CN105161708B - A kind of preparation method of manganate precursor for lithium - Google Patents
A kind of preparation method of manganate precursor for lithium Download PDFInfo
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- CN105161708B CN105161708B CN201510470361.7A CN201510470361A CN105161708B CN 105161708 B CN105161708 B CN 105161708B CN 201510470361 A CN201510470361 A CN 201510470361A CN 105161708 B CN105161708 B CN 105161708B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to the preparation field of LiMn2O4, specifically a kind of preparation method of manganate precursor for lithium, including by MnSO4Solution and NH4HCO3Solution is added in reaction kettle and is stirred to react；MnCO will be obtained after the washing of above-mentioned reaction product, filtering3；By MnCO3It is fired into Mn3O4；By Mn3O4Add in H2O2Middle reaction；It is aged again, obtains presoma MnOOH.The present invention utilizes MnSO4MnCO is prepared for bottom liquid3, then by MnCO3Mn oxide is fired into, then by obtaining presoma with adding in hydrogen peroxide, entire technological process is shorter, and process control is easy, and cost is relatively low, and the preparation for spinel lithium manganate is laid a good foundation.
Description
Technical field
The present invention relates to the preparation field of LiMn2O4, specifically a kind of preparation method of manganate precursor for lithium.
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 electric vehicle provide the power lithium battery of clean environment firendly increasingly by
To attention.At present, for power lithium battery, in manufacturing technology and application above has very big market and development prospect, adds
The technique of strong power type lithium manganate battery and application study are for pushing the fast development of New Energy Industry to be of great significance.
At present, when preparing spinel lithium manganate, the generation of presoma MnOOH directly affects the quality of LiMn2O4, by
It is less to the research of presoma in the limitation of the prior art, restrict the research of LiMn2O4 always.
Invention content
For above-mentioned technical problem, the present invention provides a kind of preparation method of manganate precursor for lithium, simple by this method
It is easy, it is of low cost.
The present invention solve the technical solution that uses of above-mentioned technical problem for：A kind of preparation method of manganate precursor for lithium,
Include the following steps：
(1) by MnSO4Solution and NH4HCO3Solution is added in reaction kettle and is stirred to react；
(2) MnCO will be obtained after the washing of above-mentioned reaction product, filtering3
(3) by MnCO3It is fired into Mn3O4；
(4) by Mn3O4Add in H2O2Middle reaction；
(5) it is aged again, obtains presoma MnOOH.
Preferably, MnSO4A concentration of 0.8-1.2mol/L, NH4HCO3A concentration of 0.8-1.2mol/L, solution
The speed for adding in reaction kettle is 10-14mL/min.
Preferably, the pH value in control reaction process is 7, reaction temperature is 50--70 DEG C, mixing speed for 500-
700r/min。
Preferably, step (1) is after reaction, washed again after being aged 2-4h.
Preferably, MnCO3During roasting, temperature is 950--1100 DEG C, and roasting time is 4-6h under oxygen atmosphere.
Preferably, H2O2With Mn3O4Enter molar ratio for (4-6):1.
Preferably, by Mn3O4H is added in after cooling2O2In, 30-45min is reacted at room temperature, and it is 8.7 to keep pH value.
Preferably, step (5) is to be aged 5--7h at 95--105 DEG C.
From above scheme it is found that the present invention utilizes MnSO4MnCO is prepared for bottom liquid3, then by MnCO3It is fired into Mn oxide,
Then by obtaining presoma with adding in hydrogen peroxide, entire technological process is shorter, and process control is easy, and cost is relatively low, for point
The preparation of spar LiMn2O4 is laid a good foundation.
Specific embodiment
The preparation method of the manganate precursor for lithium of the present invention described in detail below, including：
By MnSO4Solution and NH4HCO3Solution is added in reaction kettle and is stirred to react, and reaction solution is washed, is obtained after filtering
MnCO3；MnSO4A concentration of 0.8-1.2mol/L, NH4HCO3A concentration of 0.8-1.2mol/L, wherein NH4HCO3Solution is most
Well amount using larger concentration, can increase solution saturation degree, in reaction system the increase of crystal nucleation rate to be far above
The increase of crystal generating rate, the precipitation particle of generation are smaller；The speed that solution adds in reaction kettle is 10-14mL/min, can be made
It is smaller to obtain particle distribution；It is 7 to control the pH value in reaction process, and reaction temperature is 50--70 DEG C, this temperature condition reaction rate
Greatly, nucleation rate is fast, and reaction moment nucleation, precipitation particles grain size is smaller, meanwhile, because high temperature increases the molecule fortune in solution
It is dynamic so that the precipitation particle of generation has larger specific surface area, increases the active force reunited between 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 two conditions of reunion and particle, for most preferably
It selects；After reaction, 2-4h is aged, may be such that manganese carbonate granule-morphology is preferable, 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 subsequent technique, and roasting should carry out under oxygen atmosphere, the time is 4-6h；The product grain obtained in this way
Grain size is more uniform.
Obtain Mn3O4,Afterwards, H is added it to2O2In, according to H2O2With Mn3O4Molar ratio be (4-6):1 adds in, in this way
Mn can be destroyed completely3O4, make Mn3O4It is converted to MnOOH；In the process, it is preferably such that Mn3O4It adds in, protects after being cooled to room temperature
Card instead carries out at room temperature, because hot environment promotes Mn3O4Growth, pH value 8.7 can then ensure the progress of conversion；30-
Bubble collapse after 45min, then 5--7h is aged at 95--105 DEG C, so as to obtain presoma MnOOH.
