CN107792878B - A kind of preparation method of graded structure titanium dioxide (B) and its application in lithium ion battery - Google Patents

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

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CN107792878B
CN107792878B CN201711014922.8A CN201711014922A CN107792878B CN 107792878 B CN107792878 B CN 107792878B CN 201711014922 A CN201711014922 A CN 201711014922A CN 107792878 B CN107792878 B CN 107792878B
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graded structure
structure tio
lithium ion
milliliters
tio
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CN107792878A (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 TiO2The fast preparation method of-B and its application in lithium ion battery.By the way that glycolic to be dissolved in water, butyl titanate, the concentrated sulfuric acid and glucose is then added, stirs, autoclave has reacted rear washing and drying, then calcines, and obtains graded structure TiO2- B, graded structure TiO2- B makees cathode of lithium battery with very high specific capacity and cyclical stability, and in biggish current density 1.675A/g, charge and discharge 100 are enclosed, and capacity is stablized in 202.3mAh/g.

Description

The preparation method of a kind of graded structure titanium dioxide (B) 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 TiO2The quick preparation side of-B Method and its application in lithium ion battery.
Background technique
Do not have also at present and quickly prepares graded structure TiO2The related patents of-B are reported.Last century the nineties lithium ion Since battery is succeeded in developing, lithium ion battery, which has been obtained, to be 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 Pass as a kind of material of embedded type, because its is safe and non-toxic, the advantages that abundance, stable circulation is good by researcher Note.Titanium dioxide is a kind of oxide with a variety of crystal phases, and common crystal phase has anatase, rutile, brockite and TiO2- B phase.Wherein TiO2- B mutually belongs to metastable phase, because its structure have more open spatial channel, can more effectively into The embedding lithium of row lithium ion is deviate from, and the hot spot of recent researches is become.However, TiO2Preparing for-B is complex, generally by What the heat treatment of Hydrogen titanate obtained.
Summary of the invention
The purpose of the present invention is to provide a kind of graded structure TiO2The fast preparation method of-B and its in lithium-ion electric Application in pond.
To achieve the above object, the present invention adopts the following technical scheme:
Specifically the preparation method is as follows: 3.5 grams of glycolic is dissolved in 20-30 milliliters of water, 0.5-2 is then added The butyl titanate of milliliter, 0.1-1 milliliters of the concentrated sulfuric acid and 1-5 grams of glucose, stirring move into 50 milliliters of reaction kettle, It is placed in 100-200 DEG C of baking oven, reacts 2-10 hours, products obtained therefrom is washed with water for several times, drying, by sample at 400 DEG C 1-3 hour is calcined under air atmosphere, obtains graded structure TiO2-B。
Lithium ion battery assembling: in mass ratio by graded structure TiO2- B: Kynoar: acetylene black=70:20:10 It is equably coated on copper foil after mixed grinding and does cathode, reference electrode and be lithium metal to electrode, electrolyte is 1M LiPF6 EC+DMC+EMC (v/v of EC/DMC/EMC=1/1/1) solution.
Remarkable advantage of the invention is:
The present invention provides a kind of graded structure TiO2- B fast preparation method, this method simple process, inexpensive, Low energy consumption, favorable reproducibility, and performance is excellent.
Detailed description of the invention
Fig. 1 graded structure TiO2The X-ray diffraction spectrogram of-B；
Fig. 2 graded structure TiO2The raman spectrum of-B；
Fig. 3 graded structure TiO2The scanning electron microscope (SEM) photograph of-B；
Fig. 4 graded structure TiO2The transmission electron microscope picture of-B；
Fig. 5 graded structure TiO2The chemical property figure of-B (current density is 1.675 A/g).
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
Specifically the preparation method is as follows: 3.5 grams of glycolic is dissolved in 20-30 milliliters of water, 0.5-2 is then added The butyl titanate of milliliter, 0.1-1 milliliters of the concentrated sulfuric acid and 1-5 grams of glucose, stirring move into 50 milliliters of reaction kettle, It is placed in 100-200 DEG C of baking oven, reacts 2-10 hours, products obtained therefrom is washed with water for several times, drying, by sample at 400 DEG C 1-3 hour is calcined under air atmosphere, obtains graded structure TiO2-B。
Lithium ion battery assembling: in mass ratio by graded structure TiO2- B: Kynoar: acetylene black=70:20:10 It is equably coated on copper foil after mixed grinding and does cathode, reference electrode and be lithium metal to electrode, electrolyte is 1M LiPF6 EC+DMC+EMC (v/v of EC/DMC/EMC=1/1/1) solution.
The present invention uses one step hydro thermal method and subsequent calcination process, quickly prepares graded structure TiO2- B is answered For in lithium ion battery negative material, graded structure TiO2- B makees cathode of lithium battery with very high specific capacity and circulation Stability, in biggish 1.675 A/g of current density, charge and discharge 100 are enclosed, and capacity is stablized in 202.3 mAh/g.
Fig. 1 is graded structure TiO2The X-ray diffractogram of-B, as can be seen from the figure all diffraction maximums can all belong to In the TiO of monoclinic phase2- B (JCPDS card number: 74-1940).In addition, not finding miscellaneous peak from its diffraction pattern.This illustrates to use The graded structure TiO of method preparation of the invention2- B is the TiO of pure phase2-B。
Fig. 2 is graded structure TiO2The raman spectrum of-B, Raman peak position 125,145,199,240,252,296, 365,409,435,477,555,635 and 860 cm-1, further determined graded structure TiO2- B is the TiO of pure phase2- B。
Fig. 3 and Fig. 4 is graded structure TiO respectively2Scanning electron microscope (SEM) photograph, transmission electron microscope picture and the high-resolution-ration transmission electric-lens of-B Figure.There it can be seen that synthesized sample has apparent graded structure, microballoon of the diameter between 400-500nm is poly- It gathers together, these microballoons are assembled by smaller nanoparticle.Wherein the size of nanoparticle 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 When degree is 1.675 A/g of current density, the first discharge specific capacity of the material is that 296.1 mAh/g are put after circulation 100 is enclosed Electric specific capacity still has 202.3 mAh/g, shows higher specific capacity and stable cycle performance.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (4)

1. a kind of graded structure TiO2The preparation method of-B, it is characterised in that: specific step is as follows: 3.5 grams of glycolic is molten Then 0.5-2 milliliters of butyl titanate is added in 20-30 milliliters of water in solution, 0.1-1 milliliters of the concentrated sulfuric acid and 1-5 grams Glucose, stirring are moved into 50 milliliters of reaction kettle, are placed in 100-200 DEG C of baking oven, react 2-10 hours, gained is produced Product are washed with water for several times, and sample is calcined under 400 DEG C of air atmospheres 1-3 hour, obtains graded structure TiO by drying2- B。
2. a kind of graded structure TiO of method preparation as described in claim 12Application of-the B in lithium ion battery, feature It is: by graded structure TiO2It is equably coated on copper foil after-B, Kynoar, acetylene black, mixed grinding and does cathode, joined It is lithium metal than electrode and to electrode, electrolyte is 1M LiPF6EC+DMC+EMC solution.
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. application according to claim 2, it is characterised in that: wherein count by volume, EC:DMC:EMC=1:1:1.
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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
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
CN111017990B (en) * 2019-12-31 2021-08-31 福州大学 Preparation method of anatase titanium dioxide microspheres with hierarchical structure
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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