CN103985842A - Preparation method and application of TiO2 microsphere consisting of octahedral nanoparticles - Google Patents
Preparation method and application of TiO2 microsphere consisting of octahedral nanoparticles Download PDFInfo
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- CN103985842A CN103985842A CN201410256303.XA CN201410256303A CN103985842A CN 103985842 A CN103985842 A CN 103985842A CN 201410256303 A CN201410256303 A CN 201410256303A CN 103985842 A CN103985842 A CN 103985842A
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- tio
- micron ball
- nanometer particle
- preparation
- particle forms
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 8
- 239000004005 microsphere Substances 0.000 title abstract 4
- 239000002105 nanoparticle Substances 0.000 title abstract 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/052—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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a TiO2 microsphere consisting of octahedral nanoparticles. A TiO2 microsphere with a hierarchical structure based on octahedral nanoparticles is prepared by adopting a hydrothermal method, and the obtained TiO2 microsphere is used for assembling a lithium ion battery. The preparation method is simple, low in cost, low in energy consumption and high in reproducibility, and the prepared lithium ion battery has high specific capacity and cycling stability and excellent rate discharge performance and also has wide commercial prospect.
Description
Technical field
The invention belongs to energy technology field, be specifically related to the TiO that a kind of octahedron nanometer particle forms
2the preparation method of micron ball and application thereof.
Background technology
Lithium ion battery is the green high-capacity environment-protecting battery occurring the nineties in 20th century, owing to having outstanding advantage, has a wide range of applications.At present, the negative material of lithium ion battery also develops rapidly, there is the material of many different materials or new construction to be developed out, but will obtain good cycle, specific capacity is high, high rate during charging-discharging is good lithium ion battery negative material is scientist's research emphasis all the time.Industrial conventional negative material has lithium metal, material with carbon element, Li now
4ti
5o
12deng.There is security performance hidden danger and the shortcoming such as high rate performance is poor in lithium metal and material with carbon element; Li
4ti
5o
12synthetic difficulty.TiO
2it is one of the most popular lithium ion battery negative material of research at present.The present invention adopts simple one step hydro thermal method at lower temperature, synthetic a kind of graduation TiO forming based on octahedron nanometer particle
2micron ball.
Summary of the invention
The TiO that the object of the present invention is to provide a kind of octahedron nanometer particle to form
2the preparation method of micron ball and application thereof, its preparation method is simple, and cost is cheap, and energy consumption is low, favorable reproducibility, obtained lithium ion battery has very high specific capacity and cyclical stability, also shows excellent multiplying power discharging property, has wide commercial promise.
For achieving the above object, the present invention adopts following technical scheme:
The TiO that a kind of octahedron nanometer particle forms
2the preparation method of micron ball is to adopt hydro thermal method to prepare a kind of graded structure TiO forming based on octahedron nanometer particle
2micron ball.
Its preparation method comprises the following steps:
1) urea is dissolved in hydrochloric acid solution;
2) after urea dissolves completely, drip isopropyl titanate, stir, move in reactor;
3) through hydro-thermal reaction, centrifugal, washing, dry, make the TiO that octahedron nanometer particle forms
2micron ball.
Described in step 1), the addition of urea is 5-10g; The concentration of described hydrochloric acid solution is 1-3 mol/L.
Step 2) addition of described isopropyl titanate is 0.5-2 ml.
Described in step 3), the temperature of hydro-thermal reaction is 100-150 ℃, and the reaction time is 12-36h.
Described in step 3), washing is to wash with water 2-3 time.
The TiO that described octahedron nanometer particle forms
2micron ball is applied to assemble lithium ion battery.Its assemble method comprises: by TiO
2micron ball, Kynoar and acetylene black are coated on copper mesh after evenly for 7:2:1 mixed grinding in mass ratio, to be dried as negative pole, using lithium metal as reference electrode with to electrode, by 1mol/L LiClO
4/ EC-DMC(1:1, v/v) solution is as electrolyte, and in glove box, described lithium ion battery is made in assembling.
remarkable advantage of the present invention is:
(1) the invention provides a kind of graded structure TiO forming based on octahedron nanometer particle
2the preparation method of micron ball, the method is simple to operate, with low cost, and energy consumption is low, and favorable reproducibility has good using value.
