CN106654246B - A kind of rounded porous TiO2The preparation method and applications of nanometer sheet - Google Patents

A kind of rounded porous TiO2The preparation method and applications of nanometer sheet Download PDF

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CN106654246B
CN106654246B CN201710046132.1A CN201710046132A CN106654246B CN 106654246 B CN106654246 B CN 106654246B CN 201710046132 A CN201710046132 A CN 201710046132A CN 106654246 B CN106654246 B CN 106654246B
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nanometer sheet
rounded porous
tio
porous tio
rounded
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CN106654246A (en
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洪振生
陈晓辉
康美玲
黄志高
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Fujian Normal 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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

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Abstract

The present invention provides a kind of rounded porous TiO2The preparation method and applications of nanometer sheet.Magnetic agitation in methanol and the mixed solution of n,N-Dimethylformamide is dispersed by terephthalic acid (TPA), butyl titanate stirring is then added dropwise, it is subsequently added into cobalt chloride hexahydrate stirring, it is reacted 1-2 days at 150 DEG C -180 DEG C, then dry through centrifuge washing, it is finally annealed to obtain rounded porous TiO2Nanometer sheet.Through scanning electron microscopic observation, this disc-shaped TiO2Partial size is about 300-400 nm, and has porous pattern.With this rounded porous TiO2Nanometer sheet is as anode material of lithium-ion battery, the results showed that its specific capacity, excellent rate charge-discharge performance and good cyclical stability with higher.Current density is to remain at 220 mAhg after recycling 50 times under 0.1 A/g‑1。

