CN102328953B - Preparation method of lithium titanate with special morphology - Google Patents
Preparation method of lithium titanate with special morphology Download PDFInfo
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- CN102328953B CN102328953B CN2011102140582A CN201110214058A CN102328953B CN 102328953 B CN102328953 B CN 102328953B CN 2011102140582 A CN2011102140582 A CN 2011102140582A CN 201110214058 A CN201110214058 A CN 201110214058A CN 102328953 B CN102328953 B CN 102328953B
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Abstract
The invention discloses a preparation method of lithium titanate with special morphology. The method comprises the following steps of: crushing a biomass material, then carrying out ultrasonic dispersion on the crushed biomass material in a lithium acetate ethanol solution and adding tetrabutyl titanate drop by drop according to the mol ratio of Li to Ti being 0.8-0.84; continuously stirring for 5-10 minutes and then heating and evaporating solvent to obtain a precursor of the lithium titanate; and calcining the precursor of the lithium titanate in the air and then cooling the clacined precursor to be room temperature to obtain the lithium titanate with tubular, sheet or porous structure. According to the method disclosed by the invention, the tetrabutyl titanate is taken as a raw material, has low price and wide sources; and the green and toxic-free biomass material is taken as a template, thus the lithium titanate with special morphology is synthesized at lower temperature. The method has the advantages of simpleness, strong maneuverability, favorable repetitiveness, easiness for industrial production and wide application prospect.
Description
Technical field
The invention belongs to the electrochemical material field, be specifically related to lithium ion battery negative material, particularly a kind of preparation method with lithium titanate of special appearance.
Background technology
Pure phase lithium titanate (Li
4Ti
5O
12) be spinel structure, oxonium ion is arranged by face-centered cubic packing, is positioned at the 32e position, and 3/4 lithium ion occupies tetrahedron 8a position, and remaining lithium ion and titanium ion are arranged in the octahedral site of 16d.This crystalline structure takes off the three-dimensional diffusion passage is provided for the embedding of lithium.Along with the embedding of lithium, its lattice parameter and volume change are little, therefore are called as " zero strain material ".In the doff lithium process titanium ion flexibly electronic structure have good chemical property by lithium titanate anode material.Specific crystalline structure can stop the volume change in charge and discharge process.Thereby, lithium titanate anode material has that cycle performance is good, discharging voltage balance, embedding lithium current potential is high and be difficult for causing that metallic lithium separates out, and the good characteristic such as can intervally use at the electrolytical stabilized voltage of most liquid, coulombic efficiency is high, the lithium ion spread coefficient is large.Be with a wide range of applications and the very large market requirement.
Although lithium titanate has lot of advantages as negative material, this material exists some problems in application process.Low, the theoretical electrical capacity of electronic conductivity is low is two large shortcomings of lithium titanate material.This has limited chemical property and the application thereof of lithium titanate greatly.
Summary of the invention
Shortcoming and deficiency in order to overcome prior art, the object of the present invention is to provide a kind of preparation method with lithium titanate of special appearance; The method is take Lithium Acetate and tetrabutyl titanate as raw material, take cheap, wide material sources, green non-poisonous biological material (bamboo fibers, bagasse fibre and bamboo charcoal), makes the lithium titanate with special appearance as template; The method is simple, workable, good reproducibility, be easy to industrial production.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method with lithium titanate of special appearance comprises the following steps:
(1) biological material is pulverized rear ultra-sonic dispersion in the Lithium Acetate ethanolic soln, made suspending liquid A;
(2) be 0.8 ~ 0.84 tetrabutyl titanate dropwise to be splashed in suspending liquid A and obtains suspension B according to the Li/Ti mol ratio, continue to stir after 5-10 minute, the solvent in heating evaporate to dryness suspension B obtains the presoma of lithium titanate;
(3) presoma of lithium titanate is calcined in air, then be cooled to 25 ~ 40 ℃ obtain having tubulose, the lithium titanate of sheet or vesicular structure;
The described biological material of step (1) is a kind of in bamboo fibers, bagasse or bamboo charcoal;
In the described Lithium Acetate ethanolic soln of step (1), the concentration of Lithium Acetate is 0.5 ~ 1.0mol/L;
In the described suspending liquid A of step (1), the mass percent of biological material is 2.5 ~ 5%;
The described heating of step (2) is heating under 40 ~ 80 ℃;
The described calcining of step (3) is to calcine 5 hours under 450 ℃, calcines 10 hours under 750 ℃ again.
