CN109231277A - A kind of preparation method and applications of D50:30-35 μm of manganese dioxide particle - Google Patents
A kind of preparation method and applications of D50:30-35 μm of manganese dioxide particle Download PDFInfo
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- CN109231277A CN109231277A CN201811381270.6A CN201811381270A CN109231277A CN 109231277 A CN109231277 A CN 109231277A CN 201811381270 A CN201811381270 A CN 201811381270A CN 109231277 A CN109231277 A CN 109231277A
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- manganese dioxide
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- manganese
- dioxide particle
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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 discloses a kind of preparation method and applications of D50:30-35 μm of manganese dioxide particle, belong to manganese bioxide material preparation field.The application first prepares precipitant solution, is divided into 2 parts, and first part of precipitating reagent is slowly dropped into manganese nitrate solution；Sodium polyacrylate solution is added, is placed under 60 DEG C of bath temperature and stirs, slurry 1 is obtained after stirring；Second part of precipitating reagent is slowly added dropwise in slurry 1, sediment is stirred, is aged, filtering and to obtain, cleaning is dried to obtain powder after filtering；By powder calcination under oxygen atmosphere, up to D50:30-35 μm of manganese dioxide after calcination, manganese dioxide particle is prepared, low energy consumption, and preparation is simple, and cost is relatively low；And the period is not grown, and is suitble to produce in enormous quantities.
Description
Technical field
The invention belongs to manganese bioxide material preparation fields more particularly to a kind of D50:30-35 μm of manganese dioxide to granulate
Length of schooling Preparation Method.
Background technique
Lithium battery is using lithium metal as the general name of the electrochmical power source series of cathode, is a kind of high voltage, high energy battery.From
Since the primary prospect for proposing lithium battery for 1958, develop extremely rapid.Currently, the lithium ion battery that primary commercial uses
Positive electrode has: the lithium transition-metal phosphorus of lithium manganate having spinel structure, layer structure lithium transition-metal oxide and olivine structural
Hydrochlorate etc..Wherein spinel lithium manganate is especially standby due to excellent thermal stability, resource characteristics abundant and good safety
It attracts attention.Since manganese dioxide is material a kind of cheap and abundant, and it is with excellent electric discharge and long-term storage performance,
Therefore its active material for being typically used as dry cell unit.
Up to the present, in the world battery with manganese dioxide still mainly from electrolytic manganese dioxide.But electrolysis dioxy
Changing that manganese is long there are the production cycle, power consumption is high, environmental pollution property equipment investment secondary greatly is big etc. and not adapting to mankind nowadays society can hold
The problem of supervention exhibition.In addition the manganese dioxide of general requirements is not that particle is too small, exactly needs to obtain 0.3 millimeter of left side by crushing
Right manganese dioxide.The particle of none appropriate specification meets required for client.
Summary of the invention
It is an object of the invention to overcome conventional method to prepare high production cost existing for common manganese dioxide, complex process
And the problem that production efficiency is low, and the particle being settled out is smaller, provides a kind of simple for process, and production cost is low, production
The manganese dioxide particle chemical preparation process that high-efficient and D50 is 30-35 μm or so.Appropriate stirring intensity is found, when reaction
Between, concentration and additive, the present invention prepare a kind of D50:30-35m or so manganese dioxide particle, solve tradition preparation titanium dioxide
Particle is uneven in manganese, peak shape wider distribution, the excessive problem of little particle.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of D50:30-35 μm or so manganese dioxide particle chemical preparation process, specific preparation process is as follows:
(1) precipitant solution is prepared, is divided into 2 parts, first part and second part of mass ratio are 1:2；
(2) first part of precipitating reagent is slowly dropped into manganese nitrate solution；
(3) sodium polyacrylate solution is added after step (2) are added dropwise, is stirred evenly through 50-60r/min revolving speed, stirred
It is placed under 60 DEG C of bath temperature again and stirs 2h, slurry 1 is obtained after stirring；
(4) second part of precipitating reagent is slowly added dropwise in slurry 1, stirs, 3h is aged at 60 DEG C, filters heavy after ageing
Starch cleans impurity with deionized water repeatedly, obtains powder after suction filtration；
(5) powder is warming up to 300~400 DEG C of progress calcinations under oxygen atmosphere, up to D50:30-35 μm two after calcination
Manganese oxide.
The precipitating reagent is that sodium hydroxide or sodium carbonate one or two mix；The molar concentration of the precipitant solution is
0.5~0.8mol/L.
