CN106629858A - Method for removing fine powder in lithium manganate electrode materials in situ - Google Patents
Method for removing fine powder in lithium manganate electrode materials in situ Download PDFInfo
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- CN106629858A CN106629858A CN201610885380.0A CN201610885380A CN106629858A CN 106629858 A CN106629858 A CN 106629858A CN 201610885380 A CN201610885380 A CN 201610885380A CN 106629858 A CN106629858 A CN 106629858A
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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
- C01G45/12—Manganates manganites or permanganates
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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Abstract
The invention discloses a method for removing fine powder in lithium manganate electrode materials in situ, and belongs to the technical field of lithium ion battery anode materials. Trace niobium compounds are added into reaction raw materials, so that lithium manganate fine powder grows up by agglomeration in the high-temperature solid-phase reaction process, and lithium manganate anode materials with proper size distribution can be obtained without size grading of roasted finished materials. The method has the advantages that the size grading process of the finished materials is omitted, production procedures are decreased, production cost is reduced, electrolytic manganese dioxide is sufficiently used, and additionally, the lithium manganate materials synthesized by the method is concentrated in size distribution, small in specific surface area and excellent in electrochemical performance.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, and in particular to a kind of removal mangaic acid lithium electrode material in situ
The method of fine powder in material, the method easily can in process of production remove fine powder in manganic acid lithium electrode material.
Background technology
The advantages of lithium ion battery is due to operating voltage height (3.7V), big, safe and environment-friendly specific energy, memory-less effect, quilt
It is widely used in the small-scale lithium ion cells such as mobile phone, notebook computer, portable power source and electric bicycle, electric automobile, wind
The large-scale field of lithium ion battery such as electricity and photoelectricity energy storage.
Lithium manganate having spinel structure (LiMn2O4) material due to Mn aboundresources, cheap, specific capacity is high, have a safety feature
Many advantages, such as, it is widely applied in commercial Li-ion battery field.At present, industrial synthetic lithium manganate is main
Raw material are electrolytic manganese dioxide and lithium carbonate, and synthetic method is high temperature solid state reaction.Contain 5 in electrolytic manganese dioxide raw material
Particle of the granularity of～10wt.% less than 3 μm, referred to as manganese dioxide fine powder.This part fine particle is even across long-time
High-temperature roasting, the lithium manganate material granularity of generation is less than normal all the time, and this will result directly in LiMn2O4 finished-product material containing more
LiMn2O4 fine powder.In addition, material can produce hard aggregation phenomenon after high temperature solid state reaction, need to come through mechanical milling processes
The size distribution of adjustment material, also has in the process a certain amount of fine powder and produces.Fine powder amount meeting on the high side in lithium manganate material
Cause specific surface area bigger than normal, solid content can low impact work effect in the positive pole pulping process of lithium ion battery manufacturing process
Rate, and the easy shedding of anode pole piece made, not only increase the cost of manufacture of lithium ion battery, but also can reduce battery
Yield rate, affect battery cycle life.
At present, in order to remove lithium manganate material in fine powder, mostly using the method for mechanical classification, LiMn2O4 fine powder is led to
Cross cyclone separator and be isolated as waste disposal, returning manganese dioxide producer carries out recovery reprocessing.The side of above-mentioned way one
Face increased the production cost of LiMn2O4, and also environment is had a negative impact in addition.In document (1) Chinese invention patent application number
In 201410717053.5, Liu Qingguo et al. is reprocessed to LiMn2O4 fine powder, and method is to add toward LiMn2O4 fine powder
Lithium salts mixes, and recycles hydraulic press briquette forming, Jing long-time high-temperature roastings so that the particle size growth of fine powder.Though this method
So reclaim LiMn2O4 fine powder, but while increased production process, increased production cost.
The content of the invention
It is an object of the invention to provide a kind of method for removing fine powder in manganic acid lithium electrode material in situ, i.e., by anti-
Answer and add in raw material micro niobium compound, make during high temperature solid state reaction LiMn2O4 fine powder it is molten it is poly- grow up, so need not be right
Roasting finished-product material carries out grading and can be obtained by the manganate cathode material for lithium with suitable particle size distribution.Concrete technology is walked
It is rapid as described below：
(1) it is Li according to the ratio of lithium source material and the amount of the material of electrolytic manganese dioxide and niobium source material:(Mn+Nb)=
0.50～0.58:1, the ratio of the amount of the material of niobium source material and electrolytic manganese dioxide is Nb:Mn=0.001～0.015:1 will
Above-mentioned lithium source material, niobium source material and electrolytic manganese dioxide mix 1～6 hour, obtain a homogeneous mixture；Wherein, lithium source material
For the one kind in lithium carbonate, lithium hydroxide or its mixture, niobium source material is in niobium pentaoxide, niobium hydroxide, niobium oxalate
One or more.