Embodiment 1
By the MnSO of 0.8mol/L4Solution is bottom liquid, will be relative to MnSO4Total mole number excessive 20% 1mol/L
NH4HCO3Solution is added in reaction kettle with the speed of 10mL/min and is stirred to react, 50 DEG C of controlling reaction temperature, mixing speed 500r/
Min, pH value 7, ageing 2h, is washed out, MnCO is obtained by filtration after the completion of reaction3, then by MnCO3Under oxygen atmosphere with
Temperature is 950 DEG C of roasting 6h, according to H after product cooling2O2With Mn3O4Molar ratio is 4:1 adds in H2O2In, at room temperature, pH
Be worth be 8.7 under the conditions of reaction 45min after, 7h is aged at 95 DEG C, so as to obtain presoma.Sampling analysis, sample is clearly
Line style MnOOH, particle diameter distribution are uniform.
Embodiment 2
By the MnSO of 1mol/L4Solution is bottom liquid, will be relative to MnSO4Total mole number excessive 20% 1.2mol/L
NH4HCO3Solution is added in reaction kettle with the speed of 12mL/min and is stirred to react, 60 DEG C of controlling reaction temperature, mixing speed 600r/
Min, pH value 7, ageing 3h, is washed out, MnCO is obtained by filtration after the completion of reaction3, then by MnCO3Under oxygen atmosphere with
Temperature is 1000 DEG C of roasting 5h, according to H after product cooling2O2With Mn3O4Molar ratio is 5:1 adds in H2O2In, at room temperature, pH
Be worth be 8.7 under the conditions of reaction 40min after, 6h is aged at 100 DEG C, so as to obtain presoma.Sampling analysis, sample is clearly
Line style MnOOH, particle diameter distribution are uniform.
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 added in reaction kettle with the speed of 14mL/min and is stirred to react, 70 DEG C of controlling reaction temperature, mixing speed
700r/min, pH value 7, ageing 4h, is washed out, MnCO is obtained by filtration after the completion of reaction3, then by MnCO3In oxygen atmosphere
Under using temperature as 1000 DEG C roasting 4h, after product cooling after according to H2O2With Mn3O4Molar ratio is 6:1 adds in H2O2In, in room temperature
Under, pH value for reaction 30min under the conditions of 8.7 after, 5h is aged at 105 DEG C, so as to obtain presoma.Sampling analysis, sample are
Clearly line style MnOOH, particle diameter distribution are uniform.
The above embodiment is used for illustrative purposes only, and is not limitation of the present invention, related technical field
Those of ordinary skill, without departing from the spirit and scope of the present invention, can be with various changes can be made and modification, therefore institute
There is equivalent technical solution that should also belong to scope of the invention.
Claims (8)
1. a kind of preparation method of manganate precursor for lithium, includes the following steps：
（1）By MnSO4Solution and NH4HCO3Solution is added in reaction kettle and is stirred to react；
（2）MnCO will be obtained after the washing of above-mentioned reaction product, filtering3；
（3）By MnCO3It is fired into Mn3O4；
（4）By Mn3O4Add in H2O2Middle reaction；
（5）It is aged again, obtains precursor MnOOH.
2. preparation method according to claim 1, it is characterised in that：MnSO4A concentration of 0.8-1.2mol/L, NH4HCO3
A concentration of 0.8-1.2mol/L, solution add in reaction kettle speed be 10-14mL/min.
3. preparation method according to claim 2, it is characterised in that：Rate-determining steps（1）PH value in reaction process is 7, 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）After reaction, it is aged after 2-4h 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 Mn3O4Molar ratio be（4—6）:1.
7. preparation method according to claim 6, it is characterised in that：By Mn3O4H is added in after cooling2O2In, it reacts 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.
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| CN110767898B (en) * | 2019-09-30 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | Manganese-based nanowire bundle and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130330A (en) * | 2010-01-15 | 2011-07-20 | 清华大学 | Method for preparing lithium ion battery anode material |
| CN103367737A (en) * | 2012-04-09 | 2013-10-23 | 江苏国泰锂宝新材料有限公司 | Preparation method of high-density lithium battery anode material spinel lithium manganate |
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130330A (en) * | 2010-01-15 | 2011-07-20 | 清华大学 | Method for preparing lithium ion battery anode material |
| CN103367737A (en) * | 2012-04-09 | 2013-10-23 | 江苏国泰锂宝新材料有限公司 | Preparation method of high-density lithium battery anode material spinel lithium manganate |
| CN104409719A (en) * | 2014-12-02 | 2015-03-11 | 兰州理工大学 | Porous spherical lithium manganate cathode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Oxidation of synthetic hausmannite（Mn3O4）to manganite（MnOOH）";S.A.Kirillov et al.;《Journal of Molecular Structure》;20090324;第928卷;第89-94页 * |
| "The synthesis of birnessite，cryptomelane，and some other oxides and hydroxides of manganese";R.M.MCKENZIE et al.;《MINERALOGIGAL MAGAZINE》;19711231;第38卷;第493-502页 * |
| "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);C042-673 * |
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