Description

A kind of rounded porous TiO2The preparation method and applications of nanometer sheet
Technical field
The invention belongs to anode material of lithium-ion battery fields, and in particular to a kind of rounded porous TiO2The preparation of nanometer sheet Method and its application.
Background technique
Lithium ion battery has the remarkable advantages such as energy density is big, voltage is high and has extended cycle life and is widely used in moving The fields such as dynamic electronic equipment, national defense industry, electric car.But as a large amount of manufactures of lithium ion battery are applied, lithium (carbonic acid Lithium) price constantly rise, and reserves of the resource of lithium in the earth are inherently fewer.The reserves ratio of sodium element on earth Lithium wants far richer, and metallic sodium is from a wealth of sources and cheap, thus sodium-ion battery receives extensive attention in recent years.Currently, sodium Ion battery restricts its application due to a lack of suitable negative electrode material, and developing the anode material of lithium-ion battery haveing excellent performance is this The research emphasis and hot spot in field.
Currently without rounded porous sheet TiO2The related patents of the preparation method of anode material of lithium-ion battery are reported.
Summary of the invention
The present invention provides a kind of high-performance rounded porous sheet TiO2The preparation method of anode material of lithium-ion battery.This Invention at a lower temperature, synthesizes rounded porous TiO for the first time2Nanometer sheet.Through scanning electron microscopic observation, this disc-shaped TiO2 Partial size is about 300-400 nm, and has porous pattern.With this rounded porous TiO2Nanometer sheet is as sodium-ion battery cathode Material, the results showed that its specific capacity, excellent rate charge-discharge performance and good cyclical stability with higher.Electric current is close Degree is to remain at 220 mAhg after recycling 50 times under 0.1 A/g-1。
Rounded porous TiO2The preparation of nanometer sheet: 5-10 mL first is dispersed by the terephthalic acid (TPA) (PTA) of 2.8-3.4 g Magnetic agitation 5-20 minutes in the mixed solution of the n,N-Dimethylformamide (DMF) of alcohol (MeOH) and 52-61mL, then it is added dropwise The butyl titanate of 1.2-2 mL stirs 7-18 minutes, is subsequently added into the cobalt chloride hexahydrate (CoCl of 1-4 mg2·6H2O 6-) is stirred 15min reacts 1-2 days at 150 DEG C -180 DEG C, then obtains product after centrifuge washing is dry, most afterwards through 390 DEG C -450 DEG C annealing obtains final products.
Sodium-ion battery assembling: rounded porous sheet TiO in mass ratio2: Kynoar: acetylene black=70-75:5- 1.2 cm are equably coated in after 10:15-20 mixed grinding2Copper sheet on do anode, cathode is metallic sodium, and electrolyte is 1M NaClO4EC+DEC (v/v of EC/ DEC=1/1) solution.Battery assembly carry out in glove box under protection of argon gas (oxygen and Moisture content is below 1ppm).
Remarkable advantage of the invention is: the present invention provides rounded porous sheet TiO for the first time2Sodium-ion battery cathode material The preparation method of material, circle are the shapes most beneficial for electrochemistry uniform mass transfer and diffusion, porous and can increase electrolyte in electricity Infiltration and contact in the material of pole, and preparation method it is easy to operate, it is at low cost, with high purity, have excellent performance, can largely close At.With this rounded porous TiO2Nanometer sheet is as anode material of lithium-ion battery, the results showed that its specific capacity with higher, excellent Different rate charge-discharge performance and good cyclical stability.Current density is to remain at after recycling 50 times under 0.1 A/g 220 mAh·g-1.This product can also extend to the application in the fields such as other energy and catalysis.
Detailed description of the invention
Fig. 1 is 1 rounded porous TiO of embodiment2The XRD diagram of nanometer sheet；
Fig. 2 (a) is 1 rounded porous TiO of embodiment2The scanning electron microscope (SEM) photograph of nanometer sheet；
Fig. 2 (b) is 1 rounded porous TiO of embodiment2The transmission electron microscope picture of nanometer sheet；
Fig. 3 is the cyclic curve figure of the sodium-ion battery in embodiment 1.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality Apply example.
Embodiment 1
Rounded porous TiO2The preparation of nanometer sheet: 8 mL methanol are dispersed by the terephthalic acid (TPA) (PTA) of 3.0 g (MeOH) and magnetic agitation 10 minutes in the mixed solution of the n,N-Dimethylformamide of 55mL (DMF), 1.5 mL are then added dropwise Butyl titanate stir 15 minutes, be subsequently added into the cobalt chloride hexahydrate (CoCl of 2 mg2·6H2O 10min) is stirred, at 170 DEG C Reaction 1 day, then product is obtained after centrifuge washing is dry, most final products are obtained through 400 DEG C of annealing afterwards.
Sodium-ion battery assembling: rounded porous sheet TiO in mass ratio2: Kynoar: acetylene black=72:8:18 is mixed 1.2 cm are equably coated in after closing grinding2Copper sheet on do anode, cathode is metallic sodium, and electrolyte is 1M NaClO4EC+DEC (v/v of EC/ DEC=1/1) solution.Battery assembly carries out that (oxygen and moisture content are below in glove box under protection of argon gas 1ppm).
By Fig. 2 (a) scanning electron microscope it is found that this disc-shaped TiO2Partial size is 300-400 nm, and has porous pattern. With this rounded porous TiO2Nanometer sheet is as anode material of lithium-ion battery, the results showed that its specific capacity with higher, excellent Rate charge-discharge performance and good cyclical stability.In Fig. 3, current density is still to keep after recycling 50 times under 0.1 A/g In 220 mAhg-1。
Embodiment 2
Rounded porous TiO2The preparation of nanometer sheet: 5 mL methanol are dispersed by the terephthalic acid (TPA) (PTA) of 2.8 g (MeOH) and magnetic agitation 5 minutes in the mixed solution of the n,N-Dimethylformamide of 52mL (DMF), then it is added dropwise 1.2 mL's Butyl titanate stirs 7 minutes, is subsequently added into the cobalt chloride hexahydrate (CoCl of 1mg2·6H2O 6min) is stirred, it is anti-at 150 DEG C It answers 1 day, then obtains product after centrifuge washing is dry, most obtain final products through 390 DEG C of annealing afterwards.
Sodium-ion battery assembling: rounded porous sheet TiO in mass ratio2: Kynoar: acetylene black=70:5:15 is mixed 1.2 cm are equably coated in after closing grinding2Copper sheet on do anode, cathode is metallic sodium, and electrolyte is 1M NaClO4EC+DEC (v/v of EC/ DEC=1/1) solution.Battery assembly carries out that (oxygen and moisture content are below in glove box under protection of argon gas 1ppm).
Embodiment 3
Rounded porous TiO2The preparation of nanometer sheet: 10 mL methanol are dispersed by the terephthalic acid (TPA) (PTA) of 3.4 g (MeOH) and magnetic agitation 20 minutes in the mixed solution of the n,N-Dimethylformamide of 61mL (DMF), then it is added dropwise 2 mL's Butyl titanate stirs 18 minutes, is subsequently added into the cobalt chloride hexahydrate (CoCl of 4 mg2·6H2O 15min) is stirred, at 180 DEG C Reaction 2 days, then product is obtained after centrifuge washing is dry, most final products are obtained through 450 DEG C of annealing afterwards.
Sodium-ion battery assembling: rounded porous sheet TiO in mass ratio2: Kynoar: acetylene black=75:10:20 1.2 cm are equably coated in after mixed grinding2Copper sheet on do anode, cathode is metallic sodium, and electrolyte is 1M NaClO4EC+ DEC (v/v of EC/ DEC=1/1) solution.Battery assembly carries out that (oxygen and moisture content are equal in glove box under protection of argon gas Lower than 1ppm).
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 (3)

