CN102903899A - SiO of lithium ion battery cathode material lithium titanate2Template synthesis method - Google Patents
SiO of lithium ion battery cathode material lithium titanate2Template synthesis method Download PDFInfo
- Publication number
- CN102903899A CN102903899A CN2012102540912A CN201210254091A CN102903899A CN 102903899 A CN102903899 A CN 102903899A CN 2012102540912 A CN2012102540912 A CN 2012102540912A CN 201210254091 A CN201210254091 A CN 201210254091A CN 102903899 A CN102903899 A CN 102903899A
- Authority
- CN
- China
- Prior art keywords
- lithium
- template
- sio
- titanate
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010406 cathode material Substances 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 9
- 238000001308 synthesis method Methods 0.000 title description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005287 template synthesis Methods 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- -1 poly(ethylene oxide) Polymers 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 7
- 208000030208 low-grade fever Diseases 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 7
- 239000012153 distilled water Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses SiO of lithium ion battery cathode material lithium titanate2The template synthesis method provides a preparation method of a nano lithium titanate material with high rate performance and excellent cycle performance. The method comprises the following steps: weighing a certain amount of P123, dissolving with deionized water, and stirring until the P123 is completely dissolved; adding 2mol/L hydrochloric acid, stirring for 1-3h with low heat, slowly dripping TEO, stirring at high speed for 10-30h in water bath at 20-50 ℃, then transferring to a stainless steel reaction kettle, and crystallizing for 24-48h at 80-120 ℃; washing the product with deionized water to neutrality, drying at 100 deg.c, heating the synthesized material in a muffle furnace at 1-5 deg.c/min to 450 deg.c and 650 deg.c, maintaining for 12-24 hr to obtain nanometer mesoporous SiO2A template; nano mesoporous SiO2Heating the template to 80-120 ℃, dissolving a certain amount of lithium source and titanium source by using corresponding solvents, dripping the lithium source and the titanium source into the template, and then placing the template in a tubular furnace at the temperature of 750 ℃ and 850 DEG CSintering for 8-12 h; and (3) dissolving the template by using hot concentrated alkali solution, washing by using distilled water, drying and crushing to obtain the lithium titanate.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, particularly a kind of SiO of lithium ionic cell cathode material lithium titanate
2Template synthesis method.
Background technology
Lithium ion battery negative material adopts various embedding lithium material with carbon elements mostly at present, but the current potential of the current potential of carbon electrode and lithium is very approaching, when battery overcharge, the easy precipitating metal lithium of carbon electrodes, form dendrite and cause safety problem, lithium ion can make the material with carbon element structure be damaged, thereby cause the decay of capacity inserting repeatedly and taking off in the embedding process simultaneously.Spinel lithium titanate is as lithium ion battery negative material, and theoretical specific capacity is 175 mAh/g, and actual specific capacity has reached 150 ~ 160 mAh/g, Li
+Inserting and taking off embedding does not almost affect material structure, have that coulombic efficiency height, cycle performance are good, discharging voltage balance, embedding lithium current potential is high and be difficult for causing that lithium metal separates out, can in the interval use of the electrolytical burning voltage of most liquid, have good fail safe; Also be a kind of " zero strain " material, and material source is wide, clean environment firendly, has possessed the characteristic that the essential charging times of lithium ion battery of future generation is more, charging process is faster, safer.In addition, it also has obvious charge and discharge platform, and the platform capacity can reach more than 90% of discharge capacity.(but intrinsic conductivity is 10 to the lithium titanate material poorly conductive
-9S/cm), heavy-current discharge easily produces larger polarization and has limited its Commercialization application.
