CN107170975A - A kind of method and lithium titanate for lifting lithium titanate electrical conductivity - Google Patents

A kind of method and lithium titanate for lifting lithium titanate electrical conductivity Download PDF

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Publication number
CN107170975A
CN107170975A CN201710406256.6A CN201710406256A CN107170975A CN 107170975 A CN107170975 A CN 107170975A CN 201710406256 A CN201710406256 A CN 201710406256A CN 107170975 A CN107170975 A CN 107170975A
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China
Prior art keywords
lithium titanate
electrical conductivity
lithium
lifted
tio
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Pending
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CN201710406256.6A
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Chinese (zh)
Inventor
曹元成
程琦
汤舜
闫继
梁济元
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Jianghan University
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Jianghan University
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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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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 belongs to lithium ion cell nano field of material technology, a kind of method for lifting lithium titanate electrical conductivity is disclosed, including：Prepare carbon coating TiO2；By the carbon coating TiO2And Li2CO3It is dispersed in ball milling mixing in absolute ethyl alcohol；Compound after ball milling is subjected to charging drying, high-temperature heat treatment, obtains Li under inert gas atmosphere4Ti5O12/ C composite；Wherein, the treatment conditions of the high-temperature heat treatment are 800 DEG C, keep 12h.The present invention provides a kind of method for lifting lithium titanate electrical conductivity, reaches that powder particle size is small, pattern is homogeneous, and granule regularizing degree is high, the effect with higher specific capacity and cycle life, available for high multiplying power electrokinetic cell field.

