CN101814598A - Novel titanium dioxide cathode material of power lithium ion cell and preparation method thereof - Google Patents
Novel titanium dioxide cathode material of power lithium ion cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel titanium dioxide cathode material of a power lithium ion cell and a preparation method thereof. By using the method, anatase type laminated mesoporous titanium dioxide is formed through selective surface adsorption of acetic acid, centrifugal sedimentation and high temperature calcination under the action of double templates of a surfactant P123 and polystyrene. The laminated mesoporous titanium dioxide prepared by the method has higher charge/discharge capacity, multiplying power and circulation performance.
Description
Technical field
The present invention relates to the power lithium-ion battery field, particularly a kind of novel titanium dioxide cathode material of power lithium ion cell and preparation method thereof.
Background technology
Pure electric automobile and hybrid-electric car more and more are subjected to people's attention at present, and wherein lithium ion battery is optimal electrical source of power.Graphite is as present business-like lithium ion battery negative material, low price, Heat stability is good, environmental friendliness; But because the embedding lithium current potential of graphite is lower, cause the decomposition of electrolyte easily, cause a series of safety problem.Because the doff lithium current potential of titanium dioxide is higher, avoided the decomposition of electrolyte, can improve the fail safe that lithium ion battery uses, there be not caving in of structure in the titanium dioxide Stability Analysis of Structures in the doff lithium process simultaneously, and good high rate performance and cycle performance are arranged.But, present business-like Degussa (degussa) nano titanium oxide P25, its charge/discharge capacity is on the low side, and high rate performance is general, has influenced its development on power lithium-ion battery.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the titanium dioxide cathode material of power lithium ion cell of a kind of capacitance height, good rate capability is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned novel titanium dioxide cathode material of power lithium ion cell.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of novel titanium dioxide cathode material of power lithium ion cell comprises the steps:
(1) with the triblock copolymer P123 (EO of 0.29～0.58 mass parts
20PO
70EO
20), (water of 36～38wt%), 0.3～0.6 mass parts mixes and magnetic agitation 30～60 minutes for the hydrochloric acid of the oxalic acid of the absolute ethyl alcohol of 6～8 mass parts, 0.3～0.6 mass parts, 6～9 mass parts; The tetra-n-butyl titanate that adds 2.5～4.5 mass parts then, magnetic agitation 1～2 hour obtains mixed liquor;
(2) in described mixed liquor, add the polystyrene of 2～4 mass parts, magnetic agitation 2～4 hours, centrifugal then 1～2 time, 50～70 ℃ of bakings are 4～12 hours under the vacuum condition, obtain layered mesoporous TiO 2 precursor;
(3) under the air atmosphere, layered mesoporous TiO 2 presoma respectively 200～250 ℃ of calcinings 2～4 hours, was calcined 2～4 hours for 300～350 ℃, calcined 2～4 hours for 500～550 ℃, programming rate is 2～4 ℃/minute, obtains the lithium ion battery titanium dioxide cathode material.
In the step 2, described polystyrene is by the synthetic polystyrene sphere of emulsion polymerisation, concrete steps are: the persulfuric acid of the styrene that the NaOH of 0.1～0.2 mol handled (26～30 mass parts), 0.5～1 mass parts is received, the polyvinylpyrrolidone (PVP) of the deionized water of 240～350 mass parts, 1.8～2 mass parts, under the nitrogen atmosphere 70～80 ℃ of stirring reactions 24～30 hours, with the sedimentation and filtration that obtains, wash 1～2 time, dried 12～24 hours down at 60～70 ℃ then, obtain polystyrene sphere.
Principle of the present invention is as follows: under the effect of surfactant P123 and polystyrene bimodulus plate, by centrifugal sedimentation, form the stratiform mesoporous TiO 2.Compare with business-like titanium dioxide P25, layered mesoporous titanium dioxide more helps the migration of lithium ion in titanium dioxide and the transmission of electronics because of its particular structure, thereby higher charge/discharge capacity, multiplying power and cycle performance are arranged.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts two template to form stratiform mesoporous TiO 2 unique texture, helps the migration of lithium ion and the transmission of electronics.
(2) the present invention compares with present business-like P25, and higher charge/discharge capacity is arranged.
(3) the present invention compares with present business-like P25, and better high rate performance and cycle performance are arranged.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 layered mesoporous titanium dioxide.
Fig. 2 is the SEM figure of 1 template used dose of embodiment.
Fig. 3 is the SEM figure (a) and the TEM figure (b) of embodiment 1 layered mesoporous titanium dioxide.
