CN106830106A - A kind of method for removing lithium ion battery ternary material precursor impurity - Google Patents
A kind of method for removing lithium ion battery ternary material precursor impurity Download PDFInfo
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- CN106830106A CN106830106A CN201710178686.7A CN201710178686A CN106830106A CN 106830106 A CN106830106 A CN 106830106A CN 201710178686 A CN201710178686 A CN 201710178686A CN 106830106 A CN106830106 A CN 106830106A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2006/80—Compositional purity
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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
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Abstract
A kind of method of lithium ion battery ternary material precursor impurity washing, lithium ion battery ternary material precursor slurry is obtained and stands and settles coprecipitation is layered described slurry, releases supernatant and is precipitated slurry；2) to organic solvent is slowly added in resulting precipitate slurry, after producing crystalline material, crystalline material to separate out completely at once, standing completes to form crystal grain to crystal growth, and by the mixture solution filtration drying of gained, filtrate reclaims organic solvent recycling；Described organic solvent with arbitrary proportion with water can be dissolved each other one or more in alcohol, aldehyde, ketone；3) presoma in the solid mixture obtained by 2) step filtration drying is separated admittedly with described crystal grain, that is, obtains the ternary precursor after impurity elimination.Be one kind can improve product quality, solve the problems, such as in forerunner's production procedure Impurity removal not thoroughly and environmental pressure is big, and process is simply, effect is good, easy-operating method.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to one kind removal lithium ion battery ternary material precursor
The method of impurity.
Background technology
New-energy automobile is the direction of future automobile development, and electrokinetic cell to be new-energy automobile be different from conventional fuel oil vapour
The important component of car.Tertiary cathode material turns into because of having the advantages that energy density is high, environment-friendly, cheap
Focus of concern.It can be by high temperature solid-state method, sol-gal process, spray drying process, hydro-thermal method and co-precipitation
The serial of methods such as method synthesize.And wherein coprecipitation to material in atomic level due to that can synthesize, and can control
Appearance structure, tap density of prepared material etc., are widely used in the industrial production.
In conventional co-precipitation preparation process, what is synthesized first is the presoma of ternary material, wherein before hydroxide
Drive body most commonly seen.Reacted in the presence of complexing agent by the soluble salt and highly basic precipitating reagent of metallic element, before generation
Drive body.The most frequently used soluble metallic salt is sulfate, and highly basic is NaOH, substantial amounts of so as to exist in reaction system
Na+With SO4 2-.Due to their solubility, so as to be typically all industrially after the completion of reaction with substantial amounts of deionized water to it
Carry out washing impurity elimination.According to knowhow, the number of times of washing at least needs more than three times, and presoma per ton needs that washs to use water
Amount needs several tons, and these water finally all become industrial wastewater, and recovery value is low, and processing cost is high.Meanwhile, a small amount of Na+With
SO4 2-It is wrapped in precipitation particle, and is difficult to wash away, the Na of hundreds to thousands ppm is remained in final products+With SO4 2-It is miscellaneous
Matter, the final follow-up properties of product for being prepared into ternary anode material for lithium-ion batteries of influence.
The content of the invention
The purpose of the present invention aim to provide one kind can improve product quality, solve forerunner's production procedure in Impurity removal not
Thoroughly and the big problem of environmental pressure, and process is simple, effect it is good, it is easy-operating it is a kind of remove lithium ion battery ternary material before
The method for driving body impurity.
Technical scheme is comprised the following steps：
1)：Lithium ion battery ternary material precursor slurry is obtained and stands and settles coprecipitation makes described slurry point
Layer, releases supernatant and is precipitated slurry；
2) to organic solvent is slowly added in resulting precipitate slurry, white crystalline material, white crystals are produced at once
After material is separated out completely, standing is completed to form crystal grain to crystal growth, and by the mixture solution filtration drying of gained, filtrate is reclaimed
Organic solvent is reused；Described organic solvent with arbitrary proportion with water can to dissolve each other a kind of or several in alcohol, aldehyde, ketone
Kind；
3) presoma in the solid mixture obtained by 2) step filtration drying is separated admittedly with described crystal grain, that is, is obtained
Ternary precursor after impurity elimination.
The solution of the present invention by ternary material precursor feed liquid add can with water with arbitrary proportion dissolve each other alcohol,
In aldehyde, ketone after the organic solvent of one or more, stand and solid separate method impurity elimination；Each step of the scheme more than
Rapid collaboration treatment may be such that substantial amounts of impurities in water element (the particularly Na for being dissolved in slurry+And SO4 2-) analysed with precipitating crystalline
Go out, then the crystal of precipitation is grown up by standing process, until can be separated admittedly.The solution of the present invention can be solved effectively
Process is cumbersome in presoma impurity washing process in existing forerunner's production procedure, and environmental pressure is big, and Impurity removal is not thorough etc.
Problem, and the solution of the present invention due to process it is simple, it is easy to operate, be advantageous to process of industrialization.
