CN105152217A - Preparation method of spinel lithium manganate - Google Patents
Preparation method of spinel lithium manganate Download PDFInfo
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- CN105152217A CN105152217A CN201510470324.6A CN201510470324A CN105152217A CN 105152217 A CN105152217 A CN 105152217A CN 201510470324 A CN201510470324 A CN 201510470324A CN 105152217 A CN105152217 A CN 105152217A
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- preparation
- reaction
- lithium manganate
- ball milling
- spinel lithium
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- 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
Abstract
The invention belongs to the field of preparation of lithium manganate, and specifically relates to a preparation method of spinel lithium manganate. The preparation method comprises: adding a solution of MnSO4 and a solution of NH4HCO3 into a reaction kettle, and performing stirring for reaction; washing and filtering the reaction product to obtain MnCO3; calcining MnCO3 into Mn3O4; adding Mn3O4 into H2O2 for reaction; performing aging and suction filtration to obtain MnOOH; getting MnOOH and Li2CO3 according to a stoichiometric ratio, and adding ethanol into the mixture for ball milling; drying the obtained materials treated through ball milling; and putting the obtained product into a muffle furnace for calcination to obtain spinel 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; adding hydrogen peroxide into the manganese oxide to obtain a precursor; and performing ball milling and calicination to obtain spinel lithium manganate. The whole technical process is relatively short; the generated precursor is high in quality; and the prepared spinel lithium manganate is relatively good in quality.
Description
Technical field
The present invention relates to the preparation field of lithium manganate, is a kind of preparation method of spinel 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, when preparing spinel lithium manganate, the generation of its presoma MnOOH directly affects the quality of lithium manganate, and the process time that prior art prepares spinel lithium manganate is long, and equipment is expensive, to such an extent as to produces raw originally higher.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of preparation method of spinel lithium manganate, simple by the method, with low cost.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of preparation method of spinel lithium manganate, and it comprises the following steps:
(1) by MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor;
(2) MnCO is obtained by after above-mentioned reaction product washing, filtration
3;
(3) by MnCO
3roasting becomes Mn
3o
4;
(4) by Mn
3o
4add H
2o
2middle reaction;
(5) ageing again, suction filtration obtains MnOOH;
(6) stoichiometrically MnOOH and Li is got
2cO
3, and add ethanol ball milling;
(7) then dry the material of ball milling, then be placed in retort furnace and calcine, obtain spinel 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, after the reaction of step (1) terminates, wash again after ageing 2-4h.
As preferably, MnCO
3during roasting, temperature is 950--1100 DEG C, and under oxygen atmosphere, roasting time is 4-6h.
As preferably, H
2o
2with Mn
3o
4enter mol ratio for (4-6): 1.
As preferably, by Mn
3o
4h is added after cooling
2o
2in, at room temperature react 30-45min, keep pH value to be 8.7.
As preferably, step (5) is ageing 5--7h at 95--105 DEG C.
As preferably, ball milling carries out 2-4h at normal temperatures.
As preferably, toast 11-13h during oven dry at 70--90 DEG C, calcining calcines 22-24h at 700--900 DEG C.
From above scheme, the present invention utilizes MnSO
4for end liquid prepares MnCO
3, then by MnCO
3roasting becomes Mn oxide, then by with add hydrogen peroxide and obtain presoma, then by obtaining spinel lithium manganate after ball milling, calcining, the whole technical process used time is shorter, and the presoma quality of generation is higher, prepares spinel lithium manganate quality better.
Embodiment
Below introduce the preparation method of spinel lithium manganate of the present invention in detail, it comprises:
By MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor, and reaction solution 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
3o
4,, MnCO
3during roasting, temperature is 950--1100 DEG C, if temperature is too low have Mn
2o
3,exist, unfavorable to follow-up technique, and roasting should be carried out under oxygen atmosphere, the time is 4-6h; The product grain particle diameter obtained like this is comparatively even.
Obtain Mn
3o
4,after, joined H
2o
2in, according to H
2o
2with Mn
3o
4mol ratio be (4-6): 1 adds, and can destroy Mn completely like this
3o
4, make Mn
3o
4transform to MnOOH; In the process, preferably Mn is made
3o
4add after being cooled to room temperature, ensure instead at room temperature to carry out, because hot environment promotes Mn
3o
4growth, pH value is 8.7, then can ensure the carrying out transformed; Bubble collapse after 30-45min, then at 95--105 DEG C suction filtration after ageing 5--7h, obtain presoma MnOOH.
Then, stoichiometrically MnOOH and Li is got
2cO
3, and adding ethanol ball milling, ball milling carries out 2-4h at normal temperatures; Then at 70--90 DEG C, toast the material after 11-13h ball milling, then be placed in retort furnace calcine 22-24h at 700--900 DEG C, obtain spinel 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 950 DEG C of roasting 6h with temperature under oxygen atmosphere, according to H after product cooling
2o
2with Mn
3o
4mol ratio is that 4:1 adds H
2o
2in, at room temperature, pH value is after reacting 45min under 8.7 conditions, and at 95 DEG C, after ageing 7h, suction filtration obtains presoma, more stoichiometrically gets MnOOH and Li
2cO
3, and add ethanol ball milling ball milling 2h at normal temperatures, then at 70 DEG C, toast 13h, then be placed in retort furnace calcine 24h at 700 DEG C, obtain spinel lithium manganate.Sampling analysis, spinel lithium manganate median size is 296.5nm, even particle size distribution, and crystal formation is obvious, and degree of crystallinity is good, has smooth surface.
