CN107792878A - A kind of graded structure titanium dioxide（B）Preparation method and its application in lithium ion battery - Google Patents

A kind of graded structure titanium dioxide（B）Preparation method and its application in lithium ion battery Download PDF

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Publication number
CN107792878A
CN107792878A CN201711014922.8A CN201711014922A CN107792878A CN 107792878 A CN107792878 A CN 107792878A CN 201711014922 A CN201711014922 A CN 201711014922A CN 107792878 A CN107792878 A CN 107792878A
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graded structure
structure tio
tio
milliliters
lithium ion
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CN107792878B (en
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魏明灯
柳宇彬
陈文强
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Fuzhou University
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Fuzhou 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
    • H01M4/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • 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 technical field of lithium ion, and in particular to a kind of graded structure TiO2B fast preparation method and its application in lithium ion battery.By the way that glycolic is dissolved in water, butyl titanate, the concentrated sulfuric acid and glucose are then added, is stirred, washing and drying after autoclave has reacted, then calcine, obtain graded structure TiO2B, graded structure TiO2B, which makees cathode of lithium battery, has very high specific capacity and cyclical stability, in larger 1.675 A/g of current density discharge and recharge 100 enclose, capacity is stable in 202.3 mAh/g.

Description

A kind of graded structure titanium dioxide（B）Preparation method and its in lithium ion battery In application
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of graded structure TiO2- B quick preparation side Method and its application in lithium ion battery.
Background technology
Do not have also at present and quickly prepare graded structure TiO2- B Patents report.Last century the nineties lithium ion Since battery is succeeded in developing, lithium ion battery has been obtained for being widely applied, but to obtain good cycle, specific capacity Height, the good lithium ion battery negative material of high rate during charging-discharging are the research emphasis of scientist all the time.Titanium dioxide As a kind of material of embedded type, because its is safe and non-toxic, abundance, the advantages that stable circulation is good, is closed by researcher Note.Titanium dioxide is a kind of oxide with a variety of crystalline phases, and common crystalline phase has anatase, rutile, brockite and TiO2- B phases.Wherein TiO2- B mutually belongs to metastable phase, because its structure has more open spatial channel, can more effectively enter The embedding lithium abjection of row lithium ion, turn into the focus of recent researches.However, TiO2Preparing for-B is complex, generally by Hydrogen titanate is thermally treated resulting in.
The content of the invention
It is an object of the invention to provide a kind of graded structure TiO2- B fast preparation method and its in lithium-ion electric Application in pond.
To achieve the above object, the present invention adopts the following technical scheme that：
Specific preparation method is as follows：3.5 grams of glycolic is dissolved in the water of 20-30 milliliters, then adds 0.5-2 milliliters Butyl titanate, the concentrated sulfuric acid of 0.1-1 milliliters and 1-5 grams of glucose, stirring, move into 50 milliliters of reactor, be placed in In 100-200 DEG C of baking oven, 2-10 hours are reacted, products obtained therefrom is washed with water for several times, drying, by sample in 400 DEG C of air 1-3 hour is calcined under atmosphere, obtains graded structure TiO2-B。
Lithium ion battery assembles：In mass ratio by graded structure TiO2-B：Kynoar：Acetylene black=70：20：10 Equably it is coated in after mixed grinding on copper foil and does negative pole, reference electrode and be lithium metal to electrode, electrolyte is 1M LiPF6 EC+DMC+EMC (EC/DMC/EMC=1/1/1 v/v) solution.
The remarkable advantage of the present invention is：
The invention provides a kind of graded structure TiO2- B fast preparation methods, this method technique is simple, inexpensive, energy consumption Low, favorable reproducibility, performance is excellent.
Brief description of the drawings
Fig. 1 graded structures TiO2- B X-ray diffraction spectrogram；
Fig. 2 graded structures TiO2- B Raman spectrogram；
Fig. 3 graded structures TiO2- B scanning electron microscope (SEM) photograph；
Fig. 4 graded structures TiO2- B transmission electron microscope picture；
Fig. 5 graded structures TiO2- B chemical property figure（Current density is 1.675 A/g）.
Embodiment
For the further open rather than limitation present invention, below in conjunction with example, the present invention is described in further detail.
Embodiment 1
Specific preparation method is as follows：3.5 grams of glycolic is dissolved in the water of 20-30 milliliters, then adds 0.5-2 milliliters Butyl titanate, the concentrated sulfuric acid of 0.1-1 milliliters and 1-5 grams of glucose, stirring, move into 50 milliliters of reactor, be placed in In 100-200 DEG C of baking oven, 2-10 hours are reacted, products obtained therefrom is washed with water for several times, drying, by sample in 400 DEG C of air 1-3 hour is calcined under atmosphere, obtains graded structure TiO2-B。
Lithium ion battery assembles：In mass ratio by graded structure TiO2-B：Kynoar：Acetylene black=70：20：10 Equably it is coated in after mixed grinding on copper foil and does negative pole, reference electrode and be lithium metal to electrode, electrolyte is 1M LiPF6 EC+DMC+EMC (EC/DMC/EMC=1/1/1 v/v) solution.
The present invention uses one step hydro thermal method and subsequent calcination process, quickly prepares graded structure TiO2- B, answered For in lithium ion battery negative material, graded structure TiO2- B, which makees cathode of lithium battery, has very high specific capacity and circulation Stability, in larger 1.675 A/g of current density discharge and recharge 100 enclose, capacity is stable in 202.3 mAh/g.
Fig. 1 is graded structure TiO2- B X-ray diffractogram, as can be seen from the figure all diffraction maximums can all belong to In the TiO of monoclinic phase2- B (JCPDS card numbers：74-1940).In addition, from its diffraction pattern, miscellaneous peak is not found.This explanation is used Graded structure TiO prepared by the method for the present invention2- B is the TiO of pure phase2-B。
Fig. 2 is graded structure TiO2- B Raman spectrogram, Raman peak position is 125,145,199,240,252,296, 365th, 409,435,477,555,635 and 860 cm-1, further determined that graded structure TiO2- B is the TiO of pure phase2- B。
Fig. 3 and Fig. 4 is graded structure TiO respectively2- B scanning electron microscope (SEM) photograph, transmission electron microscope picture and high-resolution-ration transmission electric-lens Figure.There it can be seen that synthesized sample has obvious graded structure, microballoon of the diameter between 400-500nm gathers Gather together, these microballoons are assembled by smaller nano-particle.The size of wherein nano-particle only has several nanometers. From high-resolution-ration transmission electric-lens figure, it can be seen that two kinds of lattice fringes, respectively 0.62 and 0.36 nm, corresponding is TiO2-B D001And d110Spacing.
Fig. 5 is graded structure TiO2- B is 1-3 V (vs. Li/Li in voltage range+) cycle performance.It is close in electric current Spend for 1.675 A/g of current density when, the first discharge specific capacity of the material is 296.1 mAh/g, circulation 100 circle after, put Electric specific capacity still has 202.3 mAh/g, shows higher specific capacity and stable cycle performance.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, it should all belong to the covering scope of the present invention.

