CN101704681A - Method for preparing lithium titanate with spinel structure - Google Patents
Method for preparing lithium titanate with spinel structure Download PDFInfo
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- CN101704681A CN101704681A CN200910310688A CN200910310688A CN101704681A CN 101704681 A CN101704681 A CN 101704681A CN 200910310688 A CN200910310688 A CN 200910310688A CN 200910310688 A CN200910310688 A CN 200910310688A CN 101704681 A CN101704681 A CN 101704681A
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- lithium titanate
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- oxalate
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Abstract
The invention discloses a method for preparing lithium titanate with a spinel structure, which is characterized by comprising the following steps: preparing titanium salt into titanium solution at a concentration of 0.1 to 3 mol/L, adding an oxalate-containing complex into the solution in a molar ratio of oxalate to titanium being 1.5:1-4:1, and performing stirring reaction at the temperature of between 30 and 90DEG C; performing freezing crystallization at the temperature of between 0.1 and 5DEG C, standing, filtering precipitated crystals, and washing the crystals with deionized water; drying at the temperature of between 30 and 80DEG C to obtain a lithium titanate precursor H2[(TiO(C2O4)2)]; mixing a lithium source and the precursor in a molar ratio of lithium to titanium being 3.8:5-4.2:5, and performing ball milling at room temperature for 0.5 to 5 hours to obtain amorphous lithium titanate; and sintering the amorphous lithium titanate at the temperature of between 600 and 900DEG C in the air to obtain the lithium titanate with the spinel structure. In the method, the cheap inorganic titanium source is taken as a raw material; the process flow is simple; the cost is low; and the electrochemical properties of the product are excellent.
Description
Technical field
The invention belongs to the lithium ion battery negative material preparing technical field, relate to a kind of preparation method of lithium titanate with spinel structure.
Technical background
Present commercial lithium ion battery negative material adopts various carbon materials mostly, adopt carbon material to have following shortcoming: the current potential of carbon material and the current potential of metallic lithium are very approaching, when over-charging of battery, metallic lithium may be separated out and forms Li dendrite in carbon electrodes, thereby causes short circuit; First charge-discharge efficiency is low; React with electrolytic solution; There is tangible voltage delay.Compare with the carbon negative pole, the alloy type negative material generally has higher specific storage, but cycle performance is poor.Comparatively speaking, lithium titanate has remarkable advantages as lithium cell negative electrode material: it has the Yao Wen P Diao characteristic that lattice parameter changes hardly in charge and discharge process, cycle performance excellence; Have very flat charge and discharge platform, theoretical specific capacity is 175mAh/g, and concentrates on land regions; Higher (the 1.55V-vs Li/Li of its embedding lithium current potential
+), being difficult for causing separating out of metallic lithium, the anti-over-charging performance is good; Not with electrolytic solution reaction, Heat stability is good.Therefore in addition, the big order of magnitude of the chemical diffusion coefficient ratio carbon electrode material of lithium titanate also can be used as the electrode materials of ultracapacitor.
The method for preparing spinel type lithium titanate has a lot, as:
High temperature solid-state method: people such as Ohzuku are with TiO
2And Li
2CO
3(or LiOH) is raw material, prepares lithium titanate with high temperature solid-state method.This method technology is simple, but reactant needs long-time the mixing usually, the big and skewness of product particle, and the energy consumption height, product performance are poor.
Sol-gel method: energy magazine (Journal of Power Sources) 158 (2006) 1358-1364 are with Li
2CO
3[Ti (OC
4H
9)
4] be raw material, oxalic acid is coordination agent, has synthesized lithium titanate with sol-gel method, this material is with 0.5mA/cm
2Current density discharge and recharge, first discharge specific capacity reaches 171mAh/g, circulates to decay to 150mAh/g after 35 times.The commercialization purity height of Prepared by Sol Gel Method, good uniformity, thermal treatment temp are lower; But this method is a raw material with the organic titanium source usually, and the production cost height is not suitable for industrial production.
The hydro-thermal ion exchange method: electrochemistry communication (Flectrochemistry Communications) 7 (2005) 894 and Chinese patent CN1333474C water thermion exchange process have been synthesized nanotube, nemaline lithium titanate, and the specific storage of this material under the 1C multiplying power is about 120mAh/g.This method is a presoma with titanate radical nanopipe, line, and synthetic requirement and cost are higher, and product performance are also undesirable, are unsuitable for industrialization.
