CN105406042A - Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery - Google Patents

Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery Download PDF

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CN105406042A
CN105406042A CN201510782324.XA CN201510782324A CN105406042A CN 105406042 A CN105406042 A CN 105406042A CN 201510782324 A CN201510782324 A CN 201510782324A CN 105406042 A CN105406042 A CN 105406042A
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preparation
titanium dioxide
carbon
lithium ion
nanotube
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曹立新
丁蕾
董博华
苏革
高荣杰
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Ocean University of China
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Ocean University of China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method for a carbon-coated super-long titanium dioxide nanotube negative electrode material of a lithium ion battery. The preparation method comprises the following steps of preparing a titanic acid nanotube by a hydrothermal method, and acidizing the titanic acid nanotube to obtain a hydrogen-based tube; dissolving the obtained hydrogen-based tube in ethanol, adding an organic macromolecular ethanol solution, and then carrying out low-temperature stirring to obtain macromolecular-coated hydrogen-based tube serving as a carbon-coated titanium dioxide nanotube precursor; and carrying out high-temperature thermal treatment on the precursor under the production of an inert gas to obtain the carbon uniformly-coated super-long titanium dioxide nanotube negative electrode material of the lithium ion battery. The preparation method has the advantages of simplicity in process, easiness in operation, material availability, low cost and environmental friendliness, no special device is needed in the whole reaction process, industrial production is promoted, and the quality of the finally-obtained product is relatively high; and with a high-conductive phase substance composite nano tubular structure prepared according to the method, the ion transmission distance can be shortened, the conductivity of the material and the ion diffusion rate of the material are improved, so that the material has excellent rate capability, stable cycle performance and high coulombic efficiency. The material prepared according to the method is an ideal lithium ion negative electrode material having wide commercial application prospect.

