CN103346308A - Preparation method and use of fluorine-doped lithium titanate lithium ion battery cathode material - Google Patents

Preparation method and use of fluorine-doped lithium titanate lithium ion battery cathode material Download PDF

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Publication number
CN103346308A
CN103346308A CN2013102405987A CN201310240598A CN103346308A CN 103346308 A CN103346308 A CN 103346308A CN 2013102405987 A CN2013102405987 A CN 2013102405987A CN 201310240598 A CN201310240598 A CN 201310240598A CN 103346308 A CN103346308 A CN 103346308A
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lithium
cathode material
battery cathode
preparation
fluorine
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徐云龙
赵震
赵崇军
钱秀珍
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WEINA TECH Co Ltd SHANGHAI
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WEINA TECH Co Ltd SHANGHAI
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    • 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 provides a fluorine-doped lithium titanate lithium ion battery cathode material and its preparation method and use. The preparation method comprises the following steps of weighing a certain amount of titanium dioxide, a lithium compound and a fluorine compound according to a stoichiometric ratio, adding the mixed materials into a ball milling tank, adding a carbon source additive of which the weight is 0-50% of the total weight of the mixed materials into the ball milling tank, carrying out ball milling in a uniform medium, and carrying out calcination in a dry environment at a high temperature to obtain the fluorine-doped lithium titanate lithium ion battery cathode material Li4Ti5FxO12-x, wherein x is greater than or equal to 0.1 and less than or equal to 0.5. The fluorine-doped lithium titanate lithium ion battery cathode material has excellent multiplying power performances and cycle performances. The fluorine-doped lithium titanate lithium ion battery cathode material has excellent multiplying power performances and is suitable for power batteries.