Spray pyrolysis: (Journal of Physics and Chemistry ofSolids70 (2009) 40 is with LiNO for solid state physics and solid state chemistry magazine
3And Ti[OCH (CH
3)
2]
4Be raw material, prepared lithium titanate with spray pyrolysis, the capacity of this material under the 1C multiplying power is lower than 100mAh/g, and cycle performance is poor.The product of spray pyrolysis preparation is ball-type, epigranular, and tap density is big; But this method is a raw material with the organic titanium source usually, and the equipment cost height, and the product chemical property is relatively poor.
Compound cryosar melting salt method: Chinese patent CN100450930C and electrochemistry journal (Flectrochimica Acta) 54 (2008) 322 adds watery fusion salt in raw material, at high temperature mixture is calcined earlier, remove melting salt with the distilled water wash product then, dry nano-grade spinel type lithium titanate.This method adds melting salt impurity in building-up process, these impurity are difficult to Ex-all when washing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of lithium titanate with spinel structure, and this method is a raw material with the inorganic ti sources of cheapness, and technical process is simple, and cost is low, the chemical property excellence of product.
In order to solve the problems of the technologies described above, the preparation method of a kind of lithium titanate with spinel structure provided by the invention is characterized in that:
A kind of preparation method of lithium titanate with spinel structure, it is characterized in that: the solution that titanium salt is mixed with titaniferous 0.1-3mol/L, mol ratio by oxalate and titanium added the title complex that contains oxalate in 1.5: 1～4: 1 in solution, under 30～90 ℃ and agitation condition, react, then at 0.1～5 ℃ of freezing and crystallizing, leave standstill, the crystal of separating out filtered, use deionized water wash, then 30～80 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Pressing the mol ratio 3.8: 5～4.2: 5 of lithium and titanium mixes the lithium source with above-mentioned lithium titanate precursor, it is 0.02～1 micron amorphous lithium titanate that ball milling gets granularity, then with amorphous lithium titanate under 600～900 ℃, in air atmosphere, calcine, promptly get the lithium titanate of spinel structure.
Described titanium salt is a kind of in titanium sulfate, titanyl sulfate, the chlorination oxygen titanium.
Described titanium salt can be technical grade, chemical pure or analytical pure titanium salt.
The described title complex that contains oxalate is one or more in sodium oxalate, potassium oxalate, oxalic acid and the ammonium oxalate.
Described lithium source is a kind of in Quilonum Retard, lithium hydroxide, Lithium Acetate, lithium lactate, lithium nitrate, lithium oxalate and the Lithium Oxide 98min.
The described reaction times is 10 minutes～5 hours; Described time of repose is 0.5～10 hour, and the described ball milling time is 0.5～5 hour; Described calcination time is calcining 4～36 hours.
Beneficial effect:
The preparation method of a kind of spinel type lithium titanate provided by the invention, with titanium sulfate, titanyl sulfate or chlorination oxygen titanium is raw material, the novel precursor that at first prepares a kind of lithium titanate--titanium oxyoxalate acid, then presoma and lithium source mixing and ball milling are got amorphous lithium titanate, calcine again spinel type lithium titanate.The present invention does not have special requirement to the purity of raw material, can be technical grade, chemical pure or analytically pure raw material; Because presoma contains a large amount of oxalates, produce a large amount of CO and CO when therefore calcining
2Gas makes product loose porous, and granularity is tiny and even; Because at first ball milling obtains amorphous lithium titanate, therefore required temperature is lower when calcining.The lithium titanate chemical property excellence that present method makes, the charging and discharging capacity when 10C can reach more than the 140mAh/g, and the cycle performance excellence.
The present invention compares with the method that other prepares spinel type lithium titanate, and its advantage fully shows in the following areas:
1) is raw material with inorganic titanium salt, purity is not had special requirement, can be technical grade, chemical pure or analytical pure titanium salt.
2) at first synthesizing new presoma--titanium oxyoxalate acid because presoma contains a large amount of oxalates, therefore produces a large amount of CO and CO when calcining
2Gas makes product loose porous, and granularity is tiny and even.
3) since at first ball milling obtain amorphous lithium titanate, therefore required temperature is lower when calcining, and the degree of crystallinity height (as Fig. 1) of product.
4) charging and discharging capacity of lithium titanate when 10C of the present invention's preparation can reach (as Fig. 2) more than the 140mAh/g, and cycle performance excellence (as Fig. 3); Its chemical property obviously is better than commercially available lithium titanate product (specific storage during 10C is generally below 120mAh/g).