Fig. 4 is the IR figure (a) of embodiment 1 layered mesoporous TiO 2 precursor and the IR figure (b) of layered mesoporous titanium dioxide.
Fig. 5 is the TG-DSC figure of embodiment 1 layered mesoporous TiO 2 precursor.
Fig. 6 is the isothermal nitrogen adsorption curve and the BJH pore size distribution curve figure of embodiment 1 layered mesoporous titanium dioxide.
Fig. 7 is embodiment 1 layered mesoporous titanium dioxide (a) and the first five circle charging and discharging curve figure of Comparative Examples commercialization titanium dioxide P25 powder (b).
Fig. 8 be embodiment 1 layered mesoporous titanium dioxide (a) with the different current densities of Comparative Examples commercialization titanium dioxide P25 powder (b) under cycle life figure.
Fig. 9 is embodiment 1 layered mesoporous titanium dioxide and the AC impedance figure (a) of Comparative Examples commercialization titanium dioxide P25 powder under Open Circuit Potential and the equivalent circuit diagram (b) of match.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
(1) with 0.58g P123 (EO
20PO
70EO
20), the 7g absolute ethyl alcohol, 0.45g oxalic acid, 7.30g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 4.5g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation is 2.5 hours in the solution above the polystyrene sphere that 4g is synthesized by the emulsifier-free polymerization adds, the centrifugal then excessive solution of once removing, and baking is 4 hours under 60 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 2 hours at 250 ℃ respectively under the air atmosphere in Muffle furnace, calcined 2 hours for 350 ℃, calcined 2 hours for 500 ℃, programming rate is 2 ℃/minute, obtains layered mesoporous titanium dioxide cathode material.
(1) with 0.2901g P123 (EO
20PO
70EO
20), the 6g absolute ethyl alcohol, 0.3g oxalic acid, 7.30g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 4.5g tetra-n-butyl titanate, magnetic agitation 2 hours.
(2) magnetic agitation is 2.5 hours in the solution above the polystyrene sphere that 4g is synthesized by the emulsifier-free polymerization adds, the centrifugal then excessive solution of once removing, and baking is 4 hours under 70 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 2 hours at 250 ℃ respectively under the air atmosphere in Muffle furnace, calcined 2 hours for 300 ℃, calcined 2 hours for 500 ℃, programming rate is 2 ℃/minute, obtains layered mesoporous titanium dioxide.
Embodiment 3
(1) with 0.5801g P123 (EO
20PO
70EO
20), the 7g absolute ethyl alcohol, 0.6g oxalic acid, 8g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 3g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation 3 hours in the solution above 2g is added by the synthetic polystyrene sphere of emulsifier-free polymerization is removed excessive solution centrifugal then 2 times, and the baking 4 hours down of 60 ℃ of vacuum conditions obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 3 hours at 250 ℃ respectively under the air atmosphere in Muffle furnace, calcined 3 hours for 350 ℃, calcined 3 hours for 550 ℃, programming rate is 3 ℃/minute, obtains layered mesoporous titanium dioxide.
Embodiment 4
(1) with 0.2901g P123 (EO
20PO
70EO
20), the 8g absolute ethyl alcohol, 0.5g oxalic acid, 9g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 2.5g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation is 2.5 hours in the solution above the polystyrene sphere that 4g is synthesized by the emulsifier-free polymerization adds, the centrifugal then excessive solution of once removing, and baking is 4 hours under 70 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 4 hours at 200 ℃ respectively under the air atmosphere in Muffle furnace, calcined 4 hours for 300 ℃, calcined 4 hours for 500 ℃, programming rate is 2 ℃/minute, obtains layered mesoporous titanium dioxide.
(1) with 0.5801g P123 (EO
20PO
70EO
20), the 8g absolute ethyl alcohol, 0.3g oxalic acid, 8g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 3g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation is 3 hours in the solution above the polystyrene sphere that 3g is synthesized by the emulsifier-free polymerization adds, the centrifugal then excessive solution of once removing, and baking is 4 hours under 60 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 2 hours at 250 ℃ respectively under the air atmosphere in Muffle furnace, calcined 2 hours for 350 ℃, calcined 2 hours for 500 ℃, programming rate is 2 ℃/minute, obtains layered mesoporous titanium dioxide.
(1) with 0.3045g P123 (EO
20PO
70EO
20), the 5g absolute ethyl alcohol, 0.5g oxalic acid, 7g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 4.5g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation is 2.5 hours in the solution above the polystyrene sphere that 2g is synthesized by the emulsifier-free polymerization adds, and centrifugal then secondary is removed excessive solution, and baking is 4 hours under 70 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 4 hours at 250 ℃ respectively under the air atmosphere in Muffle furnace, calcined 4 hours for 350 ℃, calcined 4 hours for 500 ℃, programming rate is 3 ℃/minute, obtains layered mesoporous titanium dioxide.