Utilize biological material (bamboo fibers, bagasse fibre and bamboo charcoal) to prepare the lithium titanate of special appearance for template, this lithium titanate has larger specific surface area, thereby reduce the diffusion length of lithium ion in Quilonum Retard, be conducive to improve the storage lithium specific storage of lithium titanate, help the infiltration of electrolytic solution, thereby improve the electronic conductivity of lithium titanate anode material.
The present invention has following advantage and effect with respect to prior art:
(1) to adopt tetrabutyl titanate be raw material in the present invention, with cheap, and wide material sources, green non-poisonous biological material (bamboo fibers, bagasse fibre and bamboo charcoal) is template, has realized the lithium titanate of synthetic special appearance under the lesser temps.
(2) lithium ionic cell cathode material lithium titanate prepared take bamboo fibers, bagasse fibre and bamboo charcoal as template of the present invention has respectively micron tubular, sheet and vesicular structure.This kind micron tubular, sheet and vesicular structure can improve the specific surface area of lithium titanate, thereby reduce the diffusion length of lithium ion in lithium titanate, be conducive to improve the storage lithium specific storage of lithium titanate, help the infiltration of electrolytic solution, thereby improve the electronic conductivity of lithium titanate anode material.
(3) the present invention has absorbed the advantage of template and traditional sol-gel method, and method is simple, and is workable, and good reproducibility is easy to industrial production, is with a wide range of applications.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) (13000 times) of embodiment 1 tubulose lithium titanate.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) (1000 times) of embodiment 2 sheet lithium titanates.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) (16000 times) of embodiment 3 lithium titanates.
Fig. 4, figure (a) is the diffraction (XRD) of embodiment 1 tubulose lithium titanate powder, figure (b) is standard powdery diffractometry (XRD) figure of lithium titanate.
Fig. 5 is the first charge-discharge graphic representation of embodiment 1 tubulose lithium titanate under 0.5-3.0V, 0.1C.
Fig. 6 is the cycle performance graphic representation of embodiment 1 tubulose lithium titanate under 0.5-3.0V, 0.1C.
Fig. 7 is the high rate performance graphic representation of embodiment 1 tubulose lithium titanate under 0.5-3.0V.
Fig. 8 is the cycle performance graphic representations of embodiment 2 sheet lithium titanates under 0.5-3.0V, 0.1C.
Fig. 9 is the cycle performance graphic representations of embodiment 3 porous block lithium titanates under 0.5-3.0V, 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of method for preparing the tubulose lithium titanate take bamboo fibers as template comprises the following steps:
(1) bamboo fibers after getting 0.75g and pulverizing, adding 20ml concentration is that in the ethanolic soln of Lithium Acetate of 0.69mol/L, ultra-sonic dispersion 1 hour (hyperacoustic frequency is 35KHz), obtain suspending liquid A.
(2) according to mol ratio Li/Ti=0.8, appropriate tetrabutyl titanate is dropwise splashed in above-mentioned suspending liquid A and obtains suspension B.Continue to stir after 8 minutes, suspension B is placed on the temperature control magnetic stirring apparatus, stir evaporate to dryness in 60 ℃ and make the presoma C of tubulose lithium titanate.
(3) C is ground be placed on calcine by steps under retort furnace Air condition (calcination condition is: 450 ℃ of calcinings, 750 ℃ of calcinings 10 hours after 5 hours), then be cooled to 30 ℃ and obtain the tubulose lithium titanate product: as shown in Figure 1, the nano particle that the tubulose lithium titanate is about 10-20nm by particle diameter forms internal diameter and is about 4 microns, and external diameter is about the tubular structure of 6 microns; As shown in Figure 4, tubulose lithium titanate XRD curve is consistent with standard spinel lithium titanate XRD spectra.
Sem analysis is observed the microscopic appearance of specimen surface with the JSM-6380LA type scanning electronic microscope (SEM) of NEC (JEOL), acceleration voltage is 15KV, drips at conductive resin surface, air drying after sample preparation adopts dehydrated alcohol to disperse.Lower same.
XRD analysis instrument used is that the general XD-2 of the universal apparatus company limited type X-ray diffractometer of analysing in Beijing characterizes the crystal phase structure of prepared final product.Test condition is the Cu target, K α radiation, 36kV, 30mA, go on foot wide 0.02 °, 15～85 ° of sweep limits.Sample is that powder is placed in the pressing of sample table groove, direct-detection.
