CN104577069B - Preparation method for TiO2-B nano sheet and graphene composite of TiO2-B nano sheet - Google Patents

Preparation method for TiO2-B nano sheet and graphene composite of TiO2-B nano sheet Download PDF

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CN104577069B
CN104577069B CN201510033495.2A CN201510033495A CN104577069B CN 104577069 B CN104577069 B CN 104577069B CN 201510033495 A CN201510033495 A CN 201510033495A CN 104577069 B CN104577069 B CN 104577069B
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tio2
tio
nanometer sheet
nano sheet
preparation
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CN104577069A (en
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魏明灯
蓝通斌
柳宇彬
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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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method for a TiO2-B nano sheet and a graphene composite of the TiO2-B nano sheet. The preparation method for the TiO2-B nano sheet and the graphene composite of the TiO2-B nano sheet comprises the following steps: preparing a superfine TiO2-B nano sheet by adopting a simple hydrothermal method, and preparing a graphene composite of the superfine TiO2-B nano sheet by adopting an in-situ compositing method. The preparation method for the TiO2-B nano sheet and the graphene composite of the TiO2-B nano sheet is simple, low in cost, low in energy consumption and good in repeatability and has a broad business prospect.

Description

A kind of tio2- b nanometer sheet and its preparation method of graphene complex
Technical field
The invention belongs to electrode material preparation field is and in particular to a kind of tio2- b nanometer sheet and its graphene complex Preparation method.
Background technology
Lithium ion battery is the green high-capacity environment-protecting battery that the nineties in 20th century occurs, and has due to having the advantages that prominent And be widely applied.At present, lithium ion battery and its critical material have become the science and technology paid close attention to countries in the world and industry Jiao Point, is also one of energy that the Chinese government pays much attention to exploitation and utilization, is successively put into national Long-and Medium-term Development planning.Especially The exploitation applying to the lithium-ion-power cell of electric automobile (ev) and hybrid vehicle (hev) even more becomes new in recent years The most popular in energy field, the most rapid research field of development.Now industrial conventional negative material has lithium metal, carbon materials Material, li4ti5o12Deng.But because lithium metal and material with carbon element have security performance hidden danger and high rate performance difference and li4ti5o12Synthesis Difficult the shortcomings of, limit its large-scale application.tio2It is one of current research lithium ion battery negative material the most popular, And tio2- b has higher performance and receives much concern.
Content of the invention
It is an object of the invention to provide a kind of tio2- b nanometer sheet and its preparation method of graphene complex, its preparation Method is simple, and with low cost, energy consumption is low, favorable reproducibility, has wide commercial promise.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of tio2- b nanometer sheet, its length is 10-50 nm, and width is 3-5 nm.
Preparation method comprises the following steps:
(1) butyl titanate is dissolved in ethanol；
(2), after stirring, add potassium hydroxide solution, continue to stir；
(3) after hydro-thermal reaction, use hno3Solution washs to acidity, and in dilute hno3Stir 3h in solution, be washed with water to Neutral post-drying；
(4) sample of drying is calcined in atmosphere.
In step (1), the volume of butyl titanate is 0.5-3 ml；The volume of ethanol is 30-50 ml.
In step (2), the concentration of potassium hydroxide solution is 6-15 mol/l, and volume is 10-30 ml.
In step (3), hydrothermal temperature is 100-180 DEG C, and the reaction time is 24-72 h.
In step (4), calcining heat is 300-500 DEG C, and calcination time is 1-4 h.
A kind of tio2- b nanometer sheet/graphene complex, wherein tio2The length of-b nanometer sheet is 10-50 nm, and width is 3-5 nm.
Preparation method comprises the following steps:
(1) butyl titanate is dissolved in ethanol, adds graphene oxide；
(2), after stirring, add potassium hydroxide solution, continue to stir；
(3) after hydro-thermal reaction, use hno3Solution washs to acidity, and in dilute hno3Stir 3h in solution, be washed with water to Neutral post-drying；
(4) sample dried is calcined in argon gas.
In step (1), the volume of butyl titanate is 0.5-3 ml；The volume of ethanol is 30-50 ml；Graphene oxide Addition is 10-80 mg.
In step (2), the concentration of potassium hydroxide solution is 6-15 mol/l, and volume is 10-30 ml.
In step (3), hydrothermal temperature is 100-180 DEG C, and the reaction time is 24-72 h.
In step (4), calcining heat is 300-500 DEG C, and calcination time is 1-4 h.