Description

A kind of method and lithium titanate for lifting lithium titanate electrical conductivity
Technical field
The present invention relates to lithium ion cell nano field of material technology, more particularly to a kind of side for lifting lithium titanate electrical conductivity Method and lithium titanate.
Background technology
Li4Ti5O12Because there is tight security and stability compared with carbon material negative pole, become safe lithium ion battery and bear Wide concerned candidate materials in extremely.It is used as negative material, Li4Ti5O12With stable discharge voltage plateau (1.55V vs Li+/ Li) and charge and discharge process in volume hardly occur any change, with " zero strain " characteristic, therefore with extraordinary Cycle performance.
But Li4Ti5O12Electronic conductivity is low, high rate charge-discharge poor performance.To improve Li4Ti5O12Electrical conductivity and electrification Performance is learned, mainly increases electrical conductivity by particle nanosizing, element doping, introducing three kinds of methods of conductive phase in the prior art To improve high rate during charging-discharging.Using carbon coating to Li4Ti5O12Carry out carbon composite modified, be applied to industrial production It is central；But, the C/Li of synthesis4Ti5O12Sample chemical property is unsatisfactory, it is difficult to reach high multiplying power electrokinetic cell field Use demand.
The content of the invention
The present invention provides a kind of method for lifting lithium titanate electrical conductivity, reaches that powder particle size is small, pattern is homogeneous, particle Regularity is high, the effect with higher specific capacity and cycle life, available for high multiplying power electrokinetic cell field.
In order to solve the above technical problems, the invention provides a kind of method for lifting lithium titanate electrical conductivity, including：
Prepare carbon coating TiO2；
By the carbon coating TiO2And Li2CO3It is dispersed in ball milling mixing in absolute ethyl alcohol；
Compound after ball milling is subjected to charging drying, high-temperature heat treatment, obtains Li under inert gas atmosphere4Ti5O12/ C composite；
Wherein, the treatment conditions of the high-temperature heat treatment are 800 DEG C, keep 12h.
Further, the preparation carbon coating TiO2Including：
By TiO2Nano powder and glucose are dissolved in ethanol, are stirred at room temperature；
In thermal-arrest stirring container, the stirring solvent evaporated that is rapidly heated obtains drying composite；
The drying composite is warming up at least 500 DEG C with 2~8 DEG C/min, and is calcined under inert gas atmosphere, is obtained To carbon coating TiO2。
Further, in the thermal-arrest stirring container, solvent evaporated process temperature is maintained at 100 DEG C.
Further, the drying composite is calcined at least 3 hours under inert gas atmosphere.
Further, the glucose can be substituted with fructose or starch or dopamine or Glucosamine.
Further, the TiO2Nano powder uses rutile titanium dioxide or anatase titanium dioxide.
Further, the Li2CO3It can be substituted with lithium acetate or lithium lactate or lithium hydroxide or lithium nitrate.
Further, the inert gas uses nitrogen or argon gas.
Further, the TiO2 nano powders and Li2CO3Material amount ratio be 4.1: 5
The lithium titanate material that a kind of method using described lifting lithium titanate electrical conductivity is prepared.
The one or more technical schemes provided in the embodiment of the present application, have at least the following technical effects or advantages：
The method of the lifting lithium titanate electrical conductivity provided in the embodiment of the present application, by carrying out presoma carbon cladding two in advance Titanium oxide, and coordinate processing technology to adjust Li4Ti5O12/ C sample chemical property, improves its chemical property；Specifically, The dispensing synthesized by the advance cladding titanium dioxide of carbon as the later stage, then with lithium carbonate material fit react produce, during match somebody with somebody Grinding process is closed, high-temperature calcination make it that the carbon coating Li4Ti5O12 powder particle sizes of gained are small, and pattern is homogeneous, granule regularizing Degree is high, with higher specific capacity and cycle life, available for high multiplying power electrokinetic cell field.
Brief description of the drawings
Fig. 1 is the XRD that sample is made in carbon pre-coated method provided in an embodiment of the present invention and traditional cladding process；
Fig. 2 is the SEM figures that carbon pre-coated method provided in an embodiment of the present invention handles lithium titanate sample；
Fig. 3 schemes for the SEM of traditional sour lithium sample of cladding process titanium processing provided in an embodiment of the present invention；
Fig. 4 schemes for the SEM of untreated lithium titanate sample provided in an embodiment of the present invention；
Fig. 5 is that sample prepared by carbon pre-coated method provided in an embodiment of the present invention and traditional cladding process is tested under 2C multiplying powers Cycle charge discharge electrograph；
Fig. 6 be the sample for preparing of carbon pre-coated method provided in an embodiment of the present invention and traditional cladding process in 0.1C, Test curve under 0.5C.1C, 2C, 5C multiplying power；
Fig. 7 is the electrochemical impedance figure of sample prepared by carbon pre-coated method provided in an embodiment of the present invention and traditional cladding process Spectrum.
Embodiment
The embodiment of the present application reaches powder particle size by providing a kind of method for lifting lithium titanate electrical conductivity Small, pattern is homogeneous, and granule regularizing degree is high, the effect with higher specific capacity and cycle life, available for high magnification power electric Pond field.
In order to be better understood from above-mentioned technical proposal, below in conjunction with Figure of description and specific embodiment to upper State technical scheme to be described in detail, it should be understood that the specific features in the embodiment of the present invention and embodiment are to the application skill The detailed description of art scheme, rather than the restriction to technical scheme, in the case where not conflicting, the embodiment of the present application And the technical characteristic in embodiment can be mutually combined.
A kind of method for lifting lithium titanate electrical conductivity, including：
Prepare carbon coating TiO2；
By the carbon coating TiO2And Li2CO3It is dispersed in ball milling mixing in absolute ethyl alcohol；
Compound after ball milling is subjected to charging drying, high-temperature heat treatment, obtains Li under inert gas atmosphere4Ti5O12/ C composite；
Wherein, the treatment conditions of the high-temperature heat treatment are 800 DEG C, keep 12h.
Specifically, the preparation carbon coating TiO2Including：By TiO2Nano powder and glucose are dissolved in ethanol, and room temperature is stirred Mix；In thermal-arrest stirring container, the stirring solvent evaporated that is rapidly heated obtains drying composite；By the drying composite with 2~8 DEG C/min is warming up at least 500 DEG C, and be calcined under inert gas atmosphere, obtains carbon coating TiO2。
Wherein, in the thermal-arrest stirring container, solvent evaporated process temperature is maintained at 100 DEG C.The drying composite Calcine under inert gas atmosphere at least 3 hours.
In general, the glucose can be substituted with fructose or starch or dopamine or Glucosamine.The TiO2 Nano powder uses rutile titanium dioxide or anatase titanium dioxide.The Li2CO3Can with lithium acetate or lithium lactate or Lithium hydroxide or lithium nitrate are substituted.The inert gas uses nitrogen or argon gas.
The TiO2 nano powders and Li2CO3Material amount ratio be 4.1: 5
The present embodiment also provides the lithium titanate material that a kind of method using described lifting lithium titanate electrical conductivity is prepared Material.
Preparation embodiment below by a specific Li4Ti5O12/C composites illustrates this programme.
Li4Ti5O12The preparation process of/C composite is as follows:
By anatase nano-TiO2Commodity powder and glucose are dissolved in ethanol in certain proportion, are stirred at room temperature 1 hour.
Then it is rapidly heated in magnetic force thermal-arrest agitator to 100 DEG C of stirring solvent evaporateds, by obtained drying composite with 5 DEG C/min is warming up to 500 DEG C, nitrogen atmosphere is calcined 3 hours, produces the titanium dioxide of carbon coating.
By the TiO of the carbon coating of gained2With Li2CO3Ball milling mixing in absolute ethyl alcohol is dispersed in, the mixing after ball milling is filled Expect drying, in a nitrogen atmosphere high-temperature heat treatment, treatment conditions are 800 DEG C, and 12h obtains Li4Ti5O12/ C composite (C/ LTO-pre)。
Referring to Fig. 1~7, answered by the Li4Ti5O12/C obtained with untreated lithium titanate (LTO), traditional cladding process processing Condensation material (C/LTO-post) and the Li4Ti5O12/C composites (C/ for using the carbon pre-coated method processing of the application to obtain LTO-pre measure) compares.
It was found that, the Li4Ti5O12/C composites (C/LTO-pre) that the carbon pre-coated method processing that the application is provided is obtained, Particle size is small, and pattern is homogeneous, and granule regularizing degree is high, the effect with higher specific capacity and cycle life, chemical property Far above existing method, available for high multiplying power electrokinetic cell field.
The one or more technical schemes provided in the embodiment of the present application, have at least the following technical effects or advantages：
The method of the lifting lithium titanate electrical conductivity provided in the embodiment of the present application, by carrying out presoma carbon cladding two in advance Titanium oxide, and coordinate processing technology to adjust Li4Ti5O12/ C sample chemical property, improves its chemical property；Specifically, The dispensing synthesized by the advance cladding titanium dioxide of carbon as the later stage, then with lithium carbonate material fit react produce, during match somebody with somebody Grinding process is closed, high-temperature calcination make it that the carbon coating Li4Ti5O12 powder particle sizes of gained are small, and pattern is homogeneous, granule regularizing Degree is high, with higher specific capacity and cycle life, available for high multiplying power electrokinetic cell field.
It should be noted last that, above embodiment is merely illustrative of the technical solution of the present invention and unrestricted, Although the present invention is described in detail with reference to example, it will be understood by those within the art that, can be to the present invention Technical scheme modify or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, it all should cover Among scope of the presently claimed invention.