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 1000 DEG C of roasting 5h with temperature under oxygen atmosphere, according to H after product cooling
2o
2with Mn
3o
4mol ratio is that 5:1 adds H
2o
2in, at room temperature, pH value is after reacting 40min under 8.7 conditions, and at 100 DEG C, after ageing 6h, suction filtration obtains presoma, more stoichiometrically gets MnOOH and Li
2cO
3, and add ethanol ball milling ball milling 3h at normal temperatures, then at 80 DEG C, toast 12h, then be placed in retort furnace calcine 24h at 800 DEG C, obtain spinel lithium manganate.Sampling analysis, spinel lithium manganate median size is 211.3nm, even particle size distribution, and crystal formation is obvious, and degree of crystallinity is good, has smooth surface.
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 1000 DEG C of roasting 4h with temperature under oxygen atmosphere, according to H after product cooling
2o
2with Mn
3o
4mol ratio is that 6:1 adds H
2o
2in, at room temperature, pH value is after reacting 30min under 8.7 conditions, and at 105 DEG C, after ageing 5h, suction filtration obtains presoma, more stoichiometrically gets MnOOH and Li
2cO
3, and add ethanol ball milling ball milling 4h at normal temperatures, then at 90 DEG C, toast 11h, then be placed in retort furnace calcine 22h at 900 DEG C, obtain spinel lithium manganate.Sampling analysis, spinel lithium manganate median size is 254.1nm, even particle size distribution, and crystal formation is obvious, and degree of crystallinity is good, has smooth surface.
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 (10)
1. a preparation method for spinel lithium manganate, it comprises the following steps:
(1) by MnSO
4solution and NH
4hCO
3solution adds stirring reaction in reactor;
(2) MnCO is obtained by after above-mentioned reaction product washing, filtration
3;
(3) by MnCO
3roasting becomes Mn
3o
4;
(4) by Mn
3o
4add H
2o
2middle reaction;
(5) ageing again, suction filtration obtains MnOOH;
(6) stoichiometrically MnOOH and Li is got
2cO
3, and add ethanol ball milling;
(7) then dry the material of ball milling, then be placed in retort furnace and calcine, obtain spinel 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 the reaction of step (1) terminates, wash after ageing 2-4h again.
5. preparation method according to claim 4, is characterized in that: MnCO
3during roasting, temperature is 950--1100 DEG C, and under oxygen atmosphere, roasting time is 4-6h.
6. preparation method according to claim 1, is characterized in that: H
2o
2with Mn
3o
4enter mol ratio for (4-6): 1.
7. preparation method according to claim 6, is characterized in that: by Mn
3o
4h is added after cooling
2o
2in, at room temperature react 30-45min, keep pH value to be 8.7.
8. preparation method according to claim 7, is characterized in that: step (5) is ageing 5--7h at 95--105 DEG C.
9. preparation method according to claim 1, is characterized in that: ball milling carries out 2-4h at normal temperatures.
10. preparation method according to claim 1, it is characterized in that: at 70--90 DEG C, toast 11-13h during oven dry, calcining calcines 22-24h at 700--900 DEG C.
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|---|---|---|---|
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|---|---|---|---|
| CN201510470324.6A CN105152217B (en) | 2015-08-05 | 2015-08-05 | A kind of preparation method of spinel lithium manganate |
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| Publication Number | Publication Date |
|---|---|
| CN105152217A true CN105152217A (en) | 2015-12-16 |
| CN105152217B CN105152217B (en) | 2017-06-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107919474A (en) * | 2017-11-13 | 2018-04-17 | 苏州宇量电池有限公司 | A kind of nanometer spherical mangano-manganic oxide negative material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218443A (en) * | 1996-04-08 | 1999-06-02 | 杜拉塞尔公司 | Preparation of lithium manganese oxide spinel |
| CN102130330A (en) * | 2010-01-15 | 2011-07-20 | 清华大学 | Method for preparing lithium ion battery anode material |
-
2015
- 2015-08-05 CN CN201510470324.6A patent/CN105152217B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218443A (en) * | 1996-04-08 | 1999-06-02 | 杜拉塞尔公司 | Preparation of lithium manganese oxide spinel |
| CN102130330A (en) * | 2010-01-15 | 2011-07-20 | 清华大学 | Method for preparing lithium ion battery anode material |
Non-Patent Citations (2)
| Title |
|---|
| S.A.KIRILLOV ET AL.: ""Oxidation of synthetic hausmannite（Mn3O4）to manganite（MnOOH）"", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| 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》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107919474A (en) * | 2017-11-13 | 2018-04-17 | 苏州宇量电池有限公司 | A kind of nanometer spherical mangano-manganic oxide negative material and preparation method thereof |
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|---|---|
| CN105152217B (en) | 2017-06-20 |
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Effective date of registration: 20191227 Address after: 343400 Ji'an City, Jiangxi province Yongxin County Industrial Development Zone Industrial Park Star Patentee after: Jiangxi Huahao new energy Co., Ltd Address before: 545000 the Guangxi Zhuang Autonomous Region Liuzhou Liu Dong New Area Guantang Pioneer Park Development Center Building 2, No. 511 Patentee before: LIUZHOU HAOXIANGTE TECHNOLOGY CO., LTD. |
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Denomination of invention: A preparation method of spinel lithium manganate Effective date of registration: 20201216 Granted publication date: 20170620 Pledgee: Yongxin County sub branch of Postal Savings Bank of China Ltd. Pledgor: Jiangxi Huahao new energy Co.,Ltd. Registration number: Y2020980009417 |
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