1. a kind of rounded porous TiO2The preparation method of nanometer sheet, which is characterized in that specifically comprise the following steps:
The mixed of 5-10 mL methanol and the N,N-dimethylformamide of 52-61mL is dispersed by the terephthalic acid (TPA) of 2.8-3.4 g It closes in solution magnetic agitation 5-20 minutes, the butyl titanate that 1.2-2 mL is then added dropwise stirs 7-18 minutes, is subsequently added into 1-4 The cobalt chloride hexahydrate of mg stirs 6-15min, reacts 1-2 days at 150 DEG C -180 DEG C, then dry through centrifuge washing, most Rounded porous TiO is obtained by 390 DEG C of -450 DEG C of annealing2Nanometer sheet.
2. rounded porous TiO made from a kind of preparation method as described in claim 12Nanometer sheet.
3. a kind of rounded porous TiO as claimed in claim 22The application of nanometer sheet, which is characterized in that rounded porous TiO2It receives Application of the rice piece in sodium-ion battery, concrete application method are as follows: sodium-ion battery assembling: rounded porous sheet in mass ratio TiO2: Kynoar: 1.2 cm are equably coated in after acetylene black=70-75:5-10:15-20 mixed grinding2Copper sheet on do Anode, cathode are metallic sodium, and electrolyte is 1M NaClO4EC+DEC solution, the wherein v/v of EC/ DEC=1/1；Battery assembly It is carried out in glove box under protection of argon gas, oxygen and moisture content are below 1ppm.
CN201710046132.1A 2017-01-22 2017-01-22 A kind of rounded porous TiO2The preparation method and applications of nanometer sheet Expired - Fee Related CN106654246B (en)

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CN1607611A (en) * 2003-10-13 2005-04-20 西北工业大学 Sol-gel method for preparing cobalt ion doped titanium dioxide ferromagnetic material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1607611A (en) * 2003-10-13 2005-04-20 西北工业大学 Sol-gel method for preparing cobalt ion doped titanium dioxide ferromagnetic material

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Title
TiO2介晶:一种高性能钠离子电池负极材料;洪振生;《中国化学会第30届学术年会-第三十分会：化学电源》;20160731;第19页
金红石TiO2介晶:一种高性能钠离子电池负极材料;周凯强等;《第18届全国固态离子学学术会议暨国际电化学储能技术论坛论文集》;20161130;第101页

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