At present, the high rate performance that improves lithium titanate mainly contains two kinds of approach, and the one, prepare nano level lithium titanate; The 2nd, it is mixed and the study on the modification such as coating.At present, industrial preparation lithium titanate mainly adopts high temperature solid-state method, is with TiO
2With Li
2CO
3Or the raw material such as LiOH is lower synthetic at 800-1000 ℃, general 12-24h of reaction time, it is simple that the method has technique, is easy to large-scale production, but that shortcoming is the particle diameter of product is wayward, and mostly be greatly micron order, uniformity is relatively poor, compares with micro crystal, and coarse grained lithium ion insertion reaction path is longer, be unfavorable for high current charge-discharge, high rate capability is poor.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, a kind of SiO is provided
2Template synthesis method prepares lithium ionic cell cathode material lithium titanate.This method realizes the nano lithium titanate material preparation by control crystal grain-growth space, improves high rate performance and cycle performance.
The present invention adopts following technical scheme to achieve these goals:
A kind of SiO of lithium ionic cell cathode material lithium titanate
2Template synthesis method, the method may further comprise the steps:
(1) preparation nanoscale SiO
2Template: by poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer P123: tetraethoxysilane TEOS:HCl mol ratio 0.0165-0.0180:1:5-7 takes by weighing the presoma of corresponding chemical metering; First with the P123 deionized water dissolving, be stirred to dissolve complete, then the hydrochloric acid that adds 2mol/L, low-grade fever stirs 1-3h, under agitation slowly drip TEOS, after dropwising, high-speed stirred 10-30h under 20 ℃ of-50 ℃ of waters bath with thermostatic control, then be transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 24-48h under the 80-120 ℃ of condition; To neutral, 100 ℃ of lower oven dry are warming up to 450-650 ℃ with 1-5 ℃/min programming rate with the material after the oven dry to products therefrom in Muffle furnace with the deionized water washing, and insulation 12-24h namely obtains nanoscale SiO
2Template;
(2) preparation lithium titanate: Li:Ti is that 4.0-4.6:5 takes by weighing a certain amount of lithium source and titanium source in molar ratio, be scattered in the dispersant after, be added drop-wise to SiO
2On the template, the evaporation dispersant, with gained mixture 750-850 ℃ of lower sintering 8-12h in Muffle furnace, then the concentrated alkali solution with heat dissolves template, with the deionized water washing, after the drying and crushing, obtains the nano barium titanate lithium material.
Described lithium source is one or several whens combination in lithium acetate, the lithium oxalate, the titanium source is one or several the combination in tetraethyl titanate, metatitanic acid methyl esters, tetraisopropyl titanate, butyl titanate, the titanium tetrachloride, and dispersant is a kind of in absolute ethyl alcohol, ethylene glycol, the butyl acetate.
Described lithium source is one or several whens combination in lithium acetate, the lithium nitrate, and the titanium source is titanyl sulfate, and dispersant is deionized water.
The concentrated alkali solution of described heat is that concentration is 4-10mol/L, and temperature is the strong base solution that 60-100 ℃ NaOH, KOH etc. do not introduce foreign ion.
Advantage of the present invention:
(1) the present invention passes through the silica template of preparation nano aperture, and strictly controls sintering condition and realize the nano lithium titanate material preparation, has improved high rate performance and cycle performance;
(2) lithium titanate material of the method preparation has the purity height, particle is little and even, the characteristic such as charging and discharging capacity is high, efficiency for charge-discharge is high, fail safe is good.
Description of drawings
Fig. 1 is the SiO of the nano aperture that makes among the embodiment 1
2The scanning electron microscope (SEM) photograph of template;
Fig. 2 is the transmission electron microscope picture of the lithium titanate material that makes among the embodiment 1;
Fig. 3 is the X-ray diffracting spectrum of the lithium titanate material of preparation among the embodiment 1;
Fig. 4 is the charging and discharging curve of lithium titanate material under different multiplying of preparation among the embodiment 1, and charge-discharge magnification is 0.5C, 2C, 5C.
Embodiment
The invention will be further described below in conjunction with embodiment
,But protection scope of the present invention is not limited to these embodiment.