Wherein, step 1) in, described ternary anode material precursor is preferably Ni1-x-yCoxMy(OH)2, wherein, 0<x<
1,0<y<1, M is Mn, Al, Ti, Cr, Fe, Zn or Cu etc..Particle diameter is 1~30um.
While inventors have also discovered that, in order to reach more preferable separating effect, preferably, described organic solution is first
Alcohol, ethanol, ethylene glycol, glycerine, formaldehyde, acetaldehyde or acetone.
In order that foreign ion is fully separated out and reaches certain particle diameter, described step 2) in, the organic solvent of addition
It is 0.5 with the volume ratio of described precipitate slurry:1~2:1 is advisable.
In order that foreign ion is preferably separated with ternary precursor, as it is further preferably, addition it is organic
Solvent is 1 with the volume ratio of described precipitate slurry:1~2:1.
Wherein, step 2) in, the time of standing is 8~15h.
The inventors discovered that, standing process is also one of committed step of the invention, and crystal can be with by standing after separating out
Crystal is gradually grown up, it is separated with presoma such that it is able to pass through more simple solid-solid separation method.
The present invention passes through research and finds, the implementation result good in order to obtain the present invention program, by controlling time of repose,
And crystal grain particle diameter should be controlled to be not less than 50 μm under conditions of organic solvent and the volume ratio of described precipitate slurry.
Wherein, step 2) in, all along with mechanical agitation during adding organic solvent process and standing.
The inventors discovered that, after being filtered to mixture solution, organic solvent can be returned by the method distilled
Receive then reapply to above the step of in, which save the usage amount of organic solvent, such that it is able to reach save production
The purpose of cost.
Wherein, step 2) in, described drying temperature is 60~80 DEG C.
Wherein, step 3) in, described solid-solid separation method including vibrosieve from or pneumatic separating etc..
The inventors discovered that, in order to reach more preferable separating effect, further preferably, vibratory sieve is separated into more preferably.
Traditional impurity-removing method is that simple utilization deionized water is rinsed to presoma, and the effect of washing is poor, washes
The efficiency washed is low, and needs by repeatedly washing, and not only while serious waste of resources, impurity-eliminating effect is not still thorough.And this hair
Bright method can not only be reused to resource, and also will not bring new impurity into presoma.Compared to the prior art, originally
The content of main water-solubility impurity drops to below 100ppm in invention, and the utilization ratio of resource is high.To sum up, institute of the present invention
The method of the lithium ion battery ternary material precursor impurity washing stated, process is simple, operating process is short, low cost, washing effect
Fruit thoroughly, has been effectively promoted the industrialized production of presoma.
Brief description of the drawings
Fig. 1 be embodiment 1 obtain washed with ethanol after the presoma Ni that obtains0.8Co0.1Mn0.1(OH)2SEM figure.
Specific embodiment
Embodiment 1：
The spherical ternary cathode material presoma Ni after 48h will be reacted0.8Co0.1Mn0.1(OH)2(average grain diameter for~
It is layered after 8h is stood after 12um) being released from reactor, releases supernatant and be precipitated slurry.Take 500ml slurries and slowly stir
Mix, be slowly added to 500ml ethanol, the sediment for constantly having white is separated out, after lasting stirring stands 10h, it is filtered
Dried at a temperature of 60 DEG C, presoma is then separated into the presoma after being washed with white crystals impurity using vibratory sieve.
The presoma SEM figures dried after washing are shown in Fig. 1, Na and S content analysis, presoma are carried out to presoma by ICP
Na contents be 98mg/kg, the content of S is 30ppm for the content of 0.015%, Fe, and the content of Ca is 9ppm, and the content of Mg is
The content of 26ppm, Zn is 7ppm, and the content of Pb is 3ppm, and the content of Cu is 15ppm.
Embodiment 2：
The spherical ternary cathode material presoma Ni after 36h will be reacted0.8Co0.15Al0.05(OH)2(average grain diameter for~
It is layered after 8h is stood after 9um) being released from reactor, releases supernatant and be precipitated slurry.Take 500ml slurries and slowly stir
Mix, be slowly added to 1000ml methyl alcohol, the sediment for constantly having white is separated out, after lasting stirring stands 12h, it is filtered
Dried at a temperature of 80 DEG C, presoma is then separated into the presoma after being washed with white crystals impurity using vibratory sieve.
By ICP to Na and S content analysis, the Na contents of presoma are 84mg/kg to the presoma dried after washing, S's
Content is that the content of 0.009%, Fe is 26ppm, and the content of Ca is 18ppm, and the content of Mg is 17ppm, and the content of Zn is 3ppm,
The content of Pb is 4ppm, and the content of Cu is 7ppm.
Comparative example 1：
The spherical ternary cathode material presoma Ni after 36h will be reacted0.8Co0.15Al0.05(OH)2(average grain diameter for~
It is layered after 8h is stood after 9um) being released from reactor, releases supernatant and be precipitated slurry.Take 500ml slurries and slowly stir
Mix, be slowly added to 1000ml methyl alcohol, the sediment for constantly having white is separated out, and then it is filtered and is dried at a temperature of 80 DEG C
It is dry, using vibratory sieve by the presoma after presoma and the isolated washing of partial white crystalline impurities.
