CN107601494A - A kind of graphite cathode material purification process - Google Patents
A kind of graphite cathode material purification process Download PDFInfo
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- CN107601494A CN107601494A CN201710792704.0A CN201710792704A CN107601494A CN 107601494 A CN107601494 A CN 107601494A CN 201710792704 A CN201710792704 A CN 201710792704A CN 107601494 A CN107601494 A CN 107601494A
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- graphite cathode
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Abstract
The invention discloses a kind of graphite cathode material purification process, comprise the following steps：To removing Ferromagnetic Impurities through magnetic separation after the raw material crushing of unpurified graphite cathode material, again it is screened granularity is classified and carries out selection by winnowing respectively remove the wherein heavier impurity of proportion, then add a small amount of sour and remaining impurity and acidification reaction occurs, through press filtration depickling and add water sedimentation layering and overflow hydraulic classiciation to handle the impurity after removing layering, most obtain the raw material after purification process after centrifugal concentrating and drying process afterwards.The present invention can shorten the purification reaction time, reduce chemical reagent usage amount, reduce production cost, greatly reduce the consumption to water resource and the generation of acidic industrial effluent, and application is strong, is adapted to industrialization promotion.
Description
Technical field
The present invention relates to graphite cathode material technology for producing field, and in particular to a kind of graphite cathode material purifying side
Method.
Background technology
Mainly the negative material by the use of graphite microparticles as its conductive negative pole, its granularity are generally situated between lithium rechargeable battery at present
In 3 μm~30 μm.Graphite cathode material needs raw material carrying out purification process during preparation is produced, and removes in raw material
Impurity component, its impurity component mainly include metal, metal oxide and nonmetallic and nonmetal oxide, mainly included
Fe、Fe2O3、FeO、Al2O3、CuO、S、SiO2Deng.
Existing graphite cathode material purification treating method is mainly using the method for chemical reaction, by being added into raw material
Acid makes impurity and acid reaction, then is washed by clear water, and removes the impurity of chemical reaction and the acid solution of residual and chemical reagent,
Make raw material pH value for neutrality.But the processing of acid adding reaction purification is directly carried out to graphite cathode material and problems be present：First,
The problem of impurity inside graphite raw material is difficult to fully contact with acid reaction liquid, especially block and particle agglomeration raw material,
Cause impurity in raw material and acid reaction not thorough and reaction time increase, and chemical time occupy it is entirely pure
Change most times of processing procedure；Second, reaction needs to use substantial amounts of highly acid chemical reagent, a large amount of chemical reagent
Increased using production cost is caused；3rd, after being handled using acid reaction the raw material of graphite cathode material, generally require again
The strong acid reaction solution remained in reactant is rinsed using substantial amounts of clear water, to remove wherein acid chemical composition until
Untill reactant is in neutrality, 30~40 tons of clear water need to be consumed by often rinsing 1 ton of raw material of processing according to statistics, and this processing mode consumes
Substantial amounts of water resource simultaneously causes the generation of a large amount of acidic industrial effluents.
The content of the invention
The technical problem to be solved in the present invention is that the technical problem to be solved in the present invention is to provide a kind of graphite cathode material
Purification process, to solve：Impurity when graphite cathode material produces inside raw material is difficult to fully contact with acid causes reaction not thorough
The problem of increase in bottom and reaction time；Chemical levels cause greatly the problem of production cost increase；Consumption is big when washing acid
The problem of measuring water resource.
In order to solve the above technical problems, the present invention uses following technology path：
The method being combined from physical purification method with chemical purification method, the raw material of graphite cathode material is carried out at purifying
Reason, is first crushed raw material with physical method, and this is advantageous to follow-up process and fully removes impurity in raw material, including removes former
Impurity inside material, recycle magnetic separation to remove ferromagnetic impurity, then further carry out grain-size classification using screening, it is then right
The raw material of sorted different grain size section carries out selection by winnowing processing respectively, be vortexed using wind-force remove granularity in each granularity section it is identical but
The larger impurity of proportion.To the small part impurity in raw material, then the method using chemistry, using acidification reaction, need to only add few
The acid of amount, you can make remaining impurity that acidification reaction occur with acid, the method for recycling press filtration depickling, remove most acid
Liquid, it is well mixed with water, and adds dispersant, carry out sedimentation layering, the addition of wherein dispersant is advantageous to impurity and original
Expect the separation of particle and follow-up layering, then handled from overflow, hydraulic classiciation processing is carried out to the material after layering, removed
Impurity after layering, obtained material are the raw slurry after purification process, then carry out centrifugal concentrating dehydration and drying to it
After processing, the graphitization negative material raw material after purification process and grading is produced.