Description

A kind of preparation method and application of fluorine doped lithium titanate lithium ion battery negative material
Technical field
The invention belongs to battery critical material and technical field, be specifically related to a kind of ion secondary battery cathode material lithium and its preparation method and application, particularly relate to a kind of preparation method and application of novel fluorine doped lithium titanate lithium ion battery negative material.
Background technology
Lithium ion battery is because advantages such as its energy density height, self discharge are little, memory-less effect have leading position, on the electronic products such as extensive application and notebook, mobile phone in secondary cell market.Along with miniaturization and the microminiaturization of current electronic equipment, the research of lithium ion battery more and more comes into one's own with application.Along with the development of electric automobile, the high power type electrokinetic cell also becomes the focus of Study on Li-ion batteries using.
Recently, spinel type lithium titanate Li 4Ti 5O 12As a kind of novel negative material, lithium ion embeds and deviates from the process to keep good structural stability when battery charging and discharging, lattice constant does not change substantially, is a kind of " zero strain " insert type lithium ion battery negative material, has excellent cycle performance; It stablizes the recovery voltage that smooth voltage platform (1.55V) is higher than most of electrolyte and solvent, but thereby again electrode surface to form electronics and the ionic conductivity of passivating film lithium titanate very not low, high rate capability is relatively poor.Therefore, need be by its modification be improved its electronic conductivity, thus improve its high rate performance, can also keep its excellent cycle performance simultaneously.Can improve its fast charging and discharging performance and high-rate charge-discharge capability by mixing.
Chinese patent CN101378119A is with Li 2CO 3The lithium source, TiO 2Titanium source, water are dispersant, carry out ball milling and mix, and oven dry obtains presoma, place then under 900 ℃ of the Muffle furnaces and fire 14h, make Li 4Ti 5O 12Powder with lithium titanate joins in the ethanolic solution of phenolic resins then, stirs to make the ethanol evaporate to dryness, and sintering obtains carbon and coats lithium titanate then.What this patent adopted is the conventional high-temperature solid phase method, and product degree of crystallinity is higher, but because earlier synthetic lithium titanate, carbon coated again, and technology is comparatively complicated, and the product particle diameter is difficult to control, Li 4Ti 5O 12Average grain diameter is about 16 μ m.
Chinese patent CN102779989A discloses a kind of lithium ion battery with the preparation method of fluorine doping spherical lithium titanate, with Li 2CO 3The lithium source, TiO 2The titanium source, LiF is the fluorine doped source, pulverizes behind the high temperature sintering, stirs into suspension-turbid liquid with methylcellulose again, and the oily emulsion made of adding department class and atoleine forms water-in-oil emulsion then, and centrifugal high temperature sintering afterwards obtains spherical fluorine doped lithium titanate at last.This patent system Preparation Method complexity, fluorine doping seldom, the lithium titanate particle diameter that is prepared into is bigger, about 10 μ m.
The present invention explores simple method by systematic research, realizes effective raising of single fluorine doped lithium titanate chemical property, helps industrialization and the commercialization of lithium titanate material.
Summary of the invention
The objective of the invention is to overcome the defective that the high magnification that exists in the prior art for preparing lithium titanate anode material is transferred poor electrical performance, propose a kind of method of improving electronic conductivity, charge-discharge performance and the cycle performance of lithium ionic cell cathode material lithium titanate.The lithium titanate anode material of this method preparation demonstrates excellent chemical property.
In order to overcome Li 4Ti 5O 12The shortcoming that the electronic conductivity of material is low, the present inventor finds to adopt the solid phase high-energy ball milling method, doped with fluorine atom, the Li can composite structure stable, that particle size is less, chemical property is excellent 4Ti 5F xO 12-xPowder.
The invention provides a kind of preparation method of novel fluorine doped lithium titanate lithium ion battery negative material, it is characterized in that concrete steps are:
1) get the compound of lithium, titanium dioxide and fluorine doped source are Li according to target product 4Ti 5F xO 12-xIn the stoichiometric proportion weighing of doped chemical, add in the ball grinder; In ball grinder, add certain carbon source additive again, ball milling in uniform medium, oven dry; Wherein said carbon source additive is 0 ~ 50% of mixture gross mass;
2) with the powder of oven dry in nitrogen, argon gas, hydrogen at least a inert atmosphere or reducing atmosphere under down calcining 2 ~ 20 hours of 500 ℃ ~ 1000 ℃ of heating, namely make Li 4Ti 5F xO 12-xPowder.
Described fluorine doped source is at least a in ammonium fluoride, lithium fluoride, sodium fluoride, the aluminum fluoride.
Described titanium dioxide is Detitanium-ore-type.
The compound of described lithium is lithium nitrate or lithium carbonate or lithium chloride or lithium acetate or lithium citrate or lithium oxalate or lithium formate or lithium lactate or isopropyl lithium alkoxide, or contains organic alcohol, acid, the ester type compound of lithium.
Described carbon source additive is a kind of or its combination in active carbon, acetylene black, graphite, glucose, urea, sucrose, oxalic acid, citric acid, gluconic acid, tartaric acid, laurate, ethylenediamine tetra-acetic acid, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, soluble starch, phenolic resins, the polymethyl methacrylate.
Described ball-milling medium is a kind of in water, ethanol, acetone, the ether or its combination, and described drying means is at least a in vacuumize, the spray drying.
The invention provides a kind of ion secondary battery cathode material lithium.
The invention provides a kind of ion secondary battery cathode material lithium in the application of lithium-ion battery system.
Beneficial effect:
The chemical formula of prepared fluorine doped lithium titanate is Li 4Ti 5F xO 12-xExpression, wherein F is fluorine element, the value of x is between 0.01 ~ 0.5.500 times charging and discharging capacity is still above 130mAh/g later in the 2C circulation for this material, and conservation rate is more than 99%.
