CN106532169A - Method of recycling lithium manganate dust - Google Patents
Method of recycling lithium manganate dust Download PDFInfo
- Publication number
- CN106532169A CN106532169A CN201611173707.8A CN201611173707A CN106532169A CN 106532169 A CN106532169 A CN 106532169A CN 201611173707 A CN201611173707 A CN 201611173707A CN 106532169 A CN106532169 A CN 106532169A
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- China
- Prior art keywords
- dust
- limn2o4
- lithium manganate
- mass ratio
- oxygen atmosphere
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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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of new energy material preparation, and particularly relates to a method of recycling lithium manganate dust. The method comprises the steps of dispersing the lithium manganate dust, a sintering aid and an oxygen atmosphere improver into deionized water; adding a polyvinyl alcohol solution; and carrying out spray granulation and burning to obtain a product. Oxygen deficiency of a lithium manganate material during high-temperature reaction is effectively inhibited through adding the oxygen atmosphere improver to the lithium manganate dust; the electrochemical properties are improved through repairing one part of structure defects; and through a granulation technology, the grain growth degree is controllable, crystal balls or secondary grains tend to be spherical, the tap density of the processed product is greatly improved and the processability is improved.
Description
Technical field
The invention belongs to technical field of new energy material preparation, more particularly to a kind of method that LiMn2O4 dust is recycled.
Background technology
In the production process of anode material for lithium ion battery manganese lithium, need to material after burning till reaction due to high temperature
Grain is processed, and can reach use demand, therefore generally adopt air-flow crushing or mechanical crushing, produce during this
More LiMn2O4 dust, due to particle it is less, and it is most be surface or structural damage particle, therefore in the discharge and recharge of lithium battery
During easily react with electrolyte, battery performance is had undesirable effect, thus be rejected more without.Even if performance of loweing will
Ask, using requiring relatively low field, due to the particle diameter of these products it is less so that the technique of coating of sizing mixing is more difficult to be carried out, therefore
Without actual market.Problems are present, and not only decline material comprehensive utilization ratio, and improve production cost, storehouse
Deposit and processing cost.
To improve the utilization rate of LiMn2O4 dust, it will usually which these dust granules are sintered again, burnt by adding
Knot auxiliary agent, is allowed to grow into colony, to reach particle growth, meets the index of granularity.But when processing, still suffer from many asking
Topic：(1) it is wayward into Long grain, and tap density is too low, processing characteristics is poor；(2) pyroreaction makes material molecule structure
Produce " oxygen vacancy ", deteriorate chemical property；(3) by the material for processing, can only use as low side digital products, it is attached
Price markup value is relatively low.
In view of above-mentioned defect, the design people, actively research and innovation in addition, sharp again to founding a kind of LiMn2O4 dust
Method so as to more the value in industry.
The content of the invention
To solve above-mentioned technical problem, it is an object of the invention to provide a kind of method that LiMn2O4 dust is recycled, can
So that the oxygen vacancy generation of lithium manganate material is effectively suppressed during pyroreaction, chemical property is improved；And crystalline substance can be controlled
The big degree of grain length, after raising process, the tap density of product, improves its processing characteristics.
The method that a kind of LiMn2O4 dust proposed by the present invention is recycled, comprises the following steps：
S1. in deionized water, mass ratio is added to be 250：1：25 LiMn2O4 dust, sintering aid, oxygen atmosphere improve
Agent, fully dispersed uniform, deionized water is 1 with the mass ratio of LiMn2O4 dust：2, sintering aid is boric acid, oxygen atmosphere improver
It is mixed to get with electrolytic manganese dioxide by lithium carbonate；
S2., in the dispersion liquid for obtaining in step sl, the poly-vinyl alcohol solution for adding solid content to be 10% stirs,
Poly-vinyl alcohol solution is 1 with the mass ratio of LiMn2O4 dust：10.
S3. the mixing liquid that step S2 is obtained is spray-dried in spray-drying installation, causes average grain to exist
100～200 μm of particle；
S4. the particle obtained in step S3 is added into calciner, calcining heat is 750 DEG C～850 DEG C, and calcination time is
6h, obtains product.
Further, in step S1, the mass ratio of lithium carbonate and electrolytic manganese dioxide is 1.1：4, the chemistry under its high temperature
Reaction equation is：Li2CO3+4MnO2---2LiMn2O4+CO2↑+0.5O2↑。
Further, the particle diameter of LiMn2O4 dust is 0.1～10 μm.
