CN103058269A - Method of preparing of lithium titanate - Google Patents
Method of preparing of lithium titanate Download PDFInfo
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- CN103058269A CN103058269A CN2012105697376A CN201210569737A CN103058269A CN 103058269 A CN103058269 A CN 103058269A CN 2012105697376 A CN2012105697376 A CN 2012105697376A CN 201210569737 A CN201210569737 A CN 201210569737A CN 103058269 A CN103058269 A CN 103058269A
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- lithium titanate
- titanate
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Abstract
The invention discloses a method of preparing of lithium titanate. A lithium source and a titanate source are directly mixed, and tabletting is conducted, obtained solid mixture is roasted 3-10h with 750-990 DEG C constant temperature in a muffle furnace, and then cooled to room temperature, and lithium titanate solid is prepared. In the process of preparation, the method can be simply explained as mixing-tabletting-roasting, craft is simple, and operability is strong. Prepared active material lithium titanate (Li4Ti5O12) is low in cost, good in electrical conductivity, moderate in specific capacity and stable in product performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery material lithium titanate (Li for preparing
4Ti
5O
12) method, belong to the energy and material technical field.
Background technology
Lithium titanate is the oxide compound that is composited by metallic lithium and low potential transition metals Ti, has the spinel configuration.It is a kind of zero strain material, good cycle, and charging/discharging voltage is steady, and electrolytic solution is difficult for decomposing, and good charge and discharge platform is arranged, and theoretical specific capacity is 175 mAh/g.Li
4Ti
5O
12Compare with commercial carbon negative pole material, but high power charging-discharging has better chemical property and security usually; Compare with other alloy type negative materials, cost is lower, prepares easier.
At present, the titanium source of synthetic lithium titanate material is mainly titanium dioxide, titanium tetrachloride, phthalandione four butyl esters and barium titanate etc., and these raw material building-up processes are complicated, and cost is higher.The preparation method of lithium titanate mainly comprises solid reaction process and sol-gel method.The suitability for industrialized production technology of preparing of existing lithium titanate is mainly take high temperature solid-state method as main.High temperature solid state reaction technique is simple, is easy to realize suitability for industrialized production, but also possesses the visible shortcoming, as: powder raw material needs long ground and mixed, and mixing uniformity is limited, and diffusion process is difficult to carry out smoothly; The thermal treatment temp of having relatively high expectations and long heat treatment time, energy consumption is large; Product is very hard, is difficult to be ground into the powder that electrode needs; And material electrochemical performance is wayward etc.Sol-gel method has the advantages such as chemical uniformity is good, and chemical purity is high, and stoichiometric ratio can accurately be controlled, and thermal treatment temp is low, the reaction times is short, but simultaneously following shortcoming is arranged also: be added with organic compounds and caused the cost rising; In sintering process, it is the violent process that expands of a volume that gel becomes powder, so the utilization ratio of Reaktionsofen is lower; Organism produces a large amount of CO in the process of sintering
2Gas etc.In sum, adopt existing high temperature solid-state method and sol-gel method to prepare lithium titanate, the input cost height is produced in existence, the production cycle is long and the uppity shortcoming of product performance.Therefore, select a kind of synthesis material of cheapness and more easy working method to be still one of main contents of present lithium titanate research.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing lithium titanate, overcome conventional titanium source and prepared lithium titanate (Li
4Ti
5O
12) cost height, complicated operation, the shortcoming such as the production cycle is long, product performance are wayward.
A kind of method for preparing lithium titanate provided by the invention may further comprise the steps:
(1) molar ratio=(3～7) are pressed in lithium source, titanium source: mix (2～6), then mixture was ground 0.5～2 hour;
(2) solid mixture that step (1) is obtained carries out compressing tablet with tabletting machine, obtains flaky mixture;
(3) flaky mixture that step (2) is obtained places retort furnace, 750～990 ℃ of calcinings 3～10 hours, pulverizes, and obtains product lithium titanate (Li after the grinding
4Ti
5O
12).
Preparation method of the present invention, described lithium source is Quilonum Retard, lithium nitrate, lithium hydroxide, lithium oxalate, Lithium Acetate, Trilithium phosphate, lithium hydrogen phosphate, monometallic and lithium chloride, wherein one or more;
Preparation method of the present invention, described titanium source is titanium valve, titanium dioxide, Butyl Phthalate and barium titanate, wherein one or more.