The speed that the precipitating reagent is added dropwise is 0.3-1L/min.
The D50:30-35 μm of manganese dioxide particle is in lithium ion battery material.
Compared with prior art, the application has the beneficial effect that
(1) present invention is prepared into manganese dioxide particle using the precipitation method, old by controlling precipitant concentration, mixing speed
Change temperature, D50:30-35 μm of manganese dioxide particle can be accurately prepared in the conditions such as digestion time, convenient for it in lithium electricity
Application in sub- battery；
(2) additive Sodium Polyacrylate is added in the present invention in slurry 1, is preparing D50:30-35 μm of manganese dioxide particle
In play an important role, can not only particle be made to further increase, and between precipitating reagent also have generation cooperate with work
With solving the problem of the uneven peak shape wider distribution of particle；
(3) present invention discover that may advantageously facilitate particle aggregation precipitating reagent is divided into 2 parts of additions, growing up, through the invention
Preparation method prepare manganese dioxide particle, low energy consumption, and preparation is simple, and cost is relatively low；And the period is not grown, and is suitble to big
Batch production.
Detailed description of the invention
Fig. 1 is the grain size distribution of manganese dioxide prepared by embodiment 1.
Fig. 2 is the grain size distribution of manganese dioxide prepared by embodiment 2.
Specific implementation method
Embodiment 1
(1) weigh the manganese nitrate crystal of 6Kg, (the manganese nitrate crystal transformation rate bought be 50%), be added 33.5L go from
Sub- water dissolution, is stirred evenly with 50 revs/min, and being configured to concentration is 0.5mol/L manganese nitrate solution；
(2) sodium hydroxide 1.34Kg is weighed, 41.9L deionized water is added and stirs evenly, being configured to concentration is 0.8mol/L
Sodium hydroxide solution, be divided into 2 parts, first part and second part of mass ratio are 1:2；
(3) 14L sodium hydroxide solution is first slowly added dropwise in manganese nitrate solution, control rate of addition is 300mL/min, control
Dropping temperature processed is 30 DEG C；
(4) 6g Sodium Polyacrylate is weighed, sodium polyacrylate solution is obtained after the dissolution of 6L pure water is added, is added dropwise and ties to step (3)
Sodium polyacrylate solution is added dropwise in Shu Houzai, and slurry 1 is obtained after dropwise addition；
(5) slurry 1 is stirred 2 hours under 60 DEG C of bath temperature, the hydrogen-oxygen of remaining 27.9L is slowly added dropwise after stirring again
Change sodium solution, stir 15min after dripping, static ageing 3 hours, filter after ageing at 60 DEG C, collect filter cake and are gone with 750L
Ion water washing is passed through 350 DEG C of calcinations of oxygen into manganese dioxide in stove, and the manganese dioxide granularity being prepared into after detecting is
D50:31.32μm。
Embodiment 2
(1) the manganese nitrate crystal of 10Kg is weighed, (the manganese nitrate crystal transformation rate bought is 50%) is added 34.9L and goes
Ionized water dissolution, is stirred evenly with 55 revs/min, and being configured to concentration is 0.8mol/L manganese nitrate solution；
(2) sodium carbonate 2.96Kg is weighed, 46.5L deionized water is added and stirs evenly, being configured to concentration is 0.6mol/L's
Sodium hydroxide solution, is divided into 2 parts, and first part and second part of mass ratio are 1:2；
(3) 15.5L sodium carbonate liquor, rate of addition 350ml/min, control drop are first slowly added dropwise in manganese nitrate solution
Heating degree is 35 DEG C；
(4) 10 grams of Sodium Polyacrylates are weighed, sodium polyacrylate solution is obtained after the dissolution of 10L pure water is added, is added dropwise to step (3)
After sodium polyacrylate solution is added dropwise again, after dropwise addition slurry 1；
(5) slurry 1 is stirred 2 hours under 60 DEG C of bath temperature, the hydroxide of remaining 31L is slowly added dropwise after stirring again
Sodium solution.15min is stirred after dripping, static ageing 3 hours, are filtered after ageing at 60 DEG C, are collected filter cake and are gone with 1000L
Ionized water removes undesired impurities, 400 DEG C of calcinations of oxygen is passed through in stove into manganese dioxide, the titanium dioxide being prepared into after detecting
Manganese granularity is D50:33.44 μm.
Comparative example 1
Compared with Example 1, preparation condition is essentially identical for comparative example 1, and difference is that precipitating reagent is not divided into 2 parts of additions.