(2) TiO that the octahedron nanometer particle of preparing with the inventive method forms
2micron ball is as the negative pole of lithium ion battery, and the lithium ion battery that assembling obtains has very high specific capacity and cyclical stability, and when current density is 0.168 A/g, charge and discharge cycles 200 circle capacity are stabilized in 157.3 mAh/g, approach theoretical capacity 168 mAh/g; Meanwhile, it also shows excellent multiplying power discharging property, even its charge/discharge capacity also can be stabilized in 130.2 mAh/g when current density is 3.36 A/g.
Accompanying drawing explanation
Fig. 1 is the TiO that the prepared octahedron nanometer particle of embodiment 1 forms
2the scanning electron microscope (SEM) photograph of micron ball.
Fig. 2 is the TiO that the prepared octahedron nanometer particle of embodiment 1 forms
2the transmission electron microscope picture of micron ball.
Fig. 3 is the TiO that the prepared octahedron nanometer particle of embodiment 1 forms
2the XRD figure of micron ball.
Fig. 4 is the TiO that the prepared octahedron nanometer particle of embodiment 1 is formed
2the cycle performance curve (1C=168mA/g) that the lithium ion battery that micron ball is assembled into discharges and recharges under different multiplying.
Embodiment
Embodiment 1
The TiO that a kind of octahedron nanometer particle forms
2the preparation method of micron ball, comprises the following steps:
1) 10g urea is dissolved in 20ml 3 mol/L hydrochloric acid solutions;
2) after urea dissolves completely, drip 2.0 ml isopropyl titanates, stir, move in the reactor of 40ml;
3) reactor is put into 150 ℃ of baking ovens and reacted 24 h, take out, naturally cool to room temperature, centrifugation product, washes with water 3 times, dries, and makes the TiO that octahedron nanometer particle forms
2micron ball.
The TiO that gained octahedron nanometer particle is formed
2micron ball is used for assembling lithium ion battery, and its assemble method comprises: by TiO
2micron ball, Kynoar and acetylene black are coated on copper mesh after evenly for 7:2:1 mixed grinding in mass ratio, to be dried as negative pole, using lithium metal as reference electrode with to electrode, by 1mol/L LiClO
4/ EC-DMC(1:1, v/v) solution is as electrolyte, and in glove box, lithium ion battery is made in assembling.
The lithium ion battery of the present embodiment assembling is charge and discharge cycles 200 circles when current density is 0.168 A/g, and specific capacity is 157.3 mAh/g; Its charge and discharge cycles 50 circles when current density is 3.36 A/g, specific capacity is 130.2 mAh/g, shows that its cyclical stability is good.
Embodiment 2
The TiO that a kind of octahedron nanometer particle forms
2the preparation method of micron ball, comprises the following steps:
1) 5g urea is dissolved in 20ml 1 mol/L hydrochloric acid solution;
2) after urea dissolves completely, drip 0.5 ml isopropyl titanate, stir, move in the reactor of 40ml;
3) reactor is put into 100 ℃ of baking ovens and reacted 36 h, take out, naturally cool to room temperature, centrifugation product, washes with water 2 times, dries, and makes the TiO that octahedron nanometer particle forms
2micron ball.
The TiO that gained octahedron nanometer particle is formed
2micron ball is used for assembling lithium ion battery, and its assemble method comprises: by TiO
2micron ball, Kynoar and acetylene black are coated on copper mesh after evenly for 7:2:1 mixed grinding in mass ratio, to be dried as negative pole; Using lithium metal as reference electrode with to electrode; By 1mol/L LiClO
4/ EC-DMC(1:1, v/v) solution is as electrolyte, and in glove box, lithium ion battery is made in assembling.
The lithium ion battery of the present embodiment assembling is charge and discharge cycles 200 circles when current density is 0.168 A/g, and specific capacity is 157.3 mAh/g; Its charge and discharge cycles 50 circles when current density is 3.36 A/g, specific capacity is 130.2 mAh/g, shows that its cyclical stability is good.
Embodiment 3
The TiO that a kind of octahedron nanometer particle forms
2the preparation method of micron ball, comprises the following steps:
1) 8g urea is dissolved in 20ml 2 mol/L hydrochloric acid solutions;
2) after urea dissolves completely, drip 1.0 ml isopropyl titanates, stir, move in the reactor of 40ml;
3) reactor is put into 120 ℃ of baking ovens and reacted 12 h, take out, naturally cool to room temperature, centrifugation product, washes with water 3 times, dries, and makes the TiO that octahedron nanometer particle forms
2micron ball.