Description

The preparation method of the super long titanium dioxide nanotube lithium ion battery negative material that a kind of carbon is coated
Technical field
The invention belongs to new energy materials preparation and application field, specifically a kind of crystallinity based on the coated synthesis of large molecule is good, has excellent doubly forthright, high coulombic efficiency and stable cycle performance, the coated TiO of amorphous carbon 2the method of nanotube.
Background technology
Titanium dioxide is as a kind of " zero strain " material, in charge and discharge process, structure changes hardly, there is high security, stable cycle performance, aboundresources, cheap, advantages of environment protection, become the negative material of lithium ion cell electrode with prospects.But titanium dioxide conductivity is low by (~ 10 -13scm -1), cause high rate performance poor, be especially applied to electric automobile, large-scale energy-storage battery field is subject to great restriction.Thus, improve the conductivity of titanium dioxide electrodes material, and then raising high rate performance is that it is in lithium ion battery applications field problem demanding prompt solution.
Nanostructure can shorten the diffusion length of lithium ion in solid phase, increase the contact area between electrode and electrolyte simultaneously and then increase reactivity region, improve charge-discharge velocity, wherein nano tubular structure is because of its high specific area, and large voidage obtains especially and pays close attention to widely.But with regard to TiO 2nanotube; all there is the problem of crystallinity difference in the preparation method of its main flow; seriously limit its application; need high-temperature heat treatment to promote crystallinity; but nano material particle surface can be very high; and its surface area of always trend reduction reduces surface energy, the situation of surface area reduction, tubular construction heavy damage usually can occur in heat treatment process, therefore realize TiO 2in nanotube heat treatment process, the control of pattern becomes problem anxious to be resolved.
In addition, with highly conductor phase material compound, as metal, metal oxide, carbon-based material, be also the method for the conductivity improving titanium dioxide electrodes material, but compound highly conductor phase material need complicated technical process usually, is not suitable for large-scale production.In addition for the carbon-based material extensively adopted at present, its carbon source is generally the Small molecular such as glucose, can not realize nanotube surface coated uniformly, how meet simultaneously and keep the demand of tubular structure and even compound highly conductor phase material to be that an emphasis considers direction.
Summary of the invention
In order to overcome the defect that above-mentioned prior art exists, there is provided a kind of simple, the eco-friendly method preparing lithium ion battery negative material highly conductor phase material titanium dioxide nanotube, the method is by the coating function by organic macromolecule, the expansion of strength killer tube structure is provided from outside, and self carbonization is amorphous carbon, thus obtain the titania nanotube of the evenly coated well-crystallized of carbon, shorten lithium ion and electrons spread distance, by the bigger serface of nanotube to increase the contact area between electrode and electrolyte, by high connductivity substance amorphous carbon to improve conductivity, final raising is doubly forthright, coulombic efficiency and cycle performance, to meet the current demand to lithium ion battery.
Object of the present invention can be achieved through the following technical solutions.
A preparation method for the super long titanium dioxide nanotube lithium ion battery negative material that carbon is coated, is characterized in that comprising the following steps.
(1) titanium dioxide is placed in concentrated base, utilizes hydro thermal method to prepare sodium base titanate radical nanopipe (Na-TNT), the Na-TNT dilute acid wash will obtained subsequently, dry and collect powder, obtain hydrogen base titanate radical nanopipe (H-TNT).
(2) get the H-TNT of step (1) gained, be dissolved in absolute ethyl alcohol, mix with the ethanolic solution of polyvinylpyrrolidone (PVP), after adding thermal agitation, after washing and drying, obtain PVPTNT.
(3) by the PVPTNT of step (2) gained in an inert atmosphere high-temperature heat treatment obtain CTiO 2nanotube.
In step (1), described titanium dioxide is the one in P25, anatase, rutile.
In step (1), described highly basic must be NaOH or KOH of 10mol/L.
In step (1), HCl or HNO of described diluted acid must to be concentration be 0.1mol/L 3.
In step (2), described polyvinylpyrrolidone (PVP) molecular weight need at 5000-20000.
In step (2), the mol ratio of described H-TNT and PVP repetitive is 1:6-8.
In step (2), described heating condition is 60-90 DEG C, and heating time is 2-8h.
In step (3), described inert atmosphere adopts nitrogen or argon gas
In step (3), described high-temperature heat treatment temperature is between 400-500 DEG C, and the processing time, warming temperature was between 1-10 DEG C/min at 1.5-10h.
The invention has the advantages that the TiO by the coated after-baking of PVP 2pipe still maintains good tubular construction in high temperature environments, and because adopt to be that long-chain macromolecule carries out coated, what pipe was wound around is very even, and the homogeneity of surface carbon distribution is better than the carbon sources such as existing glucose.The crystallinity of pipe have also been obtained very large raising simultaneously.The CTiO obtained 2when nanotube is used for lithium ion cathode materials, its times of forthright, cycle performance is all compared without the coated heat treated TiO of PVP 2all obtain and improve greatly.Preparation method of the present invention has that output is high, technique is simple, easy to operate, raw material is easy to get, with low cost, advantages of environment protection, and whole course of reaction does not need special installation, is beneficial to suitability for industrialized production.Finally obtain product quality higher, show good chemical property as lithium ion battery negative material, there is excellent doubly forthright, high coulombic efficiency and stable cycle performance.