The present invention adopts the solid phase high-energy ball milling method, and the preparation method is simple, safety, and raw material sources are extensive, and cost is low, is easy to realize industrialization.The doped with fluorine ion can significantly improve the conductance of lithium titanate electrode material, significantly improves high rate performance and the cycle performance of lithium titanate electrode material.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 product;
Fig. 2 is the low power SEM photo of the embodiment of the invention 1 product;
Fig. 3 is the high power SEM photo of the embodiment of the invention 1 product;
Fig. 4 is the discharge cycles figure of the embodiment of the invention 2 under different multiplying;
Fig. 5 is circulate under the 2C multiplying power 500 times discharge curve of the embodiment of the invention 2.
Specific implementation method
The present invention is described in detail by following specific embodiment, but protection scope of the present invention is not subject to these embodiment.
Embodiment 1: the Li of synthetic 0.01mol 4Ti 5F 0.5O 11.5-, according to mol ratio Li:Ti:F=10:10:1, take by weighing the Detitanium-ore-type TiO-of 4g 2(analyzing pure), the LiF(of 0.13g analyzes pure), the Li of 1.665g 2CO 3The polyethylene glycol of (analyzing pure) and 1.7385g (analyze pure, molecular weight is 2000) is put into ball grinder, adds agate ball and absolute ethyl alcohol, the sealing ball milling, on ball mill with the rotating speed ball milling of 250r/min 6 hours, the mixed slurry that obtains mixing.Slurry is put into spray drying device, obtain dry precursor by spray drying.Precursor powder is placed in the tube furnace, under nitrogen atmosphere, is warming up to 400 ℃ of insulations with the heating rate of 5 ℃/min and presoma was tentatively decomposed in 6 hours, the heating rate with 5 ℃/min rises to 800 ℃ of constant temperature 10 hours then, obtains Li after cooling off naturally 4Ti 5F 0.5O 11.5Fig. 1 is the XRD figure of gained sample.As seen, by high-energy ball milling method doped with fluorine ion, the XRD of synthetic product scheme the position of each diffraction maximum and relative intensity all with -Li 4Ti 5O 12Standard card gentle mutually, do not have any dephasign.Fig. 2 and Fig. 3 are the SEM photo of gained sample, and particle is spherical, and particle diameter is about 40nm, is evenly distributed, and show and adopt high-energy ball milling method doped with fluorine ion, can prepare the less Li of particle size 4Ti 5O 12
Embodiment 2: the Li of synthetic 0.01mol 4Ti 5F 0.3O 11.7-, according to mol ratio Li:Ti:F=50:50:3, take by weighing the Detitanium-ore-type TiO-of 4g 2(analyzing pure), the LiF(of 0.078g analyzes pure), the Li of 1.739g 2CO 3The citric acid of (analyzing pure) and 1.7451g is put into ball grinder, adds agate ball and absolute ethyl alcohol, the sealing ball milling, on ball mill with the rotating speed ball milling of 350r/min 6 hours, the mixed slurry that obtains mixing.Slurry is put into spray drying device, obtain dry precursor by spray drying.Precursor powder is placed in the tube furnace, under argon gas atmosphere, rises to 850 ℃ of constant temperature 8 hours with the heating rate of 5 ℃/min, obtain Li after the cooling naturally 4Ti 5F 0.3O 11.7Fig. 4 and Fig. 5 are for to do positive pole with this material, and metal lithium sheet is done negative pole and is assembled into the resolution chart that simulated battery carries out high rate performance and cycle performance.Wherein Fig. 4 is the discharge cycles figure of this material under different multiplying, and specific discharge capacity remains on about 170mAh/g under the 1C multiplying power as can be seen from FIG., the specific discharge capacity 100mAh/g that still has an appointment under the 10C multiplying power.Fig. 5 is this material later discharge cycles curve that circulates under the 2C multiplying power 500 times, and 500 times circulation back discharge capacity still remains on about 150mAh/g, and enclosed pasture efficient is near 100%.
Embodiment 3: the Li of synthetic 0.01mol 4Ti 5F 0.1O 11.9-, according to mol ratio Li:Ti:F=50:50:1, take by weighing the Detitanium-ore-type TiO-of 4g 2(analyzing pure), the LiF(of 0.026g analyzes pure), the LiOH(of 1.176g analyzes pure) and the acetylene black of 2.601g, put into ball grinder, add agate ball and absolute ethyl alcohol, the sealing ball milling, on ball mill with the rotating speed ball milling of 300r/min 6 hours, the mixed slurry that obtains mixing.Slurry is put into 80 ℃ of vacuum drying chambers 12 hours, obtain dry precursor.Precursor powder is placed in the tube furnace, under argon gas atmosphere, rises to 850 ℃ of constant temperature 20 hours with the heating rate of 10 ℃/min, obtain Li after the cooling naturally 4Ti 5F 0.1O 11.9By measuring sample Li 4Ti 5F 0.1O 11.9With pure phase Li 4Ti 5O 12AC impedance, obtain Li 4Ti 5F 0.1O 11.9Electric charge transfger impedance R CtBe 35.38 Ω, and pure phase Li 4Ti 5O 12Electric charge transfger impedance R CtBe 90.98 Ω, find effectively to improve the conductivity of lithium titanate electrode material by the doped with fluorine ion.
Embodiment 4: the Li of synthetic 0.01mol 4Ti 5F 0.35O 11.65-, according to mol ratio Li:Ti:F=50:50:1, take by weighing the Detitanium-ore-type TiO-of 4g 2(analyzing pure), the LiF(of 0.091g analyzes pure), the Li of 1.7205g 2CO 3The sucrose of (analyzing pure) and 2.3246g is put into ball grinder, adds agate ball and absolute ethyl alcohol, the sealing ball milling, on ball mill with the rotating speed ball milling of 300r/min 9 hours, the mixed slurry that obtains mixing.Slurry is put into 120 ℃ of vacuum drying chambers 8 hours, obtain dry precursor.Precursor powder is placed in the tube furnace, under argon gas atmosphere, rises to 850 ℃ of constant temperature 15 hours with the heating rate of 4 ℃/min, obtain Li after the cooling naturally 4Ti 5F 0.35O 11.65
Embodiment 5: the Li of synthetic 0.01mol 4Ti 5F 0.2O 11.8, according to mol ratio Li:Ti:F=50:50:1, take by weighing the Detitanium-ore-type TiO-of 4g 2(analyzing pure), the LiF(of 0.052g analyzes pure), the Li of 1.776g 2CO 3The glucose of (analyzing pure) and 0.5828g is put into ball grinder, adds agate ball and absolute ethyl alcohol, the sealing ball milling, on ball mill with the rotating speed ball milling of 400r/min 4 hours, the mixed slurry that obtains mixing.Slurry is put into spray drying device, obtain dry precursor by spray drying.Precursor powder is placed in the tube furnace, under argon gas atmosphere, rises to 800 ℃ of constant temperature 11 hours with the heating rate of 3 ℃/min, obtain Li after the cooling naturally 4Ti 5F 0.2O 11.8