Claims (4)

  1. A kind of 1. graded structure TiO2- B preparation method, it is characterised in that：Comprise the following steps that：3.5 grams of glycolic is molten Then solution adds the butyl titanate of 0.5-2 milliliters in the water of 20-30 milliliters, the concentrated sulfuric acid of 0.1-1 milliliters and 1-5 grams Glucose, stirring, move into 50 milliliters of reactor, be placed in 100-200 DEG C of baking oven, react 2-10 hours, gained is produced Product are washed with water for several times, drying, sample are calcined into 1-3 hour under 400 DEG C of air atmospheres, obtains graded structure TiO2- B。
  2. A kind of 2. graded structure TiO that as claimed in claim 1 prepared by method2Applications of-the B in lithium ion battery, its feature It is：By graded structure TiO2Equably it is coated in after-B, Kynoar, acetylene black, mixed grinding on copper foil and does negative pole, is joined It is lithium metal than electrode and to electrode, electrolyte is 1M LiPF6EC+DMC+EMC solution.
  3. 3. application according to claim 2, it is characterised in that：Count in mass ratio, graded structure TiO2-B：Polyvinylidene fluoride Alkene：Acetylene black=70：20：10.
  4. 4. application according to claim 2, it is characterised in that：Wherein count by volume, EC：DMC：EMC=1：1：1.
CN201711014922.8A 2017-10-26 2017-10-26 A kind of preparation method of graded structure titanium dioxide (B) and its application in lithium ion battery Active CN107792878B (en)

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CN108598455A (en) * 2018-04-26 2018-09-28 福州大学 Graded structure TiO2The preparation method of-B and its application in lithium ion battery
CN108767204A (en) * 2018-03-30 2018-11-06 合肥国轩高科动力能源有限公司 A kind of lithium-sulfur cell TiO2The preparation method of/C composite
CN110790304A (en) * 2019-11-13 2020-02-14 福州大学 Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery
CN111017990A (en) * 2019-12-31 2020-04-17 福州大学 Preparation method of anatase titanium dioxide microspheres with hierarchical structure
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

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CN108767204A (en) * 2018-03-30 2018-11-06 合肥国轩高科动力能源有限公司 A kind of lithium-sulfur cell TiO2The preparation method of/C composite
CN108598455A (en) * 2018-04-26 2018-09-28 福州大学 Graded structure TiO2The preparation method of-B and its application in lithium ion battery
CN108598455B (en) * 2018-04-26 2020-08-11 福州大学 Hierarchical structure TiO2Preparation method of (E) -B and application thereof in lithium ion battery
CN110790304A (en) * 2019-11-13 2020-02-14 福州大学 Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery
CN111017990A (en) * 2019-12-31 2020-04-17 福州大学 Preparation method of anatase titanium dioxide microspheres with hierarchical structure
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

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