Accompanying drawing explanation.
The CTiO of Fig. 1 prepared by embodiment 1 2the X-ray energy spectrum figure (A) of nanotube and X-ray diffracting spectrum (B).
The CTiO of Fig. 2 prepared by embodiment 1 2the transmission electron microscope (A) of nanotube and high-resolution-ration transmission electric-lens figure (B).
The CTiO of Fig. 3 prepared by embodiment 2 2nanotube is charge-discharge performance figure when current density is 0.5C.
The CTiO of Fig. 4 prepared by embodiment 3 2nanotube is charge-discharge performance figure when current density is 10C.
The CTiO of Fig. 5 prepared by embodiment 3 2the high rate performance figure of nanotube.
Embodiment 1.
During operation, first taking 1gP25 powder in the 10mol/L sodium hydrate aqueous solution of 50mL is uniformly dispersed, and stirs 2.5h, subsequently mixed solution is placed in polytetrafluoroethylene inner liner of reaction kettle, transfers to after in water heating kettle in 150 DEG C of hydro-thermal reaction 24h in an oven.Thereafter cool to room temperature, takes out liner, outwells supernatant, obtain white precipitate, washes centrifugally to be about 7 to supernatant pH.After alcohol wash one time, precipitation is scattered in culture dish, dries 5h for 80 DEG C, collect powder.Get the above-mentioned powder of 1g, add 300mLHCl(0.1mol/L), magnetic agitation 1.5h, centrifugal with after washing is 7 to supernatant pH, then alcohol wash is scattered in culture dish, dries 5h for 80 DEG C, collects powder, obtain hydrogen base titanate radical nanopipe (H-TNT).
Get the H-TNT of 0.2-0.5g, be dissolved in absolute ethyl alcohol, magnetic force stirs 10min, ultrasonic 20min; Get 0.51768-1.2942g molecular weight be 10000 polyvinylpyrrolidone (PVP) be dissolved in 20mL absolute ethyl alcohol, the mol ratio of control H-TNT and PVP repetitive is 1:6.Mixed by said two devices, 60 DEG C are heated and stir 3h.After taking out, 10000rpm rotating speed is centrifugal, after removing supernatant, washs 3-5 time respectively with deionized water and absolute ethyl alcohol.Be scattered in culture dish with absolute ethyl alcohol, dry 12h for 80 DEG C in an oven, obtain PVPTNT.
PVP-TNT is put in tube furnace, with Ar 2for protective gas, with 5 DEG C/min for programming rate, 500 DEG C of sintering 2h, Temperature fall, obtains CTiO 2nanotube, in anatase crystal.
The material that upper step is synthesized is used for lithium ion battery negative material, take conductive black as conductive agent, polyvinylidene fluoride (PVDF) makes anode plate for lithium ionic cell for binding agent, be to electrode with lithium metal, microporous polypropylene membrane is barrier film, take volume ratio as the 1MLiPF of ethylene carbonate (the EC)/dimethyl carbonate (DMC) of 1:1 6for electrolyte, in argon gas glove box, be assembled into 2032 type button cells.Adopt LANDCT-2001A tester at room temperature to carry out electrochemical property test, test voltage scope is 1.0-3.0V.Assembled battery is at 0.5C (1C=335mAg -1) first discharge specific capacity 282mAhg under current density -1.
The X-ray energy spectrum figure of the tubular nanometer titanium dioxide of Fig. 1 obtained by the present embodiment and X ray diffracting spectrum, as can be seen from the figure obtained material is anatase crystallization, in addition also has the existence of carbon.Fig. 2 is transmission electron microscope and the high-resolution picture of tubular nanometer titanium dioxide, and as seen from the figure, titanium dioxide pattern and size are comparatively even, and length 500-1000nm, amorphous carbon is evenly coated on the surface of pipe.
Embodiment 2.
According to the condition of embodiment 1, only changing programming rate is 1 DEG C/min, obtains the anatase nanotube having wrapped up agraphitic carbon.After being assembled into battery according to embodiment 1 method, under 0.5C current density, after 100 circulations, specific discharge capacity keeps 152mAhg -1.
Fig. 3 is prepared CTiO 2nanotube high rate performance figure, show excellent high rate performance, when current density reaches 20C, capacity remains on 126mAhg -1, when 0.5C falls back in current density, current density goes back up to 162mAhg again -1, close to initial value.
Embodiment 3.
According to the condition of embodiment 2, only changing holding temperature is 400 DEG C, obtains the TiO having wrapped up agraphitic carbon 2nanotube, its crystal formation is TiO 2-Type B, after being assembled into battery according to embodiment 1 method, under 10C current density, after 100 circulations, specific discharge capacity remains on 154mAhg -1, coulombic efficiency, close to 100%, as shown in Figure 4, shows this material and has excellent chemical property.
Fig. 5 is prepared CTiO 2nanotube high rate performance figure, show excellent high rate performance, when current density reaches 20C, capacity remains on 157mAhg -1, when 0.5C falls back in current density, current density goes back up to 219mAhg again -1, close to initial value.
In sum, a kind of lithium ion battery negative material CTiO of the present invention 2the preparation method of nanotube, the method is by synthesizing the high-specific area nano pipe of bag carbon, can realize shortening ion transfer Distance geometry simultaneously and improve the conductivity of material, the ion diffusion rates of material, make the material prepared have excellent specific capacity, stable cycle performance and high coulombic efficiency.
More than show and describe general principle of the present invention and principal character and advantage of the present invention; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and application claims protection range is defined by appending claims and equivalent thereof.