The beneficial effect that the present invention obtains is as follows: (1) preparation process is not used carbon protection or other protections, and process is succinct, and cost is lower; (2) preparation process can simply be interpreted as mixing-compressing tablet-calcining, and technique is simple, strong operability; (3) compare the negative electrode active material lithium titanate (Li that the present invention prepares with the method for present production lithium titanate
4Ti
5O
12) cost is very low, electroconductibility is good, specific storage is moderate, product performance are stable.The present invention is fit to large-scale production.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the lithium titanate of embodiment 1 preparation.
Fig. 2 is scanning electronic microscope (SEM) figure of the lithium titanate of embodiment 1 preparation.
Fig. 3 is the discharge curve of the lithium titanate of embodiment 1 preparation.
Embodiment
Following examples are used for explanation the present invention.
Embodiment 1
Take by weighing respectively titanium valve 1.02g and Quilonum Retard 0.926g, titanium valve and the Quilonum Retard that weighs up placed agate mortar, ground about 50 minutes, it is fully mixed after, carry out compressing tablet; The sample that presses sheet being placed crucible, again crucible is placed retort furnace, is to calcine 4h under 900 ℃ the condition in temperature; Cooling 12h takes out crucible, and the medicine in the crucible is placed on grind into powder in the agate mortar, obtains target product Li4Ti5O12 powder.Fig. 1 X-ray diffraction analysis is the result show, prepared lithium titanate (Li
4Ti
5O
12) powder is mainly spinel type Li
4Ti
5O
12There is not impurity peaks in phase structure in the spectrogram, product purity is high.Fig. 2 is Li
4Ti
5O
12Powder amplifies 50,000 times electron micrograph, and the product particle size is substantially about 200nm.
Take by weighing respectively 0.2g Li4Ti5O12,0.025g acetylene black, 0.025g polyvinylidene difluoride (PVDF) (PVDF) binding agent, in agate mortar, splash into about 10 tetramethyleneimine N-Methyl pyrrolidone solvent after the grinding evenly, size mixing.Be applied to after mixing and make negative plate on the aluminium foil, place vacuum drying oven 120 ℃ of lower vacuum-dryings 12 hours electrode slice.Then in the nitrogen atmosphere dry glove box, take metal lithium sheet as to electrode, Celgard2400 is barrier film, NSC 11801 (EC)+ethylene carbonate methyl esters (EMC)+ethyl acetate (EA)+1molL
-1LiPF
6Be electrolytic solution, be assembled into battery.In the 0.5V-3.0V voltage range, battery is carried out the charge and discharge cycles experiment.Accompanying drawing 3 is 0.5C multiplying power battery charging and discharging curve.As seen from Figure 3, to make the lithium titanate material sparking voltage be 1.50-1.55V in the present invention.
Embodiment 2
1.11g Quilonum Retard and 2g titanium dioxide are mixed rear compressing tablet.Mix products places air dry oven, with 70 ℃ of dryings.Desciccate is placed High Temperature Furnaces Heating Apparatus, heat up in 850 ℃ of constant temperature calcining 12h with 12 ℃/min heating rate, then be cooled to room temperature with 10 ℃/min cooling rate, make lithium titanate (Li
4Ti
5O
12) powder.In the 0.5V-3.0V voltage range, battery is carried out the charge and discharge cycles experiment, sparking voltage is 1.50-1.55V.Cycle performance of battery is better, with the 0.2C rate charge-discharge, decays to 68% of loading capacity first through 10 cycle battery loading capacities.
Embodiment 3
1.26g lithium hydroxide and 2g titanium dioxide are mixed rear compressing tablet, and mix products places air dry oven, with 85 ℃ of dryings.Desciccate is placed High Temperature Furnaces Heating Apparatus, heat up in 800 ℃ of constant temperature calcining 14h with 14 ℃/min heating rate, then be cooled to room temperature with 10 ℃/min cooling rate, make Li
4Ti
5O
12Powder.It is 1.50-1.55V that the present invention makes the lithium titanate material sparking voltage.With the 0.2C rate charge-discharge, through 30 Capacity fadings to 62% of loading capacity first.