Without being stood, filter effect is excessively poor, while crystal is not grown up, causes most crystal cannot
Separated with presoma.By ICP to Na and S content analysis, the Na contents of presoma are the presoma dried after washing
The content of 204ppm, S is 36ppm for the content of 0.073%, Fe, and the content of Ca is 20ppm, and the content of Mg is 16ppm, Zn's
Content is 5ppm, and the content of Pb is 9ppm, and the content of Cu is 12ppm.
Claims (10)
1. it is a kind of remove lithium ion battery ternary material precursor impurity method, it is characterised in that comprise the following steps：
1) lithium ion battery ternary material precursor slurry is obtained and stands and settles coprecipitation is layered described slurry, puts
Go out supernatant and be precipitated slurry；
2) to organic solvent is slowly added in resulting precipitate slurry, crystalline material, crystalline material is produced to separate out completely at once
Afterwards, stand and complete to form crystal grain to crystal growth, by the mixture solution filtration drying of gained, filtrate is reclaimed organic solvent and repeated
Utilize；Described organic solvent with arbitrary proportion with water can be dissolved each other one or more in alcohol, aldehyde, ketone；
3) presoma in the solid mixture obtained by 2) step filtration drying is separated admittedly with described crystal grain, that is, obtains impurity elimination
Ternary precursor afterwards.
2. the method that lithium ion battery ternary material precursor impurity according to claim 1 is washed, it is characterised in that step
It is rapid 1) in, described ternary anode material precursor is Ni1-x-yCoxMy(OH)2, wherein, 0<x<1,0<y<1, M be Mn, Al, Ti,
Cr, Fe, Zn or Cu, particle diameter are 1~30 μm.
3. the method that a kind of lithium ion battery ternary material precursor impurity according to claim 1 is washed, its feature exists
In it is to be reused organic solvent by the method distilled that filtrate is reclaimed.
4. method according to claim 1, it is characterised in that step 2) in, the organic solvent of addition and described precipitation
The volume ratio of slurry is 0.5:1~2:1.
5. method according to claim 1, it is characterised in that step 2) in the organic solvent and described slurry that add
Precipitation volume ratio is 1:1~2:1.
6. method according to claim 1, it is characterised in that step 2) in, the time of standing is 8~15h.
7. the method according to claim any one of 1-6, it is characterised in that step 2) in, add organic solvent process with
All along with mechanical agitation during standing.
8. the method according to claim any one of 1-7, it is characterised in that by controlling time of repose and organic solvent
Cause that crystal grain particle diameter is not less than 50 μm with the volume ratio of described precipitate slurry.
9. method according to claim 1, it is characterised in that step 2) in, described drying temperature is 60~80 DEG C.
10. method according to claim 1, it is characterised in that step 3) in, it is described it is solid be separated into admittedly vibrosieve from
Or pneumatic separating.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067224A (en) * | 1991-04-22 | 1992-12-23 | 田纳科加拿大分公司 | The metathesis of the acidic by-products of chlorine dioxide production technology |
| CN102531222A (en) * | 2010-12-09 | 2012-07-04 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method for vanadium precipitating waste water |
| CN103247780A (en) * | 2013-04-18 | 2013-08-14 | 河南科隆新能源有限公司 | Positive pole material for lithium ion battery and preparation method of positive pole material |
| CN103545503A (en) * | 2012-07-17 | 2014-01-29 | 河南科隆集团有限公司 | Preparation method of low iron content ternary precursor |
| CN105070903A (en) * | 2015-07-21 | 2015-11-18 | 深圳市贝特瑞新能源材料股份有限公司 | Ternary cathode material precursor, preparation method and application thereof |
-
2017
- 2017-03-23 CN CN201710178686.7A patent/CN106830106B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067224A (en) * | 1991-04-22 | 1992-12-23 | 田纳科加拿大分公司 | The metathesis of the acidic by-products of chlorine dioxide production technology |
| CN102531222A (en) * | 2010-12-09 | 2012-07-04 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method for vanadium precipitating waste water |
| CN103545503A (en) * | 2012-07-17 | 2014-01-29 | 河南科隆集团有限公司 | Preparation method of low iron content ternary precursor |
| CN103247780A (en) * | 2013-04-18 | 2013-08-14 | 河南科隆新能源有限公司 | Positive pole material for lithium ion battery and preparation method of positive pole material |
| CN105070903A (en) * | 2015-07-21 | 2015-11-18 | 深圳市贝特瑞新能源材料股份有限公司 | Ternary cathode material precursor, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杜柯等: "碳酸盐共沉淀法制备Li[Li0.2Co0.13Ni0.13Mn0.54]O2中加料方式对产物性能的影响", 《无机化学学报》 * |
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