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 lithium titanate;
Fig. 2 is the first charge-discharge curve of embodiment 1 lithium titanate under different multiplying;
Fig. 3 is the cycle performance curve of embodiment 1 lithium titanate under different multiplying.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1:
With industrial sulphuric acid oxygen titanium is the titanium source, be mixed with the solution of titaniferous 1mol/L, mol ratio by oxalate and titanium toward solution in adds ammonium oxalate at 3: 1,50 ℃ of following stirring reactions 10 minutes, then at 3 ℃ of freezing and crystallizings, left standstill 5 hours, with the crystal of separating out filter, with deionized water wash three times, then 80 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Press the mol ratio 4: 5 of lithium and titanium lithium hydroxide mixed with above-mentioned presoma, and at room temperature ball milling 5 hours granularity (D
50) be 0.02 micron amorphous lithium titanate, then with amorphous lithium titanate under 800 ℃, calcining promptly got the lithium titanate of spinel structure in 12 hours in air atmosphere.
Embodiment 2:
With the chemical pure titanium sulfate is the titanium source, be mixed with the solution of titaniferous 0.1mol/L, mol ratio by oxalate and titanium toward solution in adds oxalic acid at 1.5: 1,30 ℃ of following stirring reactions 1 hour, then at 0.1 ℃ of freezing and crystallizing, left standstill 0.5 hour, with the crystal of separating out filter, with deionized water wash three times, then 30 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Press the mol ratio 4.1: 5 of lithium and titanium Lithium Acetate mixed with above-mentioned presoma, and at room temperature ball milling 0.5 hour granularity (D
50) be 1 micron amorphous lithium titanate, then with amorphous lithium titanate under 700 ℃, calcining promptly got the lithium titanate of spinel structure in 4 hours in air atmosphere.
Embodiment 3:
With analytical pure chlorination oxygen titanium is the titanium source, be mixed with the solution of titaniferous 0.5mol/L, mol ratio by oxalate and titanium toward solution in adds sodium oxalate at 2: 1,60 ℃ of following stirring reactions 2 hours, then at 1 ℃ of freezing and crystallizing, left standstill 2 hours, with the crystal of separating out filter, with deionized water wash three times, then 50 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Press the mol ratio 4.2: 5 of lithium and titanium Quilonum Retard mixed with above-mentioned presoma, and at room temperature ball milling 2 hours granularity (D
50) be 0.32 micron amorphous lithium titanate, then with amorphous lithium titanate under 600 ℃, calcining promptly got the lithium titanate of spinel structure in 24 hours in air atmosphere.
Embodiment 4:
With industrial sulphuric acid oxygen titanium is the titanium source, be mixed with the solution of titaniferous 3mol/L, mol ratio by oxalate and titanium toward solution in adds oxalic acid at 4: 1,90 ℃ of following stirring reactions 3 hours, then at 4 ℃ of freezing and crystallizings, left standstill 7 hours, with the crystal of separating out filter, with deionized water wash three times, then 60 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Press the mol ratio 3.9: 5 of lithium and titanium lithium nitrate mixed with above-mentioned presoma, and at room temperature ball milling 3 hours granularity (D
50) be 0.15 micron amorphous lithium titanate, then with amorphous lithium titanate under 900 ℃, calcining promptly got the lithium titanate of spinel structure in 18 hours in air atmosphere.
Embodiment 5:
With technical grade chlorination oxygen titanium is the titanium source, be mixed with the solution of titaniferous 2mol/L, mol ratio by oxalate and titanium toward solution in adds potassium oxalate at 2.5: 1,75 ℃ of following stirring reactions 5 hours, then at 5 ℃ of freezing and crystallizings, left standstill 10 hours, with the crystal of separating out filter, with deionized water wash three times, then 70 ℃ dry lithium titanate precursor--titanium oxyoxalate acid; Press the mol ratio 3.8: 5～4.2: 5 of lithium and titanium lithium oxalate mixed with above-mentioned presoma, and at room temperature ball milling 4 hours granularity (D
50) be 0.08 micron amorphous lithium titanate, then with amorphous lithium titanate under 700 ℃, calcining promptly got the lithium titanate of spinel structure in 36 hours in air atmosphere.
Although the present invention is described in each preferred embodiment, but those skilled in the art understand the present invention easily is not limited to foregoing description, it can be changed by multiple alternate manner or improve, and does not break away from the spirit and scope of illustrating in the claim of the present invention.As the title complex that contains oxalate can also be wherein several mixed ligand complex of sodium oxalate, potassium oxalate, oxalic acid and ammonium oxalate; The lithium source can also be lithium lactate and Lithium Oxide 98min.