(2) by gained mixture roasting in 750～860 DEG C of temperature ranges under oxygen or air atmosphere in step (1)
12～50 hours, room temperature is naturally cooled to, obtain product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove the bulky grain reunited, that is, gone
Except the LiMn2O4 finished-product material of fine powder.
Grain size analysis is carried out to LiMn2O4 finished-product material using the grain size analysis tester BT9300S of Dandong Bai Te, is tested
As a result it is as shown in table 1.
By LiMn2O4, acetylene black, PVDF according to 8:1:1 mass ratio is well mixed, and is coated in aluminum foil current collector, 100
Roll after DEG C drying, with sheet-punching machine the disk of a diameter of 10mm, 120 DEG C of vacuum drying 12h, with lithium in argon gas glove box are washed into
Piece is negative pole, 1molL-1LiPF6EC+DMC+DEC solution do electrolyte, Celgard 2400 is barrier film, makes CR2032
Button cell, after standing 6h, on the LAND CT2001A charge-discharge test instrument of Wuhan charge discharge loop test is carried out, electricity
Pressure scope is 3.0～4.3V (vs.Li+/ Li), electric current is 24mAg-1.Electrochemical results are also summarised in table 1.
The LiMn2O4 of the synthesis of 1. embodiment of the present invention of table 1～5 and the size distribution and electrochemical performance data of control sample
The beneficial effects of the present invention is：By adding the niobium compound to LiMn2O4 with molten poly- effect in the feed,
So that LiMn2O4 powder particle size is grown up in high-temperature calcination process, finished-product material grading process is eliminated, reduce production work
Sequence, reduces production cost, has accomplished 100% utilization of electrolytic manganese dioxide；In addition, the mangaic acid synthesized using the inventive method
Lithium material size distribution is concentrated, specific surface area is low, excellent electrochemical performance.
Description of the drawings：
Fig. 1. the particle size distribution figure of sample prepared by the embodiment of the present invention 1, embodiment 2 and comparative example 1.Wherein, abscissa
For particle size, unit is：Micron (μm), ordinate is percentage by volume, and unit is：%.
Curve a is the particle size distribution figure of LiMn2O4 sample prepared by the embodiment of the present invention 1；
Curve b is the particle size distribution figure of LiMn2O4 sample prepared by the embodiment of the present invention 2；
Curve c is the particle size distribution figure of LiMn2O4 sample prepared by comparative example 1.
Specific embodiment：
In order to deepen the understanding to inventing, the present invention is further described below in conjunction with specific embodiment, the enforcement
Example is only limitted to the explanation present invention, does not constitute limiting the scope of the present invention.
Embodiment 1：
(1) by electrolytic manganese dioxide 1000g, lithium carbonate 220g and the niobium pentaoxide 1.53g (proportionate relationships of the amount of material
For Li:(Mn+Nb)=0.5:1, and Nb:Mn=0.001:1) it is added in ball mill and mixes 1h, obtains mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 860 DEG C of oxygen atmospheres
12h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, removed
The finished product lithium manganate material of fine powder.
Embodiment 2：
(1) by electrolytic manganese dioxide 1000g, lithium hydroxide 258g and niobium pentaoxide 15.3g, (ratio of the amount of material is closed
It is for Li:(Mn+Nb)=0.53:1, and Nb:Mn=0.01:1) it is added in ball mill and mixes 4h, obtains mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 750 DEG C of air atmospheres
50h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, removed
The finished product lithium manganate material of fine powder.
Embodiment 3：
(1) by electrolytic manganese dioxide 1000g, lithium carbonate 255g and niobium pentaoxide 23g, (proportionate relationship of the amount of material is
Li:(Mn+Nb)=0.58:1, and Nb:Mn=0.015：1) it is added in ball mill and mixes 6h, obtains mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 800 DEG C of air atmospheres
20h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, removed
The finished product lithium manganate material of fine powder.