Embodiment 1
(1) is the presoma that the ratio of 0.0172 P123:1TEOS:6HCl takes by weighing the corresponding chemical metering according to mol ratio, with the P123 deionized water dissolving, is stirred to dissolve complete, add again the hydrochloric acid of 2mol/L, low-grade fever stirring 3h; Slowly drip TEOS, after dropwising, then high-speed stirred 24h under 30 ℃ of water-baths is transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 24h under 100 ℃ of conditions; Products therefrom is extremely neutral with the deionized water washing, 100 ℃ of lower oven dry; Synthetic material speed with 1 ℃/min in Muffle furnace is warming up to 550 ℃, is incubated 16h, namely obtain the SiO of nano aperture
2Template.The SiO of the nano aperture that makes
2The scanning electron microscope (SEM) photograph of template as shown in Figure 1.
(2) Li:Ti is that 4.2:5 takes by weighing a certain amount of lithium acetate and butyl titanate in molar ratio, be scattered in anhydrous ethanol solvent after, slowly be added drop-wise to the SiO of 120 ℃ of lower insulations
2On the template, obtain presoma behind the evaporating solvent; With gained mixture 850 ℃ of lower sintering 8h in tube furnace, remove template with 80 ℃ the 4mol/L NaOH aqueous solution, wash sintered product with distilled water again, oven dry namely obtains lithium titanate after pulverizing.The transmission pattern of this lithium titanate material can be found out the lithium titanate granular size homogeneous that makes as shown in Figure 2.Its X-ray diffracting spectrum does not have obvious dephasign peak as shown in Figure 3 in this spectrogram, show that prepared material is the spinel type lithium titanate of pure phase.
Embodiment 2
(1) is the presoma that the ratio of 0.0172 P123:1TEOS:6HCl takes by weighing the corresponding chemical metering according to mol ratio, with the P123 deionized water dissolving, is stirred to dissolve complete, add again the hydrochloric acid of 2mol/L, low-grade fever stirring 3h; Slowly drip TEOS, after dropwising, under 40 ℃ of water-baths, with high-speed stirred 24h, then be transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 24h under 100 ℃ of conditions; Products therefrom is extremely neutral with the deionized water washing, 100 ℃ of lower oven dry; Synthetic material speed with 1 ℃/min in Muffle furnace is warming up to 600 ℃, is incubated 12h, namely obtain the SiO of nano aperture
2Template.
(2) Li:Ti is that 4.2:5 takes by weighing a certain amount of lithium oxalate and metatitanic acid methyl esters in molar ratio, be scattered in anhydrous ethanol solvent after, slowly be added drop-wise to the SiO of 120 ℃ of lower insulations
2On the template, obtain presoma behind the evaporating solvent; With gained mixture 850 ℃ of lower sintering 8h in tube furnace, remove template with 80 ℃ the 4mol/L NaOH aqueous solution, wash sintered product with distilled water again, oven dry namely obtains lithium titanate after pulverizing.
Embodiment 3
(1) is the presoma that the ratio of 0.0172 P123:1TEOS:6HCl takes by weighing the corresponding chemical metering according to mol ratio, with the P123 deionized water dissolving, is stirred to dissolve complete, add again the hydrochloric acid of 2mol/L, low-grade fever stirring 3h; Slowly drip TEOS, after dropwising, then high-speed stirred 24h under 30 ℃ of water-baths is transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 24h under 100 ℃ of conditions; Products therefrom is extremely neutral with the deionized water washing, 100 ℃ of lower oven dry; Synthetic material speed with 3 ℃/min in Muffle furnace is warming up to 550 ℃, is incubated 16h, namely obtain the SiO of nano aperture
2Template.
(2) Li:Ti is that 4.1:5 takes by weighing a certain amount of lithium acetate and metatitanic acid methyl esters in molar ratio, is scattered in the anhydrous ethanol solvent, slowly is added drop-wise to the SiO of 120 ℃ of lower insulations
2On the template, obtain presoma behind the evaporating solvent; With gained mixture 800 ℃ of lower sintering 10h in tube furnace, remove template with 80 ℃ the 4mol/L NaOH aqueous solution, wash sintered product with distilled water again, oven dry namely obtains lithium titanate after pulverizing.
