CN105152218A - Preparation method of layered lithium manganate - Google Patents
Preparation method of layered lithium manganate Download PDFInfo
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- CN105152218A CN105152218A CN201510470333.5A CN201510470333A CN105152218A CN 105152218 A CN105152218 A CN 105152218A CN 201510470333 A CN201510470333 A CN 201510470333A CN 105152218 A CN105152218 A CN 105152218A
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- preparation
- lithium manganate
- ball milling
- reaction
- layered lithium
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Abstract
The invention belongs to the field of preparation of lithium manganate, and particularly relates to a preparation method of layered lithium manganate. The preparation method comprises: adding a solution of MnSO4 and a solution of NH4HCO3 into a reaction kettle, performing stirring for reaction, and washing and filtering the reaction product to obtain MnCO3; calcining MnCO3 into Mn2O3; mixing Mn2O3 and LiOH.H2O and adding ethanol into the mixture for ball milling; performing drying and grinding after ball milling; and washing the obtained product with deionized water to obtain layered lithium manganate. According to the preparation method, firstly, MnSO4 is taken as a base solution to prepare MnCO3; then, MnCO3 is calcined into a manganese oxide; and finally, performing ball milling of the manganese oxide and LiOH to prepare layered lithium manganate. Relatively pure layered lithium manganate is prepared at a comparably low mole ratio of Li to Mn. The whole technical process is short, and the process is easy to control and low in cost, so that the preparation method is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation field of lithium manganate, is a kind of preparation method of layered lithium manganate specifically.
Background technology
For alleviating global energy crisis, ecocrisis, some countries concentrate on focus on New Energy Industry, and Development of EV is then the emphasis of New Energy Industry; Therefore, for electromobile provides the power lithium battery of clean environment firendly more and more to come into one's own.At present, for power lithium battery, in manufacturing technology and in application, have very large market and development prospect, technique and the applied research of strengthening dynamic lithium manganate battery are significant for the fast development promoting New Energy Industry.
At present, the preparation method of layered lithium manganate has hydrothermal method, ion exchange method, solid-phase synthesis, sol-gel method etc., in these methods, react insufficient as solid-phase synthesis exists, product thing is mutually uneven, and particle is comparatively large, and skewness etc. forward, some method steps is loaded down with trivial details, require higher reaction conditions, lithium ion waste rate is high, reproducibility is low, and not easily realizes industrialization, cannot produce in batches.
Summary of the invention
For above-mentioned technical problem, the invention provides that a kind of process is easy to control, the preparation method of with low cost, output and all higher layered lithium manganate of productive rate.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of preparation method of layered lithium manganate, and it comprises the following steps:
(1) by MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor, and reaction product obtains MnCO after washing, filtration
3;
(2) by MnCO
3roasting becomes Mn
2o
3;
(3) by Mn
2o
3and LiOHH
2ethanol ball milling is added after O mixing;
(4) drying, grinding is carried out after ball milling;
(5) use deionized water wash again, obtain layered lithium manganate.
As preferably, MnSO
4concentration be 0.8-1.2mol/L, NH
4hCO
3concentration be 0.8-1.2mol/L, the speed that solution adds reactor is 10-14mL/min.
As preferably, the pH value controlled in reaction process is 7, and temperature of reaction is 50--70 DEG C, and stirring velocity is 500-700r/min.
As preferably, react after terminating, ageing 2-4h.
As preferably, MnCO
3during roasting, temperature is 500--600 DEG C, and under oxygen atmosphere, roasting time is 8-10h.
As preferably, during ball milling, ratio of grinding media to material is (30--20): the mol ratio of 1, Li and Mn is (1-2): 1.
As preferably, during ball milling, by solid-liquid mass ratio (2-3): 1 adds ethanol.
As preferably, Ball-milling Time is 6-8h.
From above scheme, the present invention utilizes MnSO
4for end liquid prepares MnCO
3, then by MnCO
3roasting becomes Mn oxide, then by with LiOH ball milling layered lithium manganate, it can prepare comparatively pure layered lithium manganate under lower Li and Mn molar ratio, and whole technical process is shorter, and process control is easy, and cost is lower, is applicable to suitability for industrialized production.