The chemical property of the tubulose lithium titanate of embodiment 1 preparation---constant current charge-discharge test:
The tubulose lithium titanate of embodiment 1 preparation is mixed in mass ratio with conductive carbon black, binding agent polyvinylidene chloride (PVDF) at 8: 1: 1, add again appropriate N-Methyl pyrrolidone (NMP) to stir, be applied on Copper Foil, oven dry under 80 ℃ in vacuum drying oven, the use sheet-punching machine is die-cut, obtains electrode slice.The electrode obtained is done negative pole, metal lithium sheet is anodal, electrolytic solution is for containing 1M LiPF6/ (EC+DMC) (volume ratio is 1: 1) mixed system, and barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box that is full of argon gas (Ar).Carry out the charge-discharge performance test with the Shenzhen's new Weir BTS51800 of Electronics Co., Ltd. battery test system.
Can find out this material at 0.5-3.0V from Fig. 5,6 and 7, under 0.1C, first discharge specific capacity reaches 178mAh/g, and discharge platform near 1.5V, maintains 162mAh/g through 50 circulation specific discharge capacities, has electrochemistry cycle performance preferably.This material returns low range and discharges and recharges after high rate charge-discharge from low range under 0.5-3.0V, specific discharge capacity still can maintain 170mAh/g,, near theoretical specific capacity, shows that this material has high rate performance preferably.
Embodiment 2
A kind of method for preparing the sheet lithium titanate take bagasse fibre as template comprises the following steps:
(1) bagasse after getting 1g and pulverizing, adding 20ml concentration is that in the ethanolic soln of Lithium Acetate of 0.5mol/L, ultra-sonic dispersion 1 hour (hyperacoustic frequency is 35KHz), obtain suspending liquid A.
(2) according to mol ratio Li/Ti=0.82, appropriate tetrabutyl titanate is dropwise splashed in above-mentioned suspending liquid A and obtains suspension B.Continue to stir after 10 minutes, suspension B is placed on the temperature control magnetic stirring apparatus, stir evaporate to dryness in 80 ℃ and make the presoma C of tubulose lithium titanate.
(3) C is ground be placed on calcine by steps under retort furnace Air condition (calcination condition is: 450 ℃ of calcinings, 750 ℃ of calcinings 10 hours after 5 hours), then be cooled to 40 ℃ and obtain the sheet lithium titanate product: as shown in Figure 2, the lithium titanate that makes mostly is shred, and this is by tubulose lithium titanate cracked forming in process of lapping.
The chemical property of the sheet lithium titanate of embodiment 2 preparations---constant current charge-discharge test:
The sheet lithium titanate of embodiment 2 preparations is mixed in mass ratio with conductive carbon black, binding agent polyvinylidene chloride (PVDF) at 8: 1: 1, add again appropriate N-Methyl pyrrolidone (NMP) to stir, be applied on Copper Foil, oven dry under 80 ℃ in vacuum drying oven, the use sheet-punching machine is die-cut, obtains electrode slice.The electrode obtained is done negative pole, and metal lithium sheet is anodal, and electrolytic solution is for containing 1M LiPF
6/ (EC+DMC) (volume ratio is 1: 1) mixed system, barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box that is full of argon gas (Ar).Use the new Weir BTS51800 of Electronics Co., Ltd. of Shenzhen battery test system to carry out the constant current charge-discharge test.
As can be seen from Figure 8 this material is at 0.5-3.0V, and the first discharge specific capacity under 0.1C reaches 187mAh/g, through 20 circulation specific discharge capacities, maintains 155mAh/g, shows that this material has chemical property preferably.
Embodiment 3
A kind of method for preparing the porous block lithium titanate take bamboo charcoal as template comprises the following steps:
(1) bamboo charcoal after getting 0.5g and pulverizing, adding 20ml concentration is that in the ethanolic soln of Lithium Acetate of 1.0mol/L, ultra-sonic dispersion 1 hour (hyperacoustic frequency is 35KHz), obtain suspending liquid A.
(2) according to mol ratio Li/Ti=0.84, appropriate tetrabutyl titanate is dropwise splashed in above-mentioned suspending liquid A and obtains suspension B.Continue to stir after 5 minutes, suspension B is placed on the temperature control magnetic stirring apparatus, stir evaporate to dryness in 40 ℃ and make the presoma C of tubulose lithium titanate.