Detailed technology scheme is as follows：
A kind of graphite cathode material purification process is designed, is comprised the following steps：
（1）Physical handles raw material：
A. the raw material of unpurified graphite cathode material is crushed, makes its granularity≤30 μm；
B. broken rear resulting material is subjected to magnetic separation processing under strong magnetic field action；
C. the material after magnetic separation is subjected to screening process；
D. the material after screening process is subjected to grain-size classification by size distribution；
E. the material after grain-size classification is subjected to selection by winnowing processing respectively；
（2）Chemical Treatment raw material：
A. step E resulting materials are respectively placed in reactor, add water and stir, while be slowly uniformly added into acid and be acidified instead
Should；
B. the slurry material after acidification reaction is pumped into progress press filtration depickling processing in filter press；
C. add water to stir in resulting material input reactor after press filtration depickling is handled, while add and disperse into reactor
Agent；
D. the material being well mixed in reactor is stood, carries out waterpower sedimentation layering；
E. the material after being layered will be settled and carry out waterpower overflow size separation processing；
F. classification processing upper strata graphite raw material layer slurries are taken to carry out centrifugal concentrating and drying process.
Preferably, crush in step A and handled comprising break process and milling, break process selects kibbler roll, is milled
Raymond mill is selected in processing.
Preferably, step B medium-high magnetic fields magnetic field intensity is 0.3~0.5T, and the magnet of high-intensity magnetic field is forever used in magnetic separation processing
Magnetic magnet.
Preferably, screening process selects high frequency shale shaker in step C, the vibration frequency of high frequency shale shaker for 8000~
10000Hz。
Preferably, stirring is batch type in step a, and each mixing time is 10~20 minutes, every time stirring interval
Time is 30~60 minutes.
Preferably, acid is sulfuric acid in step a, and sulphuric acid is the 3%~10% of material in reactor quality.
Preferably, reactor material is polytetrafluoroethylene (PTFE) in step a.
Preferably, dispersant is one kind in CMC, PAC, SHMP in step c, and the addition of dispersant is at press filtration depickling
The 0.1%~0.5% of resulting material quality after reason.
Preferably, step c reclaimed waters are pure water, and the adding proportion of pure water is in mass ratio gains after press filtration depickling processing
Material：Water=1:1~5, the μ S/cm of pure water conductivity≤1.
Preferably, the time that layering is settled in step d is 1~5 hour.
The advantageous effects of the present invention are：
1. the present invention uses the methods of crushing, sieve, be scattered so that impurity thoroughly and is easy to separate with raw material with acid reaction, and
Used by the method for magnetic separation and selection by winnowing physical purification, reduce chemical time.
2. the method that the present invention uses physical bond chemical purification, purifying chemical reagent usage amount reduces more than 80%, drop
Low production cost.
3. present invention purifying water consumption greatly reduces, starting material with water amount≤5 ton per ton are purified, greatly reduce water resource
Consumption, and reduce the generation of acidic industrial effluent.
4. the grain size distribution that the raw material of grading of the present invention is also beneficial in follow-up graphite cathode material production process is excellent
Change is handled, and facility is provided for follow-up graphite cathode material grain size distribution production process.
5. the purity of raw material its carbon after purification process of the present invention is high, up to more than 99%, and pH value is in neutrality, between
Between 6.5~7.5, beneficial to follow-up industrialized production.
6. this method application of the present invention is strong, it is highly suitable for the industrialization promotion of graphite cathode material manufacturing enterprise.
Embodiment
Illustrate the embodiment of the present invention with reference to embodiment, but following examples are used only to describe in detail
The present invention, the scope not limiting the invention in any way.Involved instrument and equipment is as without especially in the examples below
Illustrate, be routine instrument device；The involved raw material of industry is commercially available regular industrial raw material unless otherwise instructed；It is involved
And processing method, be conventional machining preparation method unless otherwise instructed.
Embodiment 1
A kind of graphite cathode material purification process, comprises the following steps：
Physical method handles raw material：
（1）First the raw material of unpurified graphite cathode material is crushed, i.e., first broken raw material in kibbler roll
Broken processing, then will it is broken after material grinding processing is carried out in Raymond mill, make its granularity≤30 μm.
（2）Again by step（1）Resulting material carries out magnetic in the case where magnetic field intensity is 0.3~0.5T strong magnetic field action after broken
Choosing is handled, and wherein the magnet of high-intensity magnetic field used in magnetic separation is permanent-magnet, has the miscellaneous of ferromagnetic characteristic to remove in impurity
Matter.
（3）By step（2）Material after magnetic separation is sieved in the high frequency shale shaker that vibration frequency is 8000~10000Hz
Manage office.