Embodiment
Below introduce the preparation method of layered lithium manganate of the present invention in detail, it comprises:
By MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor, and reaction product obtains MnCO after washing, filtration
3; MnSO
4concentration be 0.8-1.2mol/L, NH
4hCO
3concentration be 0.8-1.2mol/L, wherein NH
4hCO
3solution is preferably excessive, adopts larger concentration, and solution saturation ratio can be made to increase, and in reaction system, the increase of crystal nucleation rate will far above the increase of crystal generating rate, and the deposit seeds of generation is less; The speed that solution adds reactor is 10-14mL/min, and particle distribution can be made less; The pH value controlled in reaction process is 7, temperature of reaction is 50--70 DEG C, this temperature condition speed of reaction is large, nucleation rate is fast, reaction moment nucleation, and precipitation particles particle diameter is less, simultaneously, because high temperature adds the molecular motion in solution, make the deposit seeds generated have larger specific surface area, add the reactive force of reuniting between particle; Stirring velocity is 500-700r/min, and stirring velocity is excessive, and manganous carbonate particle collision aggravates, particle surface pattern can be destroyed, and stirring velocity is too small, and manganous carbonate particle agglomeration is comparatively serious, stirring velocity of the present invention can take into account reunion and particle two conditions, is optimal selection; After reaction terminates, ageing 2-4h, can make manganous carbonate granule-morphology better, and tap density is comparatively large, and preparation efficiency is higher.
By MnCO
3roasting becomes Mn
2o
3, MnCO
3during roasting, temperature is 500--600 DEG C, and temperature is lower, can generate MnO
2,, temperature is higher, can generate Mn
3o
4,, and roasting should be carried out under oxygen atmosphere, the time is 8-10h; The product grain particle diameter obtained like this is comparatively even.
By Mn
2o
3and LiOHH
2ethanol ball milling is added, during ball milling, by solid-liquid mass ratio (2-3): 1 adds ethanol as control agent, is conducive to ball milling after O mixing; Meanwhile, ratio of grinding media to material is (30--20): the mol ratio of 1, Li and Mn is (1-2): 1, and Ball-milling Time is 6-8h.Comparatively pure layered lithium manganate can be prepared with this understanding by lower Li and Mn mol ratio.
After ball milling, layered lithium manganate is carried out drying, then grind according to granularity requirements; Then use deionized water wash, wash residue and remaining LiOH off, final drying is preserved, and obtains comparatively pure layered lithium manganate.
Embodiment 1
By the MnSO of 0.8mol/L
4solution is end liquid, will relative to MnSO
4the NH of 1mol/L of total mole number excessive 20%
4hCO
3solution adds stirring reaction in reactor with the speed of 10mL/min, controls temperature of reaction 50 DEG C, stirring velocity 500r/min, pH value be 7, reacted rear ageing 2h, then washed, filters and obtain MnCO
3, then by MnCO
3be 500 DEG C of roasting 10h with temperature under oxygen atmosphere, then by product and LiOHH
2o mixing and ball milling, adds ethanol by solid-liquid mass ratio 2:1; Meanwhile, ensure that ratio of grinding media to material be the mol ratio of 30:1, Li and Mn is 1:1, dry after ball milling 6h, grinding, with deionized water wash, drying, obtains layered lithium manganate.Sampling analysis, sample is comparatively pure, and size distribution is comparatively even.
Embodiment 2
By the MnSO of 1mol/L
4solution is end liquid, will relative to MnSO
4the NH of 1.2mol/L of total mole number excessive 20%
4hCO
3solution adds stirring reaction in reactor with the speed of 12mL/min, controls temperature of reaction 60 DEG C, stirring velocity 600r/min, pH value be 7, reacted rear ageing 3h, then washed, filters and obtain MnCO
3, then by MnCO
3be 550 DEG C of roasting 9h with temperature under oxygen atmosphere, then by product and LiOHH
2o mixing and ball milling, adds ethanol by solid-liquid mass ratio 2.5:1; Meanwhile, ensure that ratio of grinding media to material be the mol ratio of 20:1, Li and Mn is 1.5:1, dry after ball milling 7h, grinding, with deionized water wash, drying, obtains layered lithium manganate.Sampling analysis, sample is pure, even particle size distribution.