Embodiment 4
2.07g lithium nitrate and 2g titanium dioxide are mixed rear compressing tablet.Mix products places air dry oven, with 95 ℃ of dryings.Desciccate is placed High Temperature Furnaces Heating Apparatus, in the toner seal device, heat up in 750 ℃ of constant temperature calcining 12h with 10 ℃/min heating rate, then be cooled to room temperature with 10 ℃/min cooling rate, make Li
4Ti
5O
12Powder.It is 1.50-1.55V that the present invention makes the lithium titanate material charging/discharging voltage.With the 0.2C rate charge-discharge, through 20 cycle battery capacity attenuations to 65% of loading capacity first.
Embodiment 5
3.06g two hydration Lithium Acetates and 2g titanium dioxide are mixed rear compressing tablet.Mix products places air dry oven, with 110 ℃ of dryings.Desciccate is placed High Temperature Furnaces Heating Apparatus, heat up in 850 ℃ of constant temperature calcining 10h with 14 ℃/min heating rate, then be cooled to room temperature with 10 ℃/min cooling rate, make Li
4Ti
5O
12Powder.It is 1.50-1.55V that the present invention makes the lithium titanate material sparking voltage, and reversible specific capacity is up to 100mAh/g.With the 0.2C rate charge-discharge, through 15 cycle battery capacity attenuations to 75% of loading capacity first.
Embodiment 6
3.12g monometallic and 2g titanium dioxide are mixed rear compressing tablet.Mix products places air dry oven, with 95 ℃ of dryings.Desciccate is placed High Temperature Furnaces Heating Apparatus, in Ar gas atmosphere, heat up in 850 ℃ of constant temperature calcining 9h with 14 ℃/min heating rate, then be cooled to room temperature with 10 ℃/min cooling rate, make Li
4Ti
5O
12Powder.It is 1.50-1.55V that the present invention makes the LiFePO 4 material sparking voltage, and reversible specific capacity is up to 105mAh/g.With the 0.2C rate charge-discharge, through 10 cycle battery capacity attenuations to 72% of loading capacity first.
Claims (1)
1. method for preparing lithium titanate is characterized in that may further comprise the steps:
(1) molar ratio=(3～7) are pressed in lithium source, titanium source: mix (2～6), then mixture was ground 0.5～2 hour;
(2) solid mixture that step (1) is obtained carries out compressing tablet with tabletting machine, obtains flaky mixture;
(3) flaky mixture that step (2) is obtained places retort furnace, 750～990 ℃ of calcinings 3～10 hours, pulverizes, and obtains product lithium titanate (Li after the grinding
4Ti
5O
12);
Wherein, described lithium source is Quilonum Retard, lithium nitrate, lithium hydroxide, lithium oxalate, Lithium Acetate, Trilithium phosphate, lithium hydrogen phosphate, monometallic and lithium chloride, wherein one or more; Described titanium source is titanium valve, titanium dioxide, Butyl Phthalate and barium titanate, wherein one or more.
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| CN2012105697376A CN103058269A (en) | 2012-12-25 | 2012-12-25 | Method of preparing of lithium titanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689429A (en) * | 2018-06-25 | 2018-10-23 | 东北大学秦皇岛分校 | A kind of method of new type low temperature synthesis in solid state titanate powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837057A (en) * | 2006-04-13 | 2006-09-27 | 复旦大学 | Li4Ti5O12 materials with spinel structure and preparation process and use thereof |
| CN1919736A (en) * | 2006-08-17 | 2007-02-28 | 北京理工大学 | Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material |
-
2012
- 2012-12-25 CN CN2012105697376A patent/CN103058269A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837057A (en) * | 2006-04-13 | 2006-09-27 | 复旦大学 | Li4Ti5O12 materials with spinel structure and preparation process and use thereof |
| CN1919736A (en) * | 2006-08-17 | 2007-02-28 | 北京理工大学 | Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material |
Non-Patent Citations (2)
| Title |
|---|
| I. VELJKOVIĆ ET AL.: "Solid State Synthesis of Extra Phase-Pure Li4Ti5O12 Spinel", 《SCIENCE OF SINTERING》 * |
| 王亚辉等: "准固相法制备Li4Ti5O12及其电化学性能研究，王亚辉等，第十六届全国电化学会议论文集B-019", 《第十六届全国电化学会议论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689429A (en) * | 2018-06-25 | 2018-10-23 | 东北大学秦皇岛分校 | A kind of method of new type low temperature synthesis in solid state titanate powder |
| CN108689429B (en) * | 2018-06-25 | 2020-04-14 | 东北大学秦皇岛分校 | Method for low-temperature solid-phase synthesis of titanate powder |
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Application publication date: 20130424 |