Embodiment 4
(1) is the presoma that the ratio of 0.0172 P123:1TEOS:6HCl takes by weighing the corresponding chemical metering according to mol ratio, with the P123 deionized water dissolving, is stirred to dissolve complete, add again the hydrochloric acid of 2mol/L, low-grade fever stirring 3h; Slowly drip TEOS, after dropwising, then high-speed stirred 24h under 40 ℃ of water-baths is transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 48h under 90 ℃ of conditions; Products therefrom is extremely neutral with the deionized water washing, 100 ℃ of lower oven dry; Synthetic material speed with 3 ℃/min in Muffle furnace is warming up to 650 ℃, is incubated 12h, namely obtain the SiO of nano aperture
2Template.
(2) Li:Ti is that 4.1:5 takes by weighing a certain amount of lithium nitrate and titanyl sulfate in molar ratio, is scattered in the deionized water, slowly is added drop-wise to the SiO of 120 ℃ of lower insulations
2On the template, obtain presoma behind the evaporating solvent; With gained mixture 750 ℃ of lower sintering 12h in tube furnace, remove template with 80 ℃ the 4mol/L NaOH aqueous solution, wash sintered product with distilled water again, oven dry namely obtains lithium titanate after pulverizing.
Embodiment 5
(1) is the presoma that the ratio of 0.0172 P123:1TEOS:6HCl takes by weighing the corresponding chemical metering according to mol ratio, with the P123 deionized water dissolving, is stirred to dissolve complete, add again the hydrochloric acid of 2mol/L, low-grade fever stirring 3h; Slowly drip TEOS, after dropwising, then high-speed stirred 24h under 50 ℃ of water-baths is transferred in the stainless steel cauldron that polytetrafluoroethylene is lining crystallization 48h under 90 ℃ of conditions; Products therefrom is extremely neutral with the deionized water washing, 100 ℃ of lower oven dry; Synthetic material speed with 3 ℃/min/min in Muffle furnace is warming up to 500 ℃, is incubated 24h, namely obtain the SiO of nano aperture
2Template.
(2) Li:Ti is that 4.3:5 takes by weighing a certain amount of lithium acetate and butyl titanate in molar ratio, be scattered in anhydrous ethanol solvent after, the dipping SiO
2Template, and 80 ℃ of lower insulations, obtain presoma behind the evaporating solvent; With gained mixture 850 ℃ of lower sintering 8h in tube furnace, remove template with 80 ℃ the 4mol/L NaOH aqueous solution, wash sintered product with distilled water again, oven dry namely obtains lithium titanate after pulverizing.
Lithium titanate material and the metal lithium sheet of gained in above-described embodiment are assembled into battery and carry out charge-discharge test with 0.5C, 2C, 5C multiplying power respectively.Wherein the prepared lithium titanate material charging and discharging curve of embodiment 1 as shown in Figure 4, can find out that the 0.5C specific discharge capacity is 161.95 mAh/g, the 2C specific discharge capacity is 148.36 mAh/g, the 5C specific discharge capacity is 125.60 mAh/g, presents good high rate performance.
Embodiment result shows, by the SiO in synthesis of nano aperture
2Template, and further prepare lithium titanate material, to compare with the micron lithium titanate of commonsense method preparation, its high rate performance has obtained obvious improvement.Made lithium titanate material, charge-discharge performance is good, shows excellent chemical property, is the lithium ion battery negative material that has potentiality.