Claims (5)
1. the preparation method of a lithium titanate with spinel structure, it is characterized in that: the solution that titanium salt is mixed with titaniferous 0.1-3mol/L, mol ratio by oxalate and titanium added the title complex that contains oxalate in 1.5: 1～4: 1 in solution, under 30～90 ℃ and agitation condition, react, then at 0.1～5 ℃ of freezing and crystallizing, leave standstill, the crystal of separating out filtered, use deionized water wash, then 30～80 ℃ dry the acid of lithium titanate precursor titanium oxyoxalate; Pressing the mol ratio 3.8: 5～4.2: 5 of lithium and titanium mixes the lithium source with above-mentioned lithium titanate precursor, it is 0.02～1 micron amorphous lithium titanate that ball milling gets granularity, then with amorphous lithium titanate under 600～900 ℃, in air atmosphere, calcine, promptly get the lithium titanate of spinel structure.
2. the preparation method of a kind of lithium titanate with spinel structure according to claim 1 is characterized in that: described titanium salt is a kind of in titanium sulfate, titanyl sulfate, the chlorination oxygen titanium.
3. the preparation method of a kind of lithium titanate with spinel structure according to claim 1 and 2, it is characterized in that: described titanium salt can be technical grade, chemical pure or analytical pure titanium salt.
4. the preparation method of a kind of lithium titanate with spinel structure according to claim 1, it is characterized in that: the described title complex that contains oxalate is one or more in sodium oxalate, potassium oxalate, oxalic acid and the ammonium oxalate.
5. prepare the method for ferric lithium phosphate precursor according to each described comprehensive utilization ilmenite of claim 1～4, it is characterized in that: described lithium source is a kind of in Quilonum Retard, lithium hydroxide, Lithium Acetate, lithium lactate, lithium nitrate, lithium oxalate and the Lithium Oxide 98min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817551A (en) * | 2010-05-31 | 2010-09-01 | 中南大学 | Method for preparing lithium titanate precursor from titanic iron ore |
| CN104916449A (en) * | 2015-06-16 | 2015-09-16 | 广东工业大学 | Preparation method of supercapacitor ferrous titanate nanoflower electrode material |
| CN106477623A (en) * | 2016-09-12 | 2017-03-08 | 苏州大学 | A kind of method for preparing bobbles shape lithium titanate |
| CN108598421A (en) * | 2018-04-25 | 2018-09-28 | 桑顿新能源科技有限公司 | A kind of start and stop battery |
| CN109817922A (en) * | 2019-01-23 | 2019-05-28 | 湖南摩根海容新材料有限责任公司 | High power type lithium titanate composite material and preparation method |
| CN110092413A (en) * | 2019-05-09 | 2019-08-06 | 云南中烟工业有限责任公司 | A kind of method that spray drying-solid phase method prepares lithium titanate |
| CN110564392A (en) * | 2019-09-06 | 2019-12-13 | 成都理工大学 | Double-liquid type water plugging material for oil well and preparation method thereof |
| CN114956209A (en) * | 2022-06-27 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free cathode material with single crystal structure and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172646A (en) * | 2007-11-05 | 2008-05-07 | 桂林工学院 | Method of producing spinel structured lithium titanate |
-
2009
- 2009-11-30 CN CN2009103106882A patent/CN101704681B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817551A (en) * | 2010-05-31 | 2010-09-01 | 中南大学 | Method for preparing lithium titanate precursor from titanic iron ore |
| CN104916449A (en) * | 2015-06-16 | 2015-09-16 | 广东工业大学 | Preparation method of supercapacitor ferrous titanate nanoflower electrode material |
| CN106477623A (en) * | 2016-09-12 | 2017-03-08 | 苏州大学 | A kind of method for preparing bobbles shape lithium titanate |
| CN106477623B (en) * | 2016-09-12 | 2017-10-24 | 苏州大学 | A kind of method for preparing bobbles shape lithium titanate |
| CN108598421A (en) * | 2018-04-25 | 2018-09-28 | 桑顿新能源科技有限公司 | A kind of start and stop battery |
| CN109817922A (en) * | 2019-01-23 | 2019-05-28 | 湖南摩根海容新材料有限责任公司 | High power type lithium titanate composite material and preparation method |
| CN110092413A (en) * | 2019-05-09 | 2019-08-06 | 云南中烟工业有限责任公司 | A kind of method that spray drying-solid phase method prepares lithium titanate |
| CN110564392A (en) * | 2019-09-06 | 2019-12-13 | 成都理工大学 | Double-liquid type water plugging material for oil well and preparation method thereof |
| CN110564392B (en) * | 2019-09-06 | 2021-03-30 | 成都理工大学 | Double-liquid type water plugging material for oil well and preparation method thereof |
| CN114956209A (en) * | 2022-06-27 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free cathode material with single crystal structure and preparation method and application thereof |
| CN114956209B (en) * | 2022-06-27 | 2024-02-27 | 蜂巢能源科技股份有限公司 | Medium-low nickel cobalt-free positive electrode material with single crystal structure, and preparation method and application thereof |
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