2)
1. prepare a method for carried by nano carbon fiber titanium deoxid film negative material, it is characterized in that comprising the following steps:
(1) precursor polymer of TiO 2 precursor solution, hydrolysis inhibitor, pore-foaming agent, carbon nano-fiber and organic solvent are made into the spinning solution of homogeneous;
(2) make the presoma/polymer nanofibre film of titanium dioxide with method of electrostatic spinning;
(3) by the presoma/polymer nanofibre film making after pre-oxidation, in protective gas atmosphere, roasting in addition, obtains the carbon nano-fiber composite film material that contains anatase titania in inside;
(4) the carbon nano-fiber composite film material making is immersed in the mixed solution of hydrothermal solution or hydrothermal solution and cosolvent, transfer in hydrothermal reaction kettle, through hydro-thermal reaction, obtain film product;
(5) by after the film product deionized water washing making, be placed in acid solution and 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;
Described carried by nano carbon fiber titanium deoxid film negative material, 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;
Described titanium precursor body comprises one or more combinations of butyl titanate, isopropyl titanate, titanium tetrachloride, titanium sulfate, titanyl sulfate; Described 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; Described polymer is one or both combinations in polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral resin; Described pore-foaming agent is one or more combinations of polymethyl methacrylate, PLA, polyvinylpyrrolidone, polyethylene glycol, methylcellulose, Sodium Polyacrylate, polyacrylamide; Described organic solvent is one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, chloroform; Described hydro-thermal reaction solution is the NaOH aqueous solution, the KOH aqueous solution, Na
2cO
3the aqueous solution, NaHCO
3the aqueous solution, K
2cO
3the aqueous solution or KHCO
3one or more combinations of the aqueous solution, concentration is 8-12mol/L; Described cosolvent is one or more combinations of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, glycerol, ethylenediamine, diethanol amine, triethanolamine, monochloro methane or carbon tetrachloride; Described acid solution is HCl solution, HNO
3one or more combinations of solution, acetum, oxalic acid solution, concentration is 0.1-1mol/L.
2. the method for preparing carried by nano carbon fiber titanium deoxid film negative material according to claim 1, is characterized in that in described step (4), in thermal response still, carries out hydro-thermal reaction 24-72h at 120-230 DEG C.
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| CN103531756B (en) * | 2013-11-01 | 2016-02-17 | 北京化工大学 | Carried by nano carbon fiber lithium titanate thin film material and preparation method thereof |
| CN104733704A (en) * | 2013-12-19 | 2015-06-24 | 北汽福田汽车股份有限公司 | Membrane material and preparation method thereof, cathode material of lithium ion battery and preparation method thereof |
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