Claims (4)
1. the SiO of a lithium ionic cell cathode material lithium titanate
2Template synthesis method is characterized in that the method may further comprise the steps:
(1) preparation nanoscale SiO
2Template: by poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer P123: tetraethoxysilane TEOS:HCl mol ratio is the presoma that 0.0165-0.0180:1:5-7 takes by weighing the corresponding chemical metering; First with the P123 deionized water dissolving, be stirred to dissolve complete, then the hydrochloric acid that adds 2mol/L, low-grade fever stirs 1-3h, under agitation slowly drip TEOS, after dropwising, high-speed stirred 10-30h under 20 ℃ of-50 ℃ of waters bath with thermostatic control, then be transferred in the reactor crystallization 24-48h under the 80-120 ℃ of condition; To neutral, 100 ℃ of lower oven dry are warming up to 450-650 ℃ with the material after the oven dry with 1-5 ℃/min programming rate to products therefrom with the deionized water washing, and insulation 12-24h namely obtains nanoscale SiO
2Template;
(2) preparation lithium titanate: Li:Ti is that 4.0-4.6:5 takes by weighing a certain amount of lithium source and titanium source in molar ratio, be scattered in the dispersant after, be added drop-wise to SiO
2On the template, the evaporation dispersant, with gained mixture 750-850 ℃ of lower sintering 8-12h in Muffle furnace, then the concentrated alkali solution with heat dissolves template, with the deionized water washing, after the drying and crushing, obtains the nano barium titanate lithium material.
2. the SiO of lithium ionic cell cathode material lithium titanate according to claim 1
2Template synthesis method, it is characterized in that: the lithium source described in the step (2) is one or several whens combination in lithium acetate, the lithium oxalate, the titanium source is one or several the combination in tetraethyl titanate, metatitanic acid methyl esters, tetraisopropyl titanate, butyl titanate, the titanium tetrachloride, and dispersant is a kind of in absolute ethyl alcohol, ethylene glycol, the butyl acetate.
3. the SiO of lithium ionic cell cathode material lithium titanate according to claim 1
2Template synthesis method is characterized in that: the lithium source described in the step (2) is one or several whens combination in lithium acetate, the lithium nitrate, and the titanium source is titanyl sulfate, and dispersant is deionized water.
4. the SiO of lithium ionic cell cathode material lithium titanate according to claim 1
2Template synthesis method is characterized in that: the concentrated alkali solution of the heat described in the step (2) is that concentration is 4-10mol/L, and temperature is the strong base solution that 60-100 ℃ NaOH, KOH etc. do not introduce foreign ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102540912A CN102903899A (en) | 2012-07-20 | 2012-07-20 | SiO of lithium ion battery cathode material lithium titanate2Template synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102540912A CN102903899A (en) | 2012-07-20 | 2012-07-20 | SiO of lithium ion battery cathode material lithium titanate2Template synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102903899A true CN102903899A (en) | 2013-01-30 |
Family
ID=47576039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102540912A Pending CN102903899A (en) | 2012-07-20 | 2012-07-20 | SiO of lithium ion battery cathode material lithium titanate2Template synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102903899A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105261748A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing negative electrode material mono-dispersed nano-crystalline lithium titanate by using nanometer microreactor |
| CN108365187A (en) * | 2018-01-11 | 2018-08-03 | 茆胜 | The lithium titanate material and preparation method thereof of template cladding |
| CN115676877A (en) * | 2022-10-31 | 2023-02-03 | 江苏海普功能材料有限公司 | Silica gel modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
| CN115837271A (en) * | 2022-10-28 | 2023-03-24 | 南京工程学院 | Composite material catalyst and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044662A (en) * | 2010-10-13 | 2011-05-04 | 太原理工大学 | Method for preparing spinel type lithium titanate nanowire array |
| CN102522536A (en) * | 2011-12-17 | 2012-06-27 | 合肥国轩高科动力能源有限公司 | Template synthesis method of lithium ion negative electrode material lithium titanate |
-
2012
- 2012-07-20 CN CN2012102540912A patent/CN102903899A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044662A (en) * | 2010-10-13 | 2011-05-04 | 太原理工大学 | Method for preparing spinel type lithium titanate nanowire array |
| CN102522536A (en) * | 2011-12-17 | 2012-06-27 | 合肥国轩高科动力能源有限公司 | Template synthesis method of lithium ion negative electrode material lithium titanate |