Embodiment 7
(1) with 0.4503g P123 (EO
20PO
70EO
20), the 7.5g absolute ethyl alcohol, 0.5g oxalic acid, 7g hydrochloric acid, water mixed magnetic agitation 30 minutes, then at mixed solution and dripping 4.5g tetra-n-butyl titanate, magnetic agitation 1 hour.
(2) magnetic agitation is 2.5 hours in the solution above the polystyrene sphere that 2g is synthesized by the emulsifier-free polymerization adds, the centrifugal then excessive solution of once removing, and baking is 4 hours under 70 ℃ of vacuum conditions, obtains novel lamellar mesoporous TiO 2 presoma.
(3) layered mesoporous TiO 2 precursor was calcined 4 hours at 200 ℃ respectively under the air atmosphere in Muffle furnace, calcined 4 hours for 300 ℃, calcined 4 hours for 550 ℃, programming rate is 2 ℃/minute, obtains layered mesoporous titanium dioxide.
The performance test experiment
Comparative Examples: as negative material, carry out chemical property and characterize, and compare with the layered mesoporous titanium dioxide electrochemistry that the present invention synthesizes with business-like titanium dioxide P25 powder.
(1) Fig. 1: with embodiment 1 layered mesoporous titanium dioxide, carry out the X-ray diffraction test, sweep speed is 0.1 degree per second, sweeps to 80 degree from 20.
As seen from Figure 1, the layered mesoporous titanium dioxide for preparing is Detitanium-ore-type.
(2) Fig. 2: embodiment 1 used template polystyrene sphere is coated on the conducting resinl, carries out scanning electron microscope analysis.
Fig. 3 (a): embodiment 1 layered mesoporous titanium dioxide is coated on the conducting resinl, carries out scanning electron microscope analysis.
Fig. 3 (b): with embodiment 1 layered mesoporous titanium dioxide, be dispersed in the absolute ethyl alcohol, ultrasonic dispersion 10～20min carries out TEM (transmission electron microscope) analysis.
As seen from Figure 2, by the synthetic polystyrene sphere of emulsifier-free polymerization, size is even, the about 200nm of diameter.
As seen from Figure 3, synthetic titanium dioxide is layer structure, and pore size is about about 160nm, and in the process of calcining, there be caving in of segment template agent in big or small close with polystyrene sphere simultaneously.
(3) Fig. 4: with layered mesoporous TiO 2 precursor of embodiment 1 gained and layered mesoporous titanium dioxide, disperse to grind compressing tablet among the KBr, carry out the fourier infrared test again.
As seen from Figure 4, after the calcining, the absworption peak of polystyrene and P123 has not existed, and illustrates that template removes.
(4) Fig. 5: the layered mesoporous TiO 2 precursor of embodiment 1 gained was dried 4 hours down at 100 ℃ earlier, carry out the thermogravimetric test.
As seen from Figure 5, layered mesoporous TiO 2 precursor mass loss probably is 72.87% before 420 ℃, mainly is polystyrene sphere and organic decomposition.300 ℃ to 500 ℃ be titanium dioxide from the indefinite form attitude to the anatase transforming process, do not have tangible mass loss from 600 ℃ to 900 ℃, show that decomposition reaction finishes substantially.
(5) Fig. 6: the layered mesoporous titanium dioxide of embodiment 1 gained is carried out isothermal nitrogen adsorption curve and the test of BJH pore-size distribution
As seen from Figure 6, compare with business-like titanium dioxide P25 powder, the layered mesoporous titanium dioxide of present embodiment has charge/discharge capacity preferably, may be because layered mesoporous titanium dioxide has higher specific surface area and special structure, helps the migration of lithium ion.
(7) be work electrode with layered mesoporous titanium dioxide and P25 respectively, the lithium sheet is to electrode, and Celgard 2400 is a barrier film, with 1mol/L LiPF
6In EC: DMC: EMC (1: 1: 1 volume ratio) is an electrolyte, is prepared into button cell.In current density from 16.8mAg
-1To 336mAg
-1Between carry out charge-discharge performance test, test result is as shown in Figure 7 and Figure 8.Under Open Circuit Potential, frequency between the 100kHz, is an amplitude with 5mv at 10mHz, carries out ac impedance measurement, and test result is as shown in Figure 9.
As seen from Figure 7, compare with business-like titanium dioxide P25 powder, the layered mesoporous titanium dioxide of present embodiment, the charge/discharge capacity that the first five circle obtains under identical current density is than P25 powder height.
