CN105152217B - A kind of preparation method of spinel lithium manganate - Google Patents
A kind of preparation method of spinel lithium manganate Download PDFInfo
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- CN105152217B CN105152217B CN201510470324.6A CN201510470324A CN105152217B CN 105152217 B CN105152217 B CN 105152217B CN 201510470324 A CN201510470324 A CN 201510470324A CN 105152217 B CN105152217 B CN 105152217B
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Abstract
The invention belongs to the preparation field of LiMn2O4, specifically a kind of preparation method of spinel lithium manganate, it is included MnSO4Solution and NH4HCO3Solution adds stirring reaction in reactor；MnCO will be obtained after the washing of above-mentioned product, filtering3；By MnCO3It is fired into Mn3O4；By Mn3O4Add H2O2Middle reaction；It is aged again, suction filtration obtains MnOOH；Stoichiometrically take MnOOH and Li2CO3, and add ethanol ball milling；Then the material of ball milling is dried, then is placed in calcining in Muffle furnace, obtain spinel lithium manganate.The present invention utilizes MnSO4For bottom liquid prepares MnCO3, then by MnCO3Mn oxide is fired into, then presoma is obtained by with hydrogen peroxide is added, then by obtaining spinel lithium manganate after ball milling, calcining, the whole technological process used time is shorter, and forerunner's weight of generation is higher, prepares spinel lithium manganate quality preferable.
Description
Technical field
The present invention relates to the preparation field of LiMn2O4, specifically a kind of preparation method of spinel lithium manganate.
Background technology
To alleviate global energy crisis, environmental crisis, some countries concentrate on focus on New Energy Industry, and develop electricity
Electrical automobile is then the emphasis of New Energy Industry；Therefore, for the power lithium battery that electric automobile provides clean environment firendly is increasingly received
To attention.At present, for power lithium battery, in manufacturing technology and application above have very big market and development prospect, plus
The technique of strong power type lithium manganate battery and application study are for promoting the fast-developing significant of New Energy Industry.
At present, when spinel lithium manganate is prepared, the generation of its presoma MnOOH directly affects the quality of LiMn2O4, and
The process time that prior art prepares spinel lithium manganate is long, and equipment is expensive, so that production is raw originally higher.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation method of spinel lithium manganate, simple by the method
It is easy, it is with low cost.
The present invention solve the technical scheme that uses of above-mentioned technical problem for：A kind of preparation method of spinel lithium manganate, its
Comprise the following steps：
（1）By MnSO4Solution and NH4HCO3Solution adds stirring reaction in reactor；
（2）MnCO will be obtained after the washing of above-mentioned product, filtering3；
（3）By MnCO3It is fired into Mn3O4；
（4）By Mn3O4Add H2O2Middle reaction；
（5）It is aged again, suction filtration obtains MnOOH；
（6）Stoichiometrically take MnOOH and Li2CO3, and add ethanol ball milling；
（7）Then the material of ball milling is dried, then is placed in calcining in Muffle furnace, obtain spinel lithium manganate.
Preferably, MnSO4Concentration be 0.8-1.2mol/L, NH4HCO3Concentration be 0.8-1.2mol/L, solution
The speed for adding reactor is 10-14mL/min.
Preferably, pH value in controlling course of reaction is 7, reaction temperature is 50--70 DEG C, mixing speed is 500-
700r/min。
Preferably, step（1）Reaction terminate after, ageing 2-4h after wash again.
Preferably, MnCO3During roasting, temperature is 950--1100 DEG C, and roasting time is 4-6h under oxygen atmosphere.
Preferably, H2O2With Mn3O4Entering mol ratio is（4—6）:1.
Preferably, by Mn3O4H is added after cooling2O2In, 30-45min is reacted at room temperature, it is 8.7 to keep pH value.
Preferably, step（5）It is to be aged 5--7h at 95--105 DEG C.
Preferably, ball milling carries out 2-4h at normal temperatures.
Preferably, toasting 11-13h at 70--90 DEG C during drying, calcining is to calcine 22-24h at 700--900 DEG C.
Knowable to above scheme, the present invention utilizes MnSO4For bottom liquid prepares MnCO3, then by MnCO3It is fired into Mn oxide,
Then presoma is obtained by with hydrogen peroxide is added, then by obtaining spinel lithium manganate, whole technological process after ball milling, calcining
Used time is shorter, and forerunner's weight of generation is higher, prepares spinel lithium manganate quality preferable.