By such scheme, the present invention at least has advantages below：The present invention is by adding oxygen in LiMn2O4 dust
Atmosphere improver so that the oxygen vacancy of lithium manganate material is produced and is effectively suppressed during pyroreaction, and it is scarce to repair part-structure
Fall into, improved chemical property；By prilling so that the degree that crystal grain is grown up is controllable, colony or secondary
Grain morphology tends to spherical, greatly improves the tap density of product after processing, improves its processing characteristics.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Description of the drawings
Fig. 1 is the product after processing in LiMn2O4 dust and the product after processing, embodiment 2 in the embodiment of the present invention 1
Size distribution comparison diagram；
Fig. 2 is the scanning electron microscope (SEM) photograph of LiMn2O4 dust in the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of product in the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of product in the embodiment of the present invention 2；
Fig. 5 is the product after processing in LiMn2O4 dust and the product after processing, embodiment 2 in the embodiment of the present invention 1
Cycle life test data comparison diagram.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Hereinafter implement
Example is for illustrating the present invention, but is not limited to the scope of the present invention.
Embodiment 1
Take LiMn2O4 dust 100g and add 0.4g boric acid, and add mass ratio to be 1.1：4 lithium carbonate and electrolysis titanium dioxide
The oxygen atmosphere improver 10g that manganese is mixed to prepare, it is under conditions of having deionized water 50g, fully dispersed uniform, add solid content
PVA (polyvinyl alcohol) solution 10g for 10%, stirs.
Above-mentioned mixed solution is spray-dried in spray-drying installation, average grain is caused at 100～200 μm
Particle.Above-mentioned particle is added into calciner, 750 DEG C of calcining heat, calcination time are 6 hours, obtain product.
Chemical equation of the lithium carbonate with electrolytic manganese dioxide at high temperature be：Li2CO3+4MnO2---2LiMn2O4+
CO2↑+0.5O2↑.Wherein CO2Release in pyroprocess leading portion, O2Release in pyroprocess back segment, sintering process oxygen can be improved
Atmosphere, it is to avoid produce oxygen vacancy.
After LiMn2O4 dust, process in the present embodiment, the relevant characterization datagram of product is shown in Fig. 1,2,3,5.
Embodiment 2
In the case where oxygen atmosphere improver is added without, remaining step is identical with embodiment, the correlation of the product for obtaining
Characterize data figure is shown in Fig. 1,4,5.
In sum, the present invention is can be seen that by LiMn2O4 dust from the cycle life test data comparison diagram of Fig. 5
Middle addition oxygen atmosphere improver so that the oxygen vacancy of lithium manganate material is produced and is effectively suppressed during pyroreaction, and is repaired
Part-structure defect, is improved chemical property；By prilling so that the degree that crystal grain is grown up is controllable,
Colony or subgrain pattern tend to spherical, greatly improve the tap density of product after processing, improve its processing characteristics.
The above is only the preferred embodiment of the present invention, is not limited to the present invention, it is noted that for this skill
For the those of ordinary skill in art field, on the premise of without departing from the technology of the present invention principle, can also make it is some improvement and
Modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (3)
1. a kind of method that LiMn2O4 dust is recycled, it is characterised in that：Comprise the following steps：
S1. in deionized water, mass ratio is added to be 250：1：25 LiMn2O4 dust, sintering aid, oxygen atmosphere improver, fill
It is uniformly dispersed, deionized water is 1 with the mass ratio of LiMn2O4 dust：2, sintering aid is boric acid, and oxygen atmosphere improver is by carbon
Sour lithium is mixed to get with electrolytic manganese dioxide；
S2., in the dispersion liquid for obtaining in step sl, the poly-vinyl alcohol solution for adding solid content to be 10% stirs, poly- second
Enolate solution is 1 with the mass ratio of LiMn2O4 dust：10.
S3. the mixing liquid that step S2 is obtained is spray-dried in spray-drying installation, cause average grain 100～
200 μm of particle；
S4. the particle obtained in step S3 is added into calciner, calcining heat is 750 DEG C～850 DEG C, and calcination time is 6h,
Obtain product.