Claims (9)

1. a preparation method for the super long titanium dioxide nanotube lithium ion battery negative material that carbon is coated, is characterized in that comprising the following steps:
(1) titanium dioxide is placed in concentrated base, utilizes hydro thermal method to prepare sodium base titanate radical nanopipe (Na-TNT), the Na-TNT dilute acid wash will obtained subsequently, dry and collect powder, obtain hydrogen base titanate radical nanopipe (H-TNT);
(2) get the H-TNT of step (1) gained, be dissolved in absolute ethyl alcohol, mix with the ethanolic solution of polyvinylpyrrolidone (PVP), after adding thermal agitation, after washing and drying, obtain PVPTNT;
(3) by the PVPTNT of step (2) gained in an inert atmosphere high-temperature heat treatment obtain CTiO 2nanotube.
2. preparation method as claimed in claim 1, it is characterized in that in step (1), described titanium dioxide is the one in P25, anatase, rutile.
3. preparation method as claimed in claim 1, it is characterized in that in step (1), described highly basic must be NaOH or KOH of 10mol/L.
4. preparation method as claimed in claim 1, is characterized in that in step (1), HCl or HNO of described diluted acid must to be concentration be 0.1mol/L 3.
5. preparation method as claimed in claim 1, is characterized in that, in step (2), described polyvinylpyrrolidone (PVP) molecular weight need at 5000-20000.
6. preparation method as claimed in claim 1, it is characterized in that in step (2), the mol ratio of described H-TNT and PVP repetitive is 1:6-8.
7. preparation method as claimed in claim 1, it is characterized in that, in step (2), described heating condition is 60-90 DEG C, heating time is 2-8h.
8. preparation method as claimed in claim 1, is characterized in that in step (3), and described inert atmosphere adopts nitrogen or argon gas.
9. preparation method as claimed in claim 1, it is characterized in that in step (3), described high-temperature heat treatment temperature is between 400-500 DEG C, and the processing time, warming temperature was between 1-10 DEG C/min at 1.5-10h.
CN201510782324.XA 2015-11-16 2015-11-16 Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery Pending CN105406042A (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN106207112A (en) * 2016-07-15 2016-12-07 湖北工业大学 Graphene/overlength TiO2(B) nanometer tube composite materials and preparation method thereof
CN107799756A (en) * 2017-10-31 2018-03-13 湘潭大学 A kind of Na2Ti3O7The preparation method of C nano fiber
CN108780879A (en) * 2016-02-23 2018-11-09 南洋理工大学 Titanium dioxide (TiO2) nanostructure of extraordinary capacity is used for high power and high energy lithium ion cell
CN109768244A (en) * 2018-12-29 2019-05-17 华南理工大学 A kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material and the preparation method and application thereof
CN109980214A (en) * 2019-04-26 2019-07-05 四川昆仑云熙新能源科技有限公司 A kind of preparation method and lithium ion battery of carbon nanotube-graphite combination electrode material
CN110534709A (en) * 2018-05-25 2019-12-03 深圳格林德能源有限公司 A kind of sodium-ion battery carbon coating titanium oxide nanotube cathode material preparation method
CN112694121A (en) * 2020-12-30 2021-04-23 程承 Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of
CN113511674A (en) * 2021-06-30 2021-10-19 河北工业大学 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof

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US20080274403A1 (en) * 2007-05-04 2008-11-06 Il-Doo Kim Anode for secondary battery having negative active material with nano-fiber network structure and secondary battery using the same, and fabrication method of negative active material for secondary battery
CN101575118A (en) * 2009-06-12 2009-11-11 清华大学 Method for preparing hydrogen lithium titanate nano-tube or wire with high energy density
CN102157732A (en) * 2011-03-24 2011-08-17 河南大学 Titanium dioxide/carbon composite nanotube and preparation and application thereof
CN104098134A (en) * 2014-07-07 2014-10-15 北京大学 Preparation method and application of TiO2 nanotube coated with amorphous layer
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US20080274403A1 (en) * 2007-05-04 2008-11-06 Il-Doo Kim Anode for secondary battery having negative active material with nano-fiber network structure and secondary battery using the same, and fabrication method of negative active material for secondary battery
CN101575118A (en) * 2009-06-12 2009-11-11 清华大学 Method for preparing hydrogen lithium titanate nano-tube or wire with high energy density
CN102157732A (en) * 2011-03-24 2011-08-17 河南大学 Titanium dioxide/carbon composite nanotube and preparation and application thereof
CN104098134A (en) * 2014-07-07 2014-10-15 北京大学 Preparation method and application of TiO2 nanotube coated with amorphous layer
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108780879A (en) * 2016-02-23 2018-11-09 南洋理工大学 Titanium dioxide (TiO2) nanostructure of extraordinary capacity is used for high power and high energy lithium ion cell
CN106207112A (en) * 2016-07-15 2016-12-07 湖北工业大学 Graphene/overlength TiO2(B) nanometer tube composite materials and preparation method thereof
CN106207112B (en) * 2016-07-15 2019-05-17 湖北工业大学 Graphene/overlength TiO2(B) nanometer tube composite materials and preparation method thereof
CN107799756A (en) * 2017-10-31 2018-03-13 湘潭大学 A kind of Na2Ti3O7The preparation method of C nano fiber
CN110534709A (en) * 2018-05-25 2019-12-03 深圳格林德能源有限公司 A kind of sodium-ion battery carbon coating titanium oxide nanotube cathode material preparation method
CN109768244A (en) * 2018-12-29 2019-05-17 华南理工大学 A kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material and the preparation method and application thereof
CN109980214A (en) * 2019-04-26 2019-07-05 四川昆仑云熙新能源科技有限公司 A kind of preparation method and lithium ion battery of carbon nanotube-graphite combination electrode material
CN109980214B (en) * 2019-04-26 2021-10-01 四川昆仑云熙新能源科技有限公司 Preparation method of carbon nanotube-graphite composite electrode material and lithium ion battery
CN112694121A (en) * 2020-12-30 2021-04-23 程承 Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of
CN113511674A (en) * 2021-06-30 2021-10-19 河北工业大学 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof

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