Claims (8)

1. the preparation method of a fluorine doped lithium titanate lithium ion battery negative material is characterized in that, described lithium ionic cell cathode material lithium titanate molecular formula Li 4Ti 5F xO 12-xExpression, wherein F is fluorine element, 0.1≤x≤0.5;
Described ion secondary battery cathode material lithium fluorine doped lithium titanate preparation method's concrete mode is as follows:
Get the compound of lithium, titanium dioxide and fluorine doped source are Li according to target product 4Ti 5F xO 12-xIn the stoichiometric proportion weighing of doped chemical, add in the ball grinder; In ball grinder, add certain carbon source additive again, ball milling in uniform medium, oven dry; Wherein said carbon source additive is 0 ~ 50% of mixture gross mass;
With the powder of oven dry in nitrogen, argon gas, hydrogen at least a inert atmosphere or reducing atmosphere under down calcining 2 ~ 20 hours of 500 ℃ ~ 1000 ℃ of heating, namely make Li 4Ti 5F xO 12-xPowder.
2. the preparation method of ion secondary battery cathode material lithium fluorine doped lithium titanate according to claim 1 is characterized in that, described fluorine doped source is at least a in ammonium fluoride, lithium fluoride, sodium fluoride, the aluminum fluoride.
3. the preparation method of ion secondary battery cathode material lithium fluorine doped lithium titanate according to claim 1 is characterized in that, described titanium dioxide is Detitanium-ore-type.
4. the preparation method of ion secondary battery cathode material lithium fluorine doped lithium titanate according to claim 1, it is characterized in that, the compound of described lithium is lithium nitrate or lithium carbonate or lithium chloride or lithium acetate or lithium citrate or lithium oxalate or lithium formate or lithium lactate or isopropyl lithium alkoxide, or contains organic alcohol, acid, the ester type compound of lithium.
5. the preparation method of ion secondary battery cathode material lithium fluorine doped lithium titanate according to claim 1 is characterized in that described carbon source additive is a kind of or its combination in active carbon, acetylene black, graphite, glucose, urea, sucrose, oxalic acid, citric acid, gluconic acid, tartaric acid, laurate, ethylenediamine tetra-acetic acid, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, soluble starch, phenolic resins, the polymethyl methacrylate.
6. the preparation method of ion secondary battery cathode material lithium fluorine doped lithium titanate according to claim 1, it is characterized in that, described ball-milling medium is a kind of in water, ethanol, acetone, the ether or its combination, and described drying means is at least a in vacuumize, the spray drying.
7. the ion secondary battery cathode material lithium that is obtained by the described method of one of claims 1 ~ 6.
8. by the application of claims 7 described ion secondary battery cathode material lithiums at lithium-ion battery system.
CN2013102405987A 2013-06-17 2013-06-17 Preparation method and use of fluorine-doped lithium titanate lithium ion battery cathode material Pending CN103346308A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104752707A (en) * 2015-03-03 2015-07-01 深圳市翔丰华科技有限公司 Titanium dioxide (B) negative electrode material and preparation method thereof
CN105845924A (en) * 2016-05-23 2016-08-10 扬州大学 Preparation method for fluorine-doping Li4Ti5O12 nanosheet
CN106099095A (en) * 2016-07-18 2016-11-09 扬州大学 The preparation method of fluorine nitrogen co-doped carbon cladding lithium titanate nanometer sheet
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN109473670A (en) * 2018-12-18 2019-03-15 上海纳米技术及应用国家工程研究中心有限公司 The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application
CN109659530A (en) * 2018-12-17 2019-04-19 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of fluorine-containing lithium titanate packet carbon composite and products thereof and application
CN110459761A (en) * 2019-08-21 2019-11-15 宋婷 A kind of codope lithium titanate anode material and preparation method thereof
CN111137919A (en) * 2018-11-06 2020-05-12 财团法人工业技术研究院 Doped titanium niobate and battery
CN112768648A (en) * 2020-12-29 2021-05-07 深圳石墨烯创新中心有限公司 Tin dioxide/carbon @ titanium dioxide microsphere composite material for lithium ion battery cathode and preparation method and application thereof
CN113130884A (en) * 2021-04-07 2021-07-16 福建大成新能源科技有限公司 F-doped TiO2Preparation method and application of (E) -B
CN114824245A (en) * 2022-03-24 2022-07-29 湖北钛时代新能源有限公司 Preparation method of ultralow temperature battery
WO2024024908A1 (en) * 2022-07-28 2024-02-01 住友金属鉱山株式会社 Negative electrode active material for lithium-ion secondary batteries, method for producing negative electrode active material for lithium-ion secondary batteries, and lithium-ion secondary battery