(3) C is ground be placed on calcine by steps under retort furnace Air condition (calcination condition is: 450 ℃ of calcinings, 750 ℃ of calcinings 10 hours after 5 hours), then be cooled to 25 ℃ and obtain the porous block lithium titanate product: as shown in Figure 3, the lithium titanate that makes is porous block.
The chemical property of the porous lithium titanate of embodiment 3 preparations---constant current charge-discharge test:
The porous lithium titanate of embodiment 3 preparations is mixed in mass ratio with conductive carbon black, binding agent polyvinylidene chloride (PVDF) at 8: 1: 1, add again appropriate N-Methyl pyrrolidone (NMP) to stir, be applied on Copper Foil, oven dry under 80 ℃ in vacuum drying oven, the use sheet-punching machine is die-cut, obtains electrode slice.The electrode obtained is done negative pole, metal lithium sheet is anodal, electrolytic solution is for containing 1M LiPF6/ (EC+DMC) (volume ratio is 1: 1) mixed system, and barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box that is full of argon gas (Ar).Use the new Weir BTS51800 of Electronics Co., Ltd. of Shenzhen battery test system to carry out the constant current charge-discharge test.
As can be seen from Figure 9 the first discharge specific capacity of this material under 0.5-3.0V, 0.1C reaches 178mAh/g, and specific discharge capacity maintains 165mAh/g after 20 circulations, shows that this material has chemical property preferably.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (4)
1. preparation method with lithium titanate of special appearance is characterized in that comprising the following steps:
(1) biological material is pulverized rear ultra-sonic dispersion in the Lithium Acetate ethanolic soln, made suspending liquid A;
(2) be 0.8 ~ 0.84 tetrabutyl titanate dropwise to be splashed in suspending liquid A and obtains suspension B according to the Li/Ti mol ratio, continue to stir after 5-10 minute, the solvent in heating evaporate to dryness suspension B obtains the presoma of lithium titanate;
(3) presoma of lithium titanate is calcined in air, then be cooled to 25 ~ 40 ℃ obtain having tubulose, the lithium titanate of sheet or vesicular structure;
The described biological material of step (1) is a kind of in bamboo fibers, bagasse or bamboo charcoal;
In the described suspending liquid A of step (1), the mass percent of biological material is 2.5 ~ 5%.
2. the preparation method with lithium titanate of special appearance according to claim 1, it is characterized in that: in the described Lithium Acetate ethanolic soln of step (1), the concentration of Lithium Acetate is 0.5 ~ 1.0mol/L.
3. the preparation method with lithium titanate of special appearance according to claim 1 is characterized in that: the described heating of step (2) is heating under 40 ~ 80 ℃.
4. the preparation method with lithium titanate of special appearance according to claim 1 is characterized in that: the described calcining of step (3) is calcining 5 hours under 450 ℃, calcining 10 hours under 750 ℃ again.
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| DE102012208608A1 (en) | 2012-05-23 | 2013-11-28 | Robert Bosch Gmbh | Method for producing an electrode for an electrochemical energy store and electrode |
| CN103996843B (en) * | 2014-05-23 | 2016-04-20 | 桂林电子科技大学 | A kind of porous LiMn2O4 nanometer sheet and preparation method thereof |
| CN104638255B (en) * | 2015-02-02 | 2017-11-24 | 斌源材料科技（上海）有限公司 | A kind of metatitanic acid lithium/carbon composite material and preparation method thereof |
| CN110759378B (en) * | 2019-10-23 | 2022-04-05 | 内江师范学院 | Preparation method of fibrous lithium titanate and fibrous lithium titanate |
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| CN101058438A (en) * | 2007-04-25 | 2007-10-24 | 北京理工大学 | Method for preparing nano-crystal lithium-titanium composite oxide |
| CN101847716A (en) * | 2010-05-14 | 2010-09-29 | 北大先行科技产业有限公司 | Method for preparing spherical lithium titanate cathode material |
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| CN101058438A (en) * | 2007-04-25 | 2007-10-24 | 北京理工大学 | Method for preparing nano-crystal lithium-titanium composite oxide |
| CN101847716A (en) * | 2010-05-14 | 2010-09-29 | 北大先行科技产业有限公司 | Method for preparing spherical lithium titanate cathode material |
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Effective date of registration: 20170918 Address after: 410600 No. 42, Chuangxin Road, Ningxiang economic and Technological Development Zone, Hunan Patentee after: Hunan Zhongwei Amperex Technology Limited Address before: 510642 Tianhe District, Guangdong, No. five road, No. 483, Patentee before: South China Agricultural University |