As seen from Figure 8, compare with business-like titanium dioxide P25 powder, the layered mesoporous titanium dioxide of present embodiment has high rate performance and cycle performance preferably.May be because the special construction of layered mesoporous titanium dioxide helps the migration of lithium ion.
As seen from Figure 9, compare charge-transfer resistance that the layered mesoporous titanium dioxide of present embodiment is less and electrode interface resistance with business-like titanium dioxide P25 powder.May be because the layer structure of layered mesoporous titanium dioxide helps the migration of lithium ion, mix with the effective of conductive agent simultaneously, effectively reduce interface resistance.
Claims (3)
1. the preparation method of a novel titanium dioxide cathode material of power lithium ion cell is characterized in that comprising the steps:
(1) with the triblock copolymer P123 (EO of 0.29～0.58 mass parts
20PO
70EO
20), (water of 36～38wt%), 0.3～0.6 mass parts mixes and magnetic agitation 30～60 minutes for the hydrochloric acid of the oxalic acid of the absolute ethyl alcohol of 6～8 mass parts, 0.3～0.6 mass parts, 6～9 mass parts; The tetra-n-butyl titanate that adds 2.5～4.5 mass parts then, magnetic agitation 1～2 hour obtains mixed liquor;
(2) in described mixed liquor, add the polystyrene of 2～4 mass parts, magnetic agitation 2～4 hours, centrifugal then 1～2 time, 50～70 ℃ of bakings are 4～12 hours under the vacuum condition, obtain layered mesoporous TiO 2 precursor;
(3) under the air atmosphere, layered mesoporous TiO 2 presoma respectively 200～250 ℃ of calcinings 2～4 hours, was calcined 2～4 hours for 300～350 ℃, calcined 2～4 hours for 500～550 ℃, programming rate is 2～4 ℃/minute, obtains the lithium ion battery titanium dioxide cathode material.
2. the preparation method of novel titanium dioxide cathode material of power lithium ion cell according to claim 1 is characterized in that: in the step 2, described polystyrene is the polystyrene sphere that adopts the emulsion method polymerization to prepare.
3. a novel titanium dioxide cathode material of power lithium ion cell is characterized in that: adopt claim 1 or 2 described methods to prepare.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167291A (en) * | 2011-03-18 | 2011-08-31 | 复旦大学 | Method for preparing mesoporous metal oxide through pyrolysis of oxalate |
| CN104332593A (en) * | 2014-11-21 | 2015-02-04 | 深圳市燕峰科技有限公司 | Nano titanium dioxide lithium battery and preparing method thereof |
| CN106591935A (en) * | 2016-11-29 | 2017-04-26 | 上海师范大学 | Method for preparing mesoporous monocrystal TiO2 with renewable fiber template |
| CN106784714A (en) * | 2016-12-29 | 2017-05-31 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof |
| CN110224127A (en) * | 2019-06-21 | 2019-09-10 | 燕山大学 | A kind of lithium ion battery negative material and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1719624A (en) * | 2004-07-09 | 2006-01-11 | 中国科学院化学研究所 | A kind of low temperature prepares TiO 2The method of nano-crystal porous film electrode |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1719624A (en) * | 2004-07-09 | 2006-01-11 | 中国科学院化学研究所 | A kind of low temperature prepares TiO 2The method of nano-crystal porous film electrode |
Non-Patent Citations (1)
| Title |
|---|
| 《advances in science and technology》 20061001 Ladislav kavan Nanocrystalline TiO2 for solar cells and lithium batteries 第20-29页 1-3 第51卷, 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167291A (en) * | 2011-03-18 | 2011-08-31 | 复旦大学 | Method for preparing mesoporous metal oxide through pyrolysis of oxalate |
| CN104332593A (en) * | 2014-11-21 | 2015-02-04 | 深圳市燕峰科技有限公司 | Nano titanium dioxide lithium battery and preparing method thereof |
| CN106591935A (en) * | 2016-11-29 | 2017-04-26 | 上海师范大学 | Method for preparing mesoporous monocrystal TiO2 with renewable fiber template |
| CN106784714A (en) * | 2016-12-29 | 2017-05-31 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof |
| CN106784714B (en) * | 2016-12-29 | 2019-04-02 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof |
| CN110224127A (en) * | 2019-06-21 | 2019-09-10 | 燕山大学 | A kind of lithium ion battery negative material and its preparation method and application |
| CN110224127B (en) * | 2019-06-21 | 2021-05-07 | 燕山大学 | Lithium ion battery cathode material and preparation method and application thereof |
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