(1) weigh the manganese nitrate crystal of 6Kg, (the manganese nitrate crystal transformation rate bought be 50%), be added 33.5L go from
Sub- water dissolution, is stirred evenly with 50 revs/min, and being configured to concentration is 0.5mol/L manganese nitrate solution；
(2) sodium hydroxide 1.34Kg is weighed, 41.9L deionized water is added and stirs evenly, being configured to concentration is 0.8mol/L
Sodium hydroxide solution；
(3) sodium hydroxide solution of step (2) is first slowly added dropwise in manganese nitrate solution, control rate of addition is 300mL/
Min, control dropping temperature are 30 DEG C
(4) 6g Sodium Polyacrylate is weighed, sodium polyacrylate solution is obtained after the dissolution of 6L pure water is added, is added dropwise and ties to step (3)
Sodium polyacrylate solution is added dropwise in Shu Houzai, and slurry 1 is obtained after dropwise addition；
(5) slurry 1 is stirred under 60 DEG C of bath temperature 2 hours, then static ageing 3 hours, ageing at 60 DEG C
After filter, collect filter cake washed with 750L deionized water, 350 DEG C of calcinations of oxygen are passed through in stove at manganese dioxide, through detecting
The manganese dioxide granularity being prepared into afterwards is D50:6.88 μm.
Comparative example 2
Compared with Example 1, preparation condition is essentially identical for comparative example 2, and difference is that sodium polyacrylate solution is not added.
(1) weigh the manganese nitrate crystal of 6Kg, (the manganese nitrate crystal transformation rate bought be 50%), be added 33.5L go from
Sub- water dissolution, is stirred evenly with 50 revs/min, and being configured to concentration is 0.5mol/L manganese nitrate solution；
(2) sodium hydroxide 1.34Kg is weighed, 41.9L deionized water is added and stirs evenly, being configured to concentration is 0.8mol/L
Sodium hydroxide solution, be divided into 2 parts, first part and second part of mass ratio are 1:2；
(3) 14L sodium hydroxide solution is first slowly added dropwise in manganese nitrate solution, control rate of addition is 300mL/min, control
Dropping temperature processed is 30 DEG C；
(4) slurry 1 is stirred 2 hours under 60 DEG C of bath temperature, the hydrogen-oxygen of remaining 27.9L is slowly added dropwise after stirring again
Change sodium solution, stir 15min after dripping, static ageing 3 hours, filter after ageing at 60 DEG C, collect filter cake and are gone with 750L
Ion water washing is passed through 350 DEG C of calcinations of oxygen into manganese dioxide in stove, and the manganese dioxide granularity being prepared into after detecting is
D50:13.32μm。
Comparative example 3
Compared with Example 1, preparation condition is essentially identical for comparative example 3, and difference is, not the water-bath to slurry 1 at 60 DEG C
At a temperature of stir 2 hours.
(1) weigh the manganese nitrate crystal of 6Kg, (the manganese nitrate crystal transformation rate bought be 50%), be added 33.5L go from
Sub- water dissolution, is stirred evenly with 50 revs/min, and being configured to concentration is 0.5mol/L manganese nitrate solution；
(2) sodium hydroxide 1.34Kg is weighed, 41.9L deionized water is added and stirs evenly, being configured to concentration is 0.8mol/L
Sodium hydroxide solution, be divided into 2 parts, first part and second part of mass ratio are 1:2；
(3) 14L sodium hydroxide solution is first slowly added dropwise in manganese nitrate solution, control rate of addition is 300mL/min, control
Dropping temperature processed is 30 DEG C；
(4) 6g Sodium Polyacrylate is weighed, sodium polyacrylate solution is obtained after the dissolution of 6L pure water is added, is added dropwise and ties to step (3)
Sodium polyacrylate solution is added dropwise in Shu Houzai, and slurry 1 is obtained after dropwise addition；
(5) slurry 1 is stirred 2 hours at room temperature, the sodium hydroxide solution of remaining 27.9L is slowly added dropwise after stirring again, dripped
15min is stirred after adding, static ageing 3 hours, filter after ageing at room temperature, and it collects filter cake and is washed with 750L deionized water,
350 degree of calcinations of oxygen are passed through in stove into manganese dioxide, the manganese dioxide granularity being prepared into after detecting is D50:18.18 μ
m。
Claims (6)
1. a kind of preparation method of D50:30-35 μm of manganese dioxide particle, which is characterized in that specific preparation step are as follows:
(1) precipitant solution is prepared, is divided into 2 parts, first part and second part of mass ratio are 1:2；
(2) first part of precipitating reagent is slowly dropped into manganese nitrate solution；
(3) sodium polyacrylate solution is added after step (2) are added dropwise, is stirred evenly through 50-60r/min revolving speed, obtains slurry
1；
(4) slurry 1 is stirred under 60 DEG C of bath temperature, second part of precipitating reagent, stirring, ageing, mistake is slowly added dropwise after stirring
Sediment is filtered to obtain, impurity is cleaned repeatedly with deionized water, obtains powder after suction filtration；
(5) powder is warming up to 300~400 DEG C of progress calcinations under oxygen atmosphere, up to D50:30-35 μm of titanium dioxide after calcination
Manganese.