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CN102779989A (en) * 2012-08-14 2012-11-14 天津巴莫科技股份有限公司 Method for preparing fluorine-doped spherical lithium titanate for lithium ion battery
CN103107324A (en) * 2013-03-04 2013-05-15 江苏大学 Preparation methods of fluorine-containing lithium ion battery cathode material lithium titanate (Li4Ti5O12)

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CN101759227A (en) * 2008-12-24 2010-06-30 比亚迪股份有限公司 Lithium titanate composite material and preparation method thereof
CN102779989A (en) * 2012-08-14 2012-11-14 天津巴莫科技股份有限公司 Method for preparing fluorine-doped spherical lithium titanate for lithium ion battery
CN103107324A (en) * 2013-03-04 2013-05-15 江苏大学 Preparation methods of fluorine-containing lithium ion battery cathode material lithium titanate (Li4Ti5O12)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104752707A (en) * 2015-03-03 2015-07-01 深圳市翔丰华科技有限公司 Titanium dioxide (B) negative electrode material and preparation method thereof
CN105845924A (en) * 2016-05-23 2016-08-10 扬州大学 Preparation method for fluorine-doping Li4Ti5O12 nanosheet
CN105845924B (en) * 2016-05-23 2019-01-15 扬州大学 The preparation method of the lithium titanate nanometer sheet of Fluorin doped
CN106099095A (en) * 2016-07-18 2016-11-09 扬州大学 The preparation method of fluorine nitrogen co-doped carbon cladding lithium titanate nanometer sheet
CN108417785A (en) * 2018-01-11 2018-08-17 茆胜 Fluorine nitrogen-doped graphene coats lithium titanate composite material and preparation method thereof
CN108417785B (en) * 2018-01-11 2020-11-17 茆胜 Fluorine-nitrogen doped graphene coated lithium titanate composite material and preparation method thereof
CN111137919A (en) * 2018-11-06 2020-05-12 财团法人工业技术研究院 Doped titanium niobate and battery
CN109659530A (en) * 2018-12-17 2019-04-19 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of fluorine-containing lithium titanate packet carbon composite and products thereof and application
CN109473670A (en) * 2018-12-18 2019-03-15 上海纳米技术及应用国家工程研究中心有限公司 The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application
CN110459761A (en) * 2019-08-21 2019-11-15 宋婷 A kind of codope lithium titanate anode material and preparation method thereof
CN110459761B (en) * 2019-08-21 2022-05-17 江西优灿新能源科技有限公司 Codoped lithium titanate negative electrode material and preparation method thereof
CN112768648A (en) * 2020-12-29 2021-05-07 深圳石墨烯创新中心有限公司 Tin dioxide/carbon @ titanium dioxide microsphere composite material for lithium ion battery cathode and preparation method and application thereof
CN113130884A (en) * 2021-04-07 2021-07-16 福建大成新能源科技有限公司 F-doped TiO2Preparation method and application of (E) -B
CN113130884B (en) * 2021-04-07 2024-02-13 福建大成新能源科技有限公司 F-doped TiO 2 Preparation method and application of-B
CN114824245A (en) * 2022-03-24 2022-07-29 湖北钛时代新能源有限公司 Preparation method of ultralow temperature battery
WO2024024908A1 (en) * 2022-07-28 2024-02-01 住友金属鉱山株式会社 Negative electrode active material for lithium-ion secondary batteries, method for producing negative electrode active material for lithium-ion secondary batteries, and lithium-ion secondary battery

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Application publication date: 20131009