Embodiment 3
By the MnSO of 1.2mol/L
4solution is end liquid, will relative to MnSO
4the NH of 0.8mol/L of total mole number excessive 20%
4hCO
3solution adds stirring reaction in reactor with the speed of 14mL/min, controls temperature of reaction 70 DEG C, stirring velocity 700r/min, pH value be 7, reacted rear ageing 4h, then washed, filters and obtain MnCO
3, then by MnCO
3be 600 DEG C of roasting 8h with temperature under oxygen atmosphere, then by product and LiOHH
2o mixing and ball milling, adds ethanol by solid-liquid mass ratio 3:1; Meanwhile, ensure that ratio of grinding media to material be the mol ratio of 25:1, Li and Mn is 3:1, dry after ball milling 8h, grinding, with deionized water wash, drying, obtains layered lithium manganate.Sampling analysis, sample is pure, even particle size distribution.Wherein, the product of embodiment 2 is the most excellent.
Above-mentioned embodiment is used for illustrative purposes only, and be not limitation of the present invention, the those of ordinary skill of relevant technical field, without departing from the spirit and scope of the present invention, can also make various change and modification, therefore all equivalent technical schemes also should belong to category of the present invention.
Claims (8)
1. a preparation method for layered lithium manganate, it comprises the following steps:
(1) by MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor, and reaction product obtains MnCO after washing, filtration
3;
(2) by MnCO
3roasting becomes Mn
2o
3;
(3) by Mn
2o
3and LiOHH
2ethanol ball milling is added after O mixing;
(4) drying, grinding is carried out after ball milling;
(5) use deionized water wash again, obtain layered lithium manganate.
2. preparation method according to claim 1, is characterized in that: MnSO
4concentration be 0.8-1.2mol/L, NH
4hCO
3concentration be 0.8-1.2mol/L, the speed that solution adds reactor is 10-14mL/min.
3. preparation method according to claim 2, is characterized in that: the pH value controlled in reaction process is 7, and temperature of reaction is 50--70 DEG C, and stirring velocity is 500-700r/min.
4. preparation method according to claim 3, is characterized in that: after reaction terminates, ageing 2-4h.
5. preparation method according to claim 4, is characterized in that: MnCO
3during roasting, temperature is 500--600 DEG C, and under oxygen atmosphere, roasting time is 8-10h.
6. preparation method according to claim 1, it is characterized in that: during ball milling, ratio of grinding media to material is (30--20): the mol ratio of 1, Li and Mn is (1-2): 1.
7. preparation method according to claim 6, is characterized in that: during ball milling, by solid-liquid mass ratio (2-3): 1 adds ethanol.
8. preparation method according to claim 7, is characterized in that: Ball-milling Time is 6-8h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394204A (en) * | 2017-07-18 | 2017-11-24 | 中北大学 | A kind of preparation method of positive electrode laminated cell lithium manganate of lithium ion |
| CN109336183A (en) * | 2018-10-10 | 2019-02-15 | 北京科技大学 | It is a kind of to be raw material preparation Mn with value Mn and low price manganese compound2O3Method |
| CN112968166A (en) * | 2021-03-22 | 2021-06-15 | 安徽博石高科新材料股份有限公司 | Preparation method of lithium manganate positive electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249341A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Manufacturing method for layered lithium manganate cathode material for lithium ion battery |
| CN103413934A (en) * | 2013-09-03 | 2013-11-27 | 中北大学 | Preparation method of layered lithium manganate (positive electrode material) of lithium ion battery |
-
2015
- 2015-08-05 CN CN201510470333.5A patent/CN105152218A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249341A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Manufacturing method for layered lithium manganate cathode material for lithium ion battery |
| CN103413934A (en) * | 2013-09-03 | 2013-11-27 | 中北大学 | Preparation method of layered lithium manganate (positive electrode material) of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 杨婧: ""碳酸锰热解法制备尖晶石锰酸锂及其掺杂改性研究"", 《中国优秀硕士论文全文数据库 工程科技Ⅱ辑》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394204A (en) * | 2017-07-18 | 2017-11-24 | 中北大学 | A kind of preparation method of positive electrode laminated cell lithium manganate of lithium ion |
| CN109336183A (en) * | 2018-10-10 | 2019-02-15 | 北京科技大学 | It is a kind of to be raw material preparation Mn with value Mn and low price manganese compound2O3Method |
| CN112968166A (en) * | 2021-03-22 | 2021-06-15 | 安徽博石高科新材料股份有限公司 | Preparation method of lithium manganate positive electrode material |
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Application publication date: 20151216 |
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