2. the method that LiMn2O4 dust according to claim 1 is recycled, it is characterised in that：In step S1, lithium carbonate and
The mass ratio of electrolytic manganese dioxide is 1.1：4, the chemical equation under its high temperature is：Li2CO3+4MnO2---2LiMn2O4+
CO2↑+0.5O2↑。
3. the method that LiMn2O4 dust according to claim 1 is recycled, it is characterised in that：The particle diameter of LiMn2O4 dust is
0.1～10 μm.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173707.8A CN106532169A (en) | 2016-12-16 | 2016-12-16 | Method of recycling lithium manganate dust |
| JP2018566625A JP6700438B2 (en) | 2016-12-16 | 2017-12-10 | Reuse method of lithium manganate dust |
| PCT/CN2017/115364 WO2018108043A1 (en) | 2016-12-16 | 2017-12-10 | Method for recycling lithium manganate dust |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173707.8A CN106532169A (en) | 2016-12-16 | 2016-12-16 | Method of recycling lithium manganate dust |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106532169A true CN106532169A (en) | 2017-03-22 |
Family
ID=58340312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611173707.8A Pending CN106532169A (en) | 2016-12-16 | 2016-12-16 | Method of recycling lithium manganate dust |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6700438B2 (en) |
| CN (1) | CN106532169A (en) |
| WO (1) | WO2018108043A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018108043A1 (en) * | 2016-12-16 | 2018-06-21 | 无锡晶石新型能源股份有限公司 | Method for recycling lithium manganate dust |
| CN115133021A (en) * | 2022-06-27 | 2022-09-30 | 广西华桂兴时代新能源科技股份有限公司 | Method for improving compaction density of lithium manganate battery positive electrode material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6150050A (en) * | 1998-03-09 | 2000-11-21 | Valence Technology, Inc | Method for recovering particulate material from electrical components |
| CN104183839A (en) * | 2013-05-22 | 2014-12-03 | 无锡晶石新型能源有限公司 | Lithium manganate fine particle processing method |
| CN104425814A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium manganate material and preparation method thereof and lithium ion battery cathode material |
| CN104466164A (en) * | 2014-12-02 | 2015-03-25 | 赵县强能电源有限公司 | Treatment method of lithium manganate fine powder |
| CN104577104A (en) * | 2015-01-15 | 2015-04-29 | 兰州理工大学 | Regeneration method of positive material lithium manganate waste of lithium ion battery |
| WO2016008813A1 (en) * | 2014-07-15 | 2016-01-21 | Lars Walch Gmbh & Co. Kg | Recycling method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004349210A (en) * | 2003-05-26 | 2004-12-09 | Toyota Motor Corp | Regenerating method of anode active material for lithium secondary battery |
| JP5535716B2 (en) * | 2009-09-30 | 2014-07-02 | Ｄｏｗａエコシステム株式会社 | Lithium recovery method |
| CN102709542B (en) * | 2012-05-25 | 2014-11-05 | 青岛乾运高科新材料股份有限公司 | Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material |
| CN106058353B (en) * | 2016-08-11 | 2018-05-25 | 荆门市格林美新材料有限公司 | The reparative regeneration method of old and useless battery positive electrode |
| CN106532169A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Method of recycling lithium manganate dust |
-
2016
- 2016-12-16 CN CN201611173707.8A patent/CN106532169A/en active Pending
-
2017
- 2017-12-10 JP JP2018566625A patent/JP6700438B2/en active Active
- 2017-12-10 WO PCT/CN2017/115364 patent/WO2018108043A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6150050A (en) * | 1998-03-09 | 2000-11-21 | Valence Technology, Inc | Method for recovering particulate material from electrical components |
| CN104183839A (en) * | 2013-05-22 | 2014-12-03 | 无锡晶石新型能源有限公司 | Lithium manganate fine particle processing method |
| CN104425814A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium manganate material and preparation method thereof and lithium ion battery cathode material |
| WO2016008813A1 (en) * | 2014-07-15 | 2016-01-21 | Lars Walch Gmbh & Co. Kg | Recycling method |
| CN104466164A (en) * | 2014-12-02 | 2015-03-25 | 赵县强能电源有限公司 | Treatment method of lithium manganate fine powder |
| CN104577104A (en) * | 2015-01-15 | 2015-04-29 | 兰州理工大学 | Regeneration method of positive material lithium manganate waste of lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018108043A1 (en) * | 2016-12-16 | 2018-06-21 | 无锡晶石新型能源股份有限公司 | Method for recycling lithium manganate dust |
| CN115133021A (en) * | 2022-06-27 | 2022-09-30 | 广西华桂兴时代新能源科技股份有限公司 | Method for improving compaction density of lithium manganate battery positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6700438B2 (en) | 2020-05-27 |
| JP2019510728A (en) | 2019-04-18 |
| WO2018108043A1 (en) | 2018-06-21 |
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Application publication date: 20170322 |
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