The remarkable advantage of the present invention is: the invention provides a kind of synthesizing superfine tio2- b nanometer sheet and its Graphene are multiple The method of compound, the method is simple to operate, with low cost, and energy consumption is low, favorable reproducibility, has good using value.
Brief description
Fig. 1 is the ultra-fine tio obtained by embodiment 12- b nanometer sheet (a) and its graphene complex (b) transmission electron microscope picture.
Specific embodiment
Embodiment 1
A kind of ultra-fine tio2- b nanometer sheet and its preparation method of graphene complex, comprise the following steps:
(1) 1 ml butyl titanate respectively is dissolved in two polytetrafluoroethyllining lining equipped with 40 ml alcohol solvents, one Part is added without graphene oxide, and another adds 20 mg graphene oxides；
(2), after stirring, add 20 ml12 mol/l potassium hydroxide solutions, continue to stir；
(3) after 120 DEG C of hydro-thermal reaction 48 h, with 0.1 mol/l hno3Solution washs to acidity, then 0.05 mol/l hno3It is washed with water to neutral post-drying after stirring 3h in solution；
(4) by the powder of above-mentioned drying, do not add sample 400 DEG C of calcining 2 h in atmosphere of Graphene, have addition graphite The sample of alkene then 400 DEG C of calcining 2 h in argon atmosphere.
Can be seen that tio from transmission electron microscope in figure2- b becomes ultrathin nanometer chip architecture, and its length is in 10-50 nm, wide Spend for 3-5 nm about.
Tio prepared by the present embodiment2The discharge and recharge when current density is 5 c of the lithium ion battery of-b nanometer sheet assembling follows Ring 400 circle capacity is maintained at more than 185 ma h/g, has superior long circulating performance；Meanwhile, it also shows excellent times Rate discharge performance, even if its charge/discharge capacity also can be stablized in more than 150 ma h/g when current density is 40 c.And tio2- After b nanometer sheet and Graphene are combined, under the excess current densities of 20 c, remain to after circulation 300 circle to keep 175 ma h/g with On specific capacity, show more excellent big high rate performance.
Embodiment 2
A kind of ultra-fine tio2- b nanometer sheet and its preparation method of graphene complex, comprise the following steps:
(1) 1 ml butyl titanate respectively is dissolved in two polytetrafluoroethyllining lining equipped with 30 ml alcohol solvents, one Part is added without graphene oxide, and another adds 20 mg graphene oxides；
(2), after stirring, add 30 ml12 mol/l potassium hydroxide solutions, continue to stir；
(3) after 100 DEG C of hydro-thermal reaction 48 h, washed to acidity with 0.1 mol/l solution, then in 0.05 mol/l hno3It is washed with water to neutral post-drying after stirring 3h in solution；
(4) by the powder of above-mentioned drying, do not add sample 400 DEG C of calcining 2 h in atmosphere of Graphene, have addition graphite The sample of alkene then 400 DEG C of calcining 2 h in argon atmosphere.
Tio prepared by the present embodiment2The discharge and recharge when current density is 5 c of the lithium ion battery of-b nanometer sheet assembling follows Ring 400 circle capacity is maintained at more than 185 ma h/g, has superior long circulating performance；Meanwhile, it also shows excellent times Rate discharge performance, even if its charge/discharge capacity also can be stablized in more than 150 ma h/g when current density is 40 c.And tio2- After b nanometer sheet and Graphene are combined, under the excess current densities of 20 c, remain to after circulation 300 circle to keep 175 ma h/g with On specific capacity, show more excellent big high rate performance.
Embodiment 3
A kind of ultra-fine tio2- b nanometer sheet and its preparation method of graphene complex, comprise the following steps:
(1) 1 ml butyl titanate respectively is dissolved in two polytetrafluoroethyllining lining equipped with 35 ml alcohol solvents, one Part is added without graphene oxide, and another adds 80 mg graphene oxides；
(2), after stirring, add 25 ml12 mol/l potassium hydroxide solutions, continue to stir；
(3) after 120 DEG C of hydro-thermal reaction 48 h, with 0.1 mol/l hno3Solution washs to acidity, then 0.05 mol/l hno3It is washed with water to neutral post-drying after stirring 3h in solution；
(4) by the powder of above-mentioned drying, do not add sample 450 DEG C of calcining 2 h in atmosphere of Graphene, have addition graphite The sample of alkene then 450 DEG C of calcining 2 h in argon atmosphere.
Tio prepared by the present embodiment2The discharge and recharge when current density is 5 c of the lithium ion battery of-b nanometer sheet assembling follows Ring 400 circle capacity is maintained at more than 185 ma h/g, has superior long circulating performance；Meanwhile, it also shows excellent times Rate discharge performance, even if its charge/discharge capacity also can be stablized in more than 150 ma h/g when current density is 40 c.And tio2- After b nanometer sheet and Graphene are combined, under the excess current densities of 20 c, remain to after circulation 300 circle to keep 175 ma h/g with On specific capacity, show more excellent big high rate performance.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modify, all should belong to the covering scope of the present invention.