Specific embodiment
The preparation method of spinel lithium manganate of the invention described in detail below, it includes：
By MnSO4Solution and NH4HCO3Solution adds stirring reaction in reactor, and reaction solution is scrubbed, obtain after filtering
MnCO3；MnSO4Concentration be 0.8-1.2mol/L, NH4HCO3Concentration be 0.8-1.2mol/L, wherein NH4HCO3Solution
It is preferably excessive, using larger concentration, can increase solution saturation degree, the increase of crystal nucleation rate is remote high in reaction system
In the increase of crystal generating rate, the precipitation particle of generation is smaller；It is 10-14mL/min that solution adds the speed of reactor, can
So that particle distribution is smaller；It is 7 to control the pH value in course of reaction, and reaction temperature is 50--70 DEG C, this temperature conditions reaction speed
Rate is big, and nucleation rate is fast, reacts moment nucleation, and precipitation particles particle diameter is smaller, meanwhile, because high temperature increased the molecule in solution
Motion so that the precipitation particle of generation has larger specific surface area, the active force reunited between increased particle；Mixing speed is
500-700r/min, mixing speed is excessive, and manganese carbonate particles collision aggravation, particle surface pattern can be destroyed, mixing speed mistake
Small, manganese carbonate particle agglomeration is more serious, and mixing speed of the invention can take into account reunion and two conditions of particle, be most preferably
Select；After reaction terminates, 2-4h is aged, may be such that manganese carbonate granule-morphology preferably, tap density is larger, and preparation efficiency is higher.
By MnCO3It is fired into Mn3O4,, MnCO3During roasting, temperature is 950--1100 DEG C, if temperature is too low to have Mn2O3,
In the presence of, it is unfavorable to follow-up technique, and be calcined and should be carried out under oxygen atmosphere, the time is 4-6h；The product grain for so obtaining
Particle diameter is more uniform.
Obtain Mn3O4,Afterwards, H is added it to2O2In, according to H2O2With Mn3O4Mol ratio be（4—6）:1 adds, so
Mn can completely be destroyed3O4, make Mn3O4Converted to MnOOH；In the process, it is preferably such that Mn3O4Added after being cooled to room temperature, protected
Card is instead carried out at room temperature, because hot environment promotes Mn3O4Growth, pH value is 8.7, then can ensure the carrying out of conversion；30-
Bubble collapse after 45min, then the suction filtration after ageing 5--7h at 95--105 DEG C, obtain presoma MnOOH.
Then, MnOOH and Li is stoichiometrically taken2CO3, and ethanol ball milling is added, ball milling carries out 2-4h at normal temperatures；
Then the material after 11-13h ball millings is toasted at 70--90 DEG C, then is placed in Muffle furnace and is calcined 22- at 700--900 DEG C
24h, obtains spinel lithium manganate.
Embodiment 1
By the MnSO of 0.8 mol/L4Solution is bottom liquid, will be relative to MnSO4Total mole number excessive 20% 1 mol/L
NH4HCO3Solution is with stirring reaction, 50 DEG C of controlling reaction temperature, mixing speed in the speed addition reactor of 10mL/min
500r/min, pH value are 7, and 2h is aged after the completion of reaction, are washed out, are filtrated to get MnCO3, then by MnCO3In oxygen atmosphere
Under with temperature be 950 DEG C roasting 6h, after product cooling after according to H2O2With Mn3O4Mol ratio is 4:1 adds H2O2In, in room temperature
Under, pH value be that suction filtration obtains presoma after 7h is aged at 95 DEG C, then stoichiometrically takes after reacting 45min under the conditions of 8.7
MnOOH and Li2CO3, and ethanol ball milling ball milling 2h at normal temperatures is added, 13h is then toasted at 70 DEG C, then be placed in Muffle furnace
To calcine 24h at 700 DEG C, spinel lithium manganate is obtained.Sampling analysis, spinel lithium manganate average grain diameter is 296.5nm, particle diameter
It is evenly distributed, substantially, crystallinity is good, with smooth surface for crystal formation.
Embodiment 2
By the MnSO of 1 mol/L4Solution is bottom liquid, will be relative to MnSO4Total mole number excessive 20% 1.2 mol/L
NH4HCO3Solution is with stirring reaction, 60 DEG C of controlling reaction temperature, mixing speed in the speed addition reactor of 12mL/min
600r/min, pH value are 7, and 3h is aged after the completion of reaction, are washed out, are filtrated to get MnCO3, then by MnCO3In oxygen atmosphere
Under with temperature be 1000 DEG C roasting 5h, after product cooling after according to H2O2With Mn3O4Mol ratio is 5:1 adds H2O2In, in room temperature
Under, pH value be that suction filtration obtains presoma after 6h is aged at 100 DEG C after reacting 40min under the conditions of 8.7, then stoichiometrically
Take MnOOH and Li2CO3, and ethanol ball milling ball milling 3h at normal temperatures is added, 12h is then toasted at 80 DEG C, then be placed in Muffle furnace
In to calcine 24h at 800 DEG C, obtain spinel lithium manganate.Sampling analysis, spinel lithium manganate average grain diameter is 211.3nm, grain
Footpath is evenly distributed, and substantially, crystallinity is good, with smooth surface for crystal formation.