2. the preparation method of D50:30-35 μm of manganese dioxide particle according to claim 1, it is characterised in that: the precipitating
Agent is the mixing of one or both of sodium hydroxide or sodium carbonate；The molar concentration of the precipitant solution is 0.5~0.8mol/
L。
3. the preparation method of D50:30-35 μm of manganese dioxide particle according to claim 1, it is characterised in that: described is old
Changing temperature is 60 DEG C, digestion time 3h.
4. the preparation method of D50:30-35 μm of manganese dioxide particle according to claim 1, it is characterised in that: described is heavy
The speed that shallow lake agent is added dropwise is 0.3-1L/min.
5. the preparation method of D50:30-35 μm of manganese dioxide particle according to claim 1, it is characterised in that: the slurry
Material 1 stirs 2h under 60 DEG C of bath temperature.
6. the application of D50:30-35 μm of manganese dioxide particle of any one of -5 the method preparations according to claim 1, feature
Be: the manganese dioxide is in lithium ion battery material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655113A (en) * | 2019-09-29 | 2020-01-07 | 南昌大学 | Na-doped MnO2Preparation method of electrode material |
| CN110697785A (en) * | 2019-10-16 | 2020-01-17 | 蚌埠学院 | Preparation of manganese oxide-nitrogen modified graphene composite material and lithium battery application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647375A (en) * | 1969-10-22 | 1972-03-07 | Japan Metals & Chem Co Ltd | Method of producing manganese dioxide |
| CN1919741A (en) * | 2006-09-19 | 2007-02-28 | 北京科技大学 | Method for preparing high apparent density manganese dioxide using manganese sulfate solution |
| CN102040247A (en) * | 2010-11-20 | 2011-05-04 | 湖北开元化工科技股份有限公司 | Method and device for producing chemical manganese dioxide |
| CN102557145A (en) * | 2012-02-22 | 2012-07-11 | 中信大锰矿业有限责任公司 | Method for preparing low-impurity manganese oxide |
| CN105502490A (en) * | 2015-04-21 | 2016-04-20 | 江西晶安高科技股份有限公司 | Coarse-grained sphere-like zirconium hydroxide with large specific surface area and preparation method of zirconium hydroxide |
-
2018
- 2018-11-20 CN CN201811381270.6A patent/CN109231277B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647375A (en) * | 1969-10-22 | 1972-03-07 | Japan Metals & Chem Co Ltd | Method of producing manganese dioxide |
| CN1919741A (en) * | 2006-09-19 | 2007-02-28 | 北京科技大学 | Method for preparing high apparent density manganese dioxide using manganese sulfate solution |
| CN102040247A (en) * | 2010-11-20 | 2011-05-04 | 湖北开元化工科技股份有限公司 | Method and device for producing chemical manganese dioxide |
| CN102557145A (en) * | 2012-02-22 | 2012-07-11 | 中信大锰矿业有限责任公司 | Method for preparing low-impurity manganese oxide |
| CN105502490A (en) * | 2015-04-21 | 2016-04-20 | 江西晶安高科技股份有限公司 | Coarse-grained sphere-like zirconium hydroxide with large specific surface area and preparation method of zirconium hydroxide |
Non-Patent Citations (2)
| Title |
|---|
| 李家玉等: "石英晶体微天平分析不同介孔二氧化锰材料的电化学性能", 《分析化学研究报告》 * |
| 陈南雄等: "氨缓冲体系强化高纯重质碳酸锰的制备", 《化工学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655113A (en) * | 2019-09-29 | 2020-01-07 | 南昌大学 | Na-doped MnO2Preparation method of electrode material |
| CN110697785A (en) * | 2019-10-16 | 2020-01-17 | 蚌埠学院 | Preparation of manganese oxide-nitrogen modified graphene composite material and lithium battery application |
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