The TiO that gained octahedron nanometer particle is formed
2micron ball is used for assembling lithium ion battery, and its assemble method comprises: by TiO
2micron ball, Kynoar and acetylene black are coated on copper mesh after evenly for 7:2:1 mixed grinding in mass ratio, to be dried as negative pole; Using lithium metal as reference electrode with to electrode; By 1mol/L LiClO
4/ EC-DMC(1:1, v/v) solution is as electrolyte, and in glove box, lithium ion battery is made in assembling.
The lithium ion battery of the present embodiment assembling is charge and discharge cycles 200 circles when current density is 0.168 A/g, and specific capacity is 157.3 mAh/g; Its charge and discharge cycles 50 circles when current density is 3.36 A/g, specific capacity is 130.2 mAh/g, shows that its cyclical stability is good.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. the TiO that an octahedron nanometer particle forms
2the preparation method of micron ball, is characterized in that: adopt hydro thermal method to prepare a kind of graded structure TiO forming based on octahedron nanometer particle
2micron ball.
2. the TiO that octahedron nanometer particle forms according to claim 1
2the preparation method of micron ball, is characterized in that: comprise the following steps:
1) urea is dissolved in hydrochloric acid solution;
2) after urea dissolves completely, drip isopropyl titanate, stir, move in reactor;
3) through hydro-thermal reaction, centrifugal, washing, dry, make the TiO that octahedron nanometer particle forms
2micron ball.
3. the TiO that octahedron nanometer particle forms according to claim 1
2the preparation method of micron ball, is characterized in that: described in step 1), the addition of urea is 5-10g; The concentration of described hydrochloric acid solution is 1-3 mol/L.
4. the TiO that octahedron nanometer particle forms according to claim 1
2the preparation method of micron ball, is characterized in that: step 2) addition of described isopropyl titanate is 0.5-2 ml.
5. the TiO that octahedron nanometer particle forms according to claim 1
2the preparation method of micron ball, is characterized in that: described in step 3), the temperature of hydro-thermal reaction is 100-150 ℃, and the reaction time is 12-36h.
6. the TiO that octahedron nanometer particle forms according to claim 1
2the preparation method of micron ball, is characterized in that: described in step 3), washing is to wash with water 2-3 time.
7. the TiO that octahedron nanometer particle forms as claimed in claim 1
2the application of micron ball, is characterized in that: for assembling lithium ion battery.
8. the TiO that octahedron nanometer particle forms according to claim 7
2the application of micron ball, is characterized in that: the assemble method of described lithium ion battery comprises: by TiO
2micron ball, Kynoar and acetylene black mixed grinding are evenly coated on copper mesh, to be dried rear as negative pole, using lithium metal as reference electrode with to electrode, by LiClO
4/ EC-DMC solution is as electrolyte, and in glove box, described lithium ion battery is made in assembling.
9. the TiO that octahedron nanometer particle forms according to claim 8
2the application of micron ball, is characterized in that: TiO
2the mass ratio of micron ball, Kynoar and acetylene black is 7:2:1.
10. graded structure TiO according to claim 8
2the application of micron ball, is characterized in that: described LiClO
4the concentration of/EC-DMC solution is 1mol/L, and wherein the volume ratio of EC and DMC is 1:1.
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CN201410256303.XA CN103985842B (en) | 2014-06-11 | 2014-06-11 | A kind of TiO of octahedron nanometer particle composition 2the preparation method of micron ball and application |
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CN103985842A true CN103985842A (en) | 2014-08-13 |
CN103985842B CN103985842B (en) | 2016-01-27 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106698503A (en) * | 2015-11-13 | 2017-05-24 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide nano-powder |
CN106887574A (en) * | 2017-03-10 | 2017-06-23 | 辽宁大学 | A kind of preparation method of regular octahedron pattern lithium ion battery negative material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103657623A (en) * | 2013-12-04 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Microballoon-type titanium dioxide photocatalyst and preparation method thereof |
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2014
- 2014-06-11 CN CN201410256303.XA patent/CN103985842B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103657623A (en) * | 2013-12-04 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Microballoon-type titanium dioxide photocatalyst and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
PINLIANG JIANG等: ""Electrochemical construction of micro–nano spongelike structure ontitanium substrate for enhancing corrosion resistance and bioactivity"", 《ELECTROCHIMICA ACTA》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106698503A (en) * | 2015-11-13 | 2017-05-24 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide nano-powder |
CN106698503B (en) * | 2015-11-13 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of synthetic method of titanic oxide nano |
CN106887574A (en) * | 2017-03-10 | 2017-06-23 | 辽宁大学 | A kind of preparation method of regular octahedron pattern lithium ion battery negative material |
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