Claims (10)

1. a kind of method for lifting lithium titanate electrical conductivity, it is characterised in that including：
Prepare carbon coating TiO2；
By the carbon coating TiO2And Li2CO3It is dispersed in ball milling mixing in absolute ethyl alcohol；
Compound after ball milling is subjected to charging drying, high-temperature heat treatment, obtains Li under inert gas atmosphere4Ti5O12/ C is combined Material；
Wherein, the treatment conditions of the high-temperature heat treatment are 800 DEG C, keep 12h.
2. the method for lithium titanate electrical conductivity is lifted as claimed in claim 1, it is characterised in that the preparation carbon coating TiO2Bag Include：
By TiO2Nano powder and glucose are dissolved in ethanol, are stirred at room temperature；
In thermal-arrest stirring container, the stirring solvent evaporated that is rapidly heated obtains drying composite；
The drying composite is warming up at least 500 DEG C with 2~8 DEG C/min, and is calcined under inert gas atmosphere, carbon is obtained Coat TiO2。
3. the method for lithium titanate electrical conductivity is lifted as claimed in claim 2, it is characterised in that in the thermal-arrest stirring container In, solvent evaporated process temperature is maintained at 100 DEG C.
4. the method for lithium titanate electrical conductivity is lifted as claimed in claim 2, it is characterised in that：The drying composite is in inertia Calcined under gas atmosphere at least 3 hours.
5. the method for lithium titanate electrical conductivity is lifted as claimed in claim 2, it is characterised in that：The glucose can use fructose Or starch or dopamine or Glucosamine replacement.
6. the method for lithium titanate electrical conductivity is lifted as claimed in claim 2, it is characterised in that：The TiO2Nano powder is using gold Red stone titanium dioxide or anatase titanium dioxide.
7. the method for lithium titanate electrical conductivity is lifted as claimed in claim 1, it is characterised in that：The Li2CO3Acetic acid can be used Lithium or lithium lactate or lithium hydroxide or lithium nitrate are substituted.
8. the method for lithium titanate electrical conductivity is lifted as claimed in claim 1, it is characterised in that：The inert gas uses nitrogen Or argon gas.
9. the method for the lifting lithium titanate electrical conductivity as described in any one of claim 1~8, it is characterised in that：The TiO2 receives Ground rice and Li2CO3Material amount ratio be 4.1: 5.
10. the lithium titanate material that a kind of method using lifting lithium titanate electrical conductivity as claimed in claim 9 is prepared.
CN201710406256.6A 2017-06-01 2017-06-01 A kind of method and lithium titanate for lifting lithium titanate electrical conductivity Pending CN107170975A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654607A (en) * 2018-04-10 2018-10-16 苏州大学 The preparation method of silver nano-grain/carbon/nano titania compound of nucleocapsid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102001701A (en) * 2010-11-12 2011-04-06 合肥国轩高科动力能源有限公司 Method for preparing carbon-coated nano lithium titanate material
CN102945952A (en) * 2012-12-05 2013-02-27 吉林大学 Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102001701A (en) * 2010-11-12 2011-04-06 合肥国轩高科动力能源有限公司 Method for preparing carbon-coated nano lithium titanate material
CN102945952A (en) * 2012-12-05 2013-02-27 吉林大学 Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654607A (en) * 2018-04-10 2018-10-16 苏州大学 The preparation method of silver nano-grain/carbon/nano titania compound of nucleocapsid

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Application publication date: 20170915