Non-Patent Citations (3)
| Title |
|---|
| DAN SHAO ET AL: "Synthesis and electrochemical performance of nanoporous Li4Ti5O12 anode material for lithium-ion batteries", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 * |
| HYESUN KIM ET AL: "Hard templating synthesis of mesoporous and nanowire SnO2 lithium battery anode materials", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| SUNHYE LIM ET AL: "Synthesis of Nanowire and Hollow LiFePO4 Cathodes for High-Performance Lithium Batteries", 《CHEMISTRY OF MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105261748A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing negative electrode material mono-dispersed nano-crystalline lithium titanate by using nanometer microreactor |
| CN108365187A (en) * | 2018-01-11 | 2018-08-03 | 茆胜 | The lithium titanate material and preparation method thereof of template cladding |
| CN115837271A (en) * | 2022-10-28 | 2023-03-24 | 南京工程学院 | Composite material catalyst and preparation and application thereof |
| CN115676877A (en) * | 2022-10-31 | 2023-02-03 | 江苏海普功能材料有限公司 | Silica gel modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
| CN115676877B (en) * | 2022-10-31 | 2024-04-02 | 江苏海普功能材料有限公司 | Silica gel modified meta-titanic acid type lithium ion sieve precursor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Potassium vanadates with stable structure and fast ion diffusion channel as cathode for rechargeable aqueous zinc-ion batteries | |
| Xu et al. | Preparation and electrochemical properties of carbon-doped TiO2 nanotubes as an anode material for lithium-ion batteries | |
| Xu et al. | The preparation and role of Li2ZrO3 surface coating LiNi0. 5Co0. 2Mn0. 3O2 as cathode for lithium-ion batteries | |
| CN104617271B (en) | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof | |
| CN105206831B (en) | One kind is used for sodium-ion battery positive material Na3V2O2x(PO4)2F3‑2xThe preparation method of microballoon | |
| CN102881881B (en) | Negative pole material of lithium ion battery, preparation method of material and lithium ion battery | |
| CN101635348B (en) | Tantalum-containing lithium ion battery cathode material lithium titanate preparation method | |
| CN101609884B (en) | Method for preparing negative pole material SnS2 of lithium ion battery | |
| CN103594707A (en) | High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2 | |
| Luo et al. | Bamboo carbon assisted sol–gel synthesis of Li4Ti5O12 anode material with enhanced electrochemical activity for lithium ion battery | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| CN103022461A (en) | Rare-earth metal doped micro-nanometer lithium titanate cathode material and preparation method thereof | |
| CN105406042A (en) | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery | |
| CN105304885A (en) | Aluminum secondary battery vanadium oxide positive material and preparation method thereof | |
| CN103094549A (en) | Supercritical hydro-thermal synthesizing method of lithium ion battery negative material lithium titanate | |
| CN104466155A (en) | Method for preparing high-coulombic-efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania | |
| CN102956880A (en) | Method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material and Li4Ti5O12-TiO2 nano composite material thereof | |
| CN108899481A (en) | A kind of Preparation method and use of manganese dioxide | |
| CN102903899A (en) | SiO of lithium ion battery cathode material lithium titanate2Template synthesis method | |
| CN106299344A (en) | A kind of sodium-ion battery nickel titanate negative material and preparation method thereof | |
| Wang et al. | Synthesis of Fe-doped Mn-based Prussian blue hierarchical architecture for high-performance sodium ion batteries | |
| CN106450179A (en) | Preparation method of titanium-doping ferric fluoride positive electrode material | |
| CN103682343A (en) | Cobalt stannide/polyaniline composite material, and preparation method and application thereof | |
| Li et al. | Ti2Nb10O29@ C hollow submicron ribbons for superior lithium storage | |
| CN102522536A (en) | Template synthesis method of lithium ion negative electrode material lithium titanate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 230011, No. 7 D Road, Yaohai Industrial Park, Hefei, Anhui, China Applicant after: Hefei Guoxuan High-Tech Power Energy Co.,Ltd. Address before: 230011, No. 7 D Road, Yaohai Industrial Park, Hefei, Anhui, China Applicant before: Gotion High-tech Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: HEFEI GUOXUAN HIGH-TECH POWER ENERGY CO., LTD. TO: HEFEI GUOXUAN HIGH-TECH POWER ENERGY CO., LTD. |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130130 |