Embodiment 3
By the MnSO of 1 .2mol/L4Solution is bottom liquid, will be relative to MnSO4Total mole number excessive 20% 0.8mol/L
NH4HCO3Solution is with stirring reaction, 70 DEG C of controlling reaction temperature, mixing speed in the speed addition reactor of 14mL/min
700r/min, pH value are 7, and 4h is aged after the completion of reaction, are washed out, are filtrated to get MnCO3, then by MnCO3In oxygen atmosphere
Under with temperature be 1000 DEG C roasting 4h, after product cooling after according to H2O2With Mn3O4Mol ratio is 6:1 adds H2O2In, in room temperature
Under, pH value be that suction filtration obtains presoma after 5h is aged at 105 DEG C after reacting 30min under the conditions of 8.7, then stoichiometrically
Take MnOOH and Li2CO3, and ethanol ball milling ball milling 4h at normal temperatures is added, 11h is then toasted at 90 DEG C, then be placed in Muffle furnace
In to calcine 22h at 900 DEG C, obtain spinel lithium manganate.Sampling analysis, spinel lithium manganate average grain diameter is 254.1nm, grain
Footpath is evenly distributed, and substantially, crystallinity is good, with smooth surface for crystal formation.
Above-mentioned implementation method is used for illustrative purposes only, and is not limitation of the present invention, relevant technical field
Those of ordinary skill, without departing from the spirit and scope of the present invention, can be so that various changes can be made and modification, therefore institute
Having equivalent technical scheme should also belong to scope of the invention.
Claims (10)
1. a kind of preparation method of spinel lithium manganate, it is comprised the following steps：
（1）By MnSO4Solution and NH4HCO3Solution adds stirring reaction in reactor；
（2）MnCO will be obtained after the washing of above-mentioned product, filtering3；
（3）By MnCO3It is fired into Mn3O4；
（4）By Mn3O4Add H2O2Middle reaction；
（5）It is aged again, suction filtration obtains MnOOH；
（6）Stoichiometrically take MnOOH and Li2CO3, and add ethanol ball milling；
（7）Then the material of ball milling is dried, then is placed in calcining in Muffle furnace, obtain spinel lithium manganate.
2. preparation method according to claim 1, it is characterised in that：MnSO4Concentration be 0.8-1.2mol/L, NH4HCO3
Concentration be 0.8-1.2mol/L, solution add reactor speed be 10-14mL/min.
3. preparation method according to claim 2, it is characterised in that：It is 7 to control the pH value during the stirring reaction, instead
It is 50--70 DEG C to answer temperature, and mixing speed is 500-700r/min.
4. preparation method according to claim 3, it is characterised in that：Step（1）Reaction terminate after, ageing 2-4h after again
Washing.
5. preparation method according to claim 4, it is characterised in that：MnCO3During roasting, temperature is 950--1100 DEG C, in oxygen
Roasting time is 4-6h under gas atmosphere.
6. preparation method according to claim 1, it is characterised in that：H2O2With Mn3O4Mol ratio is（4—6）:1.
7. preparation method according to claim 6, it is characterised in that：By Mn3O4H is added after cooling2O2In, react at room temperature
30-45min, it is 8.7 to keep pH value.
8. preparation method according to claim 7, it is characterised in that：Step（5）It is to be aged 5--7h at 95--105 DEG C.
9. preparation method according to claim 1, it is characterised in that：Ball milling carries out 2-4h at normal temperatures.
10. preparation method according to claim 1, it is characterised in that：11-13h is toasted at 70--90 DEG C during drying, is calcined
It is to calcine 22-24h at 700--900 DEG C.
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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 |
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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 |
|---|
| "Oxidation of synthetic hausmannite（Mn3O4）to manganite（MnOOH）";S.A.Kirillov et al.;《Journal of Molecular Structure》;20090324;第928卷;第89页第4段 * |
| "碳酸锰热解法制备尖晶石锰酸锂及其掺杂改性研究";杨婧;《中国优秀硕士论文全文数据库 工程科技Ⅱ辑》;20140515(第5期);第18页倒数第1段、第19页第2段、第35页第4-7段、第36页第1段 * |
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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 |