Claims (5)

1. a kind of tio2- b nanometer sheet it is characterised in that: tio2The length of-b nanometer sheet is 10-50 nm, and width is 3-5 nm；
Described tio2The preparation method of-b nanometer sheet comprises the following steps:
(1) butyl titanate is dissolved in ethanol；
(2), after stirring, add potassium hydroxide solution, continue to stir；
(3) after hydro-thermal reaction, use hno3Solution washs to acidity, and in dilute hno3Stir 3h in solution, be washed with water to neutrality Post-drying；
(4) sample of drying is calcined in atmosphere；
In step (1), the volume of butyl titanate is 0.5-3 ml；The volume of ethanol is 30-50 ml；
In step (2), the concentration of potassium hydroxide solution is 6-15 mol/l, and volume is 10-30 ml.
2. a kind of tio2- b nanometer sheet/graphene complex it is characterised in that: tio2The length of-b nanometer sheet is 10-50 nm, Width is 3-5 nm；
Described tio2The preparation method of-b nanometer sheet/graphene complex comprises the following steps:
(1) butyl titanate is dissolved in ethanol, adds graphene oxide；
(2), after stirring, add potassium hydroxide solution, continue to stir；
(3) after hydro-thermal reaction, use hno3Solution washs to acidity, and in dilute hno3Stir 3h in solution, be washed with water to neutrality Post-drying；
(4) sample dried is calcined in argon gas；
In step (1), the volume of butyl titanate is 0.5-3 ml；The volume of ethanol is 30-50 ml；
In step (2), the concentration of potassium hydroxide solution is 6-15 mol/l, and volume is 10-30 ml.
3. method according to claim 2 it is characterised in that: in step (1) addition of graphene oxide be 10-80 mg.
4. method according to claim 1 and 2 it is characterised in that: in step (3) hydrothermal temperature be 100-180 DEG C, the reaction time is 24-72 h.
5. method according to claim 1 and 2 it is characterised in that: in step (4) calcining heat be 300-500 DEG C, forge The burning time is 1-4 h.
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Publication number Priority date Publication date Assignee Title
CN106732493A (en) * 2016-12-06 2017-05-31 吉林大学 A kind of preparation method of nano-sheet monocline crystal titanium dioxide B photochemical catalysts
CN106531968A (en) * 2016-12-23 2017-03-22 中国工程物理研究院材料研究所 Preparation method of reduced graphene oxide/TiO2-B composite material for negative electrode of lithium-ion battery
CN107758734B (en) * 2017-10-26 2019-07-09 福州大学 A kind of preparation of graded structure titanium dioxide hollow sub-microsphere and its application in dye-sensitized solar cells
CN110342572B (en) * 2019-07-15 2020-10-30 西南化工研究设计院有限公司 Preparation method of anatase type nano titanium dioxide

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN102275986A (en) * 2011-05-27 2011-12-14 吉林大学 Controllable hydro-thermal preparation method for titanium dioxide nanobelts of different crystal forms
CN102437321A (en) * 2011-12-20 2012-05-02 中国科学院新疆理化技术研究所 Graphene-TiO2(B) nanotube composite material and preparation method thereof
CN103700829A (en) * 2014-01-09 2014-04-02 重庆大学 Preparation method for titanium dioxide (B)-graphene self-winding nano composite material
CN103803644A (en) * 2012-11-14 2014-05-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for controlling product crystal form and morphology of titanium-based nanometer material

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CN102437321A (en) * 2011-12-20 2012-05-02 中国科学院新疆理化技术研究所 Graphene-TiO2(B) nanotube composite material and preparation method thereof
CN103803644A (en) * 2012-11-14 2014-05-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for controlling product crystal form and morphology of titanium-based nanometer material
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