Embodiment 4：
(1) by electrolytic manganese dioxide 1000g, lithium carbonate 231g and the niobium pentaoxide 7.65g (proportionate relationships of the amount of material
For Li:(Mn+Nb)=0.525:1, and Nb:Mn=0.005：1) it is added in ball mill and mixes 4h, obtains mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 770 DEG C of air atmospheres
30h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, removed
The finished product lithium manganate material of fine powder.
Embodiment 5：
(1) by electrolytic manganese dioxide 1000g, lithium carbonate 120g and lithium hydroxide 134g, niobium pentaoxide 15.3g (materials
Amount proportionate relationship be Li:(Mn+Nb)=0.54:1, and Nb:Mn=0.01:1) it is added in ball mill and mixes 6h, obtains
Mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 750 DEG C of oxygen atmospheres
30h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, removed
The finished product lithium manganate material of fine powder.
Comparative example 1：
(1) by electrolytic manganese dioxide 1000g, lithium carbonate 220g, (proportionate relationship of the amount of material is Li:Mn=0.5:1) add
Enter and mix 3h in ball mill, obtain mixture；
(2) step (1) gained mixture is loaded into saggar, in being put into electrothermal kiln, the roasting under 840 DEG C of oxygen atmospheres
12h, obtains product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove reunion bulky grain, that is, contrasted
LiMn2O4 sample.
Claims (3)
1. a kind of method that original position removes fine powder in manganic acid lithium electrode material, it is characterised in that comprise the steps：
(1) it is Li according to the ratio of lithium source material and the amount of the material of electrolytic manganese dioxide and niobium source material:(Mn+Nb)=0.50
～0.58:1, the ratio of the amount of the material of niobium source material and electrolytic manganese dioxide is Nb:Mn=0.001～0.015:1 will be above-mentioned
Lithium source material, niobium source material and electrolytic manganese dioxide mix 1～6 hour, obtain a homogeneous mixture；
(2) by gained mixture in step (1) under oxygen or air atmosphere in 750～860 DEG C of temperature ranges roasting 12～
50 hours, room temperature is naturally cooled to, obtain product of roasting；
(3) product of roasting is put in batch mixer and is well mixed, cross 325 mesh sieves, remove the bulky grain reunited, that is, obtain removing carefully
The LiMn2O4 finished-product material of powder.
2. preparation method according to claim 1, it is characterised in that lithium source material described in step (1) is lithium carbonate, hydrogen-oxygen
Change the one kind or its mixture in lithium.
3. preparation method according to claim 1, it is characterised in that niobium source material described in step (1) be niobium pentaoxide,
One or more in niobium hydroxide, niobium oxalate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090142255A1 (en) * | 2007-11-29 | 2009-06-04 | Korea Institute Of Geoscience And Mineral Resources | Lithium-manganese oxides, method for preparing the same, and lithium adsorbent using the same |
| CN101540399A (en) * | 2009-04-24 | 2009-09-23 | 济宁市无界科技有限公司 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
| CN102208643A (en) * | 2011-04-28 | 2011-10-05 | 河间市金鑫新能源有限公司 | Multi-element doped modified anode material for lithium ion power battery and preparation method thereof |
| CN102683669A (en) * | 2011-12-19 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Cathode material of lithium ion battery and preparation method of cathode material |
| CN102779993A (en) * | 2012-07-31 | 2012-11-14 | 临沂杰能新能源材料有限公司 | Lithium ion battery anode material and preparation method |
-
2016
- 2016-10-10 CN CN201610885380.0A patent/CN106629858A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090142255A1 (en) * | 2007-11-29 | 2009-06-04 | Korea Institute Of Geoscience And Mineral Resources | Lithium-manganese oxides, method for preparing the same, and lithium adsorbent using the same |
| CN101540399A (en) * | 2009-04-24 | 2009-09-23 | 济宁市无界科技有限公司 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
| CN102208643A (en) * | 2011-04-28 | 2011-10-05 | 河间市金鑫新能源有限公司 | Multi-element doped modified anode material for lithium ion power battery and preparation method thereof |
| CN102683669A (en) * | 2011-12-19 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Cathode material of lithium ion battery and preparation method of cathode material |
| CN102779993A (en) * | 2012-07-31 | 2012-11-14 | 临沂杰能新能源材料有限公司 | Lithium ion battery anode material and preparation method |
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Application publication date: 20170510 |