（4）Material after screening process is subjected to grain-size classification by size distribution, can be divided into three classes, i.e. particulate class, equal grain
Class, coarse grain class, its corresponding particle size range is respectively 1~5 μm, 5~15 μm, 15~30 μm.
（5）Material after grain-size classification is subjected to selection by winnowing processing respectively, using impurity in the case of same particle sizes proportion compared with
The characteristics of big, in wind-force scroll fluid environment, further remove the impurity in material.
Raw material is handled using the method for above physics, in raw material more than 80% impurity can be removed.Wherein granularity
The raw material of classification is also beneficial to the grain size distribution optimization processing in follow-up graphite cathode material production process.
Embodiment 2
A kind of graphite cathode material purification process, comprises the following steps：
Chemical method handles raw material：
（1）Resulting material after selection by winnowing in embodiment 1 is respectively placed in the reactor that material is polytetrafluoroethylene (PTFE), and added thereto
Enter water and stir so that material is well mixed with water, slowly uniform into reactor while stirring to add thing in reactor
Expect that 3%~10% sulfuric acid of quality carries out acidification reaction, wherein stirring is batch type, each mixing time is 10~20 points
Clock, every time stirring are spaced 30~60 minutes.Whole acidificatoin time is 3~6 hours.
（2）Slurry material after acidification reaction is pumped into progress press filtration depickling processing in filter press, removes acid therein
Liquid, the acid solution clearance through press filtration depickling processing is up to more than 95%.
（3）In the resulting material input reactor after press filtration depickling and the μ S/cm of electrical conductivity≤1 pure water will be added carry out again
Stirring, and material is well mixed with water, stirring adds dispersant carboxymethyl cellulose into reactor simultaneously（CMC）, wherein
Pure water adding proportion in mass ratio is depickling resulting material：Water=1:（1~5）, institute after dispersant addition is handled for press filtration depickling
Obtain the 0.1%~0.5% of material quality.
（4）Stop stirring, make step（3）Well mixed material carries out waterpower sedimentation layering, sedimentation point in a kettle
The layer time is 1~5 hour, and its upper strata is graphite raw material layer, and bottom is the larger unreacted impurity layer of proportion.
（5）The material after layering will be settled and carry out waterpower overflow size separation processing, and by slurries obtained by the graphite raw material layer of upper strata
It is the graphite cathode material raw material after purification process to carry out centrifugal concentrating and drying process, gained.
Using the purity of raw material its carbon after this method purification process up to more than 99%, pH value in neutrality, between 6.5~
Between 7.5.
Embodiment 3
A kind of graphite cathode material purification process, difference from Example 2 be, step（3）Middle dispersant from it is poly- it is cloudy from
Subbundle element（PAC）.
Embodiment 4
A kind of graphite cathode material purification process, difference from Example 2 be, step（3）Middle dispersant selects six inclined phosphorus
Sour sodium（SHMP）.
The present invention is described in detail above in conjunction with embodiment, still, person of ordinary skill in the field can
Understand, on the premise of present inventive concept is not departed from, each design parameter in above-described embodiment can also be changed, shape
Into multiple specific embodiments, it is common excursion of the invention, is no longer described in detail one by one herein.
Claims (10)
1. a kind of graphite cathode material purification process, it is characterised in that comprise the following steps：
（1）Physical handles raw material：
A. the raw material of unpurified graphite cathode material is crushed, makes its granularity≤30 μm；
B. the broken rear resulting material is subjected to magnetic separation processing under strong magnetic field action；
C. the material after the magnetic separation is subjected to screening process；
D. the material after the screening process is subjected to grain-size classification by size distribution；
E. the material after the grain-size classification is subjected to selection by winnowing processing respectively；
（2）Chemical Treatment raw material：
A. step E resulting materials are respectively placed in reactor, add water and stir, while be slowly uniformly added into acid and be acidified instead
Should；
B. the slurry material after the acidification reaction is pumped into progress press filtration depickling processing in filter press；
C. will resulting material is put into the reactor after press filtration depickling processing plus water stirs, while to the reaction
Dispersant is added in kettle；
D. the material being well mixed in the reactor is stood, carries out waterpower sedimentation layering；
E. the material after the sedimentation layering is subjected to waterpower overflow size separation processing；
F. the classification processing upper strata graphite raw material layer slurries are taken to carry out centrifugal concentrating and drying process.
2. graphite cathode material purification process according to claim 1, it is characterised in that described in step to crush bag
Handled containing break process and milling, the break process selects kibbler roll, and Raymond mill is selected in the milling processing.
3. graphite cathode material purification process according to claim 1, it is characterised in that the high-intensity magnetic field in stepb
Magnetic field intensity is 0.3~0.5T, and the magnet of high-intensity magnetic field is permanent-magnet used in the magnetic separation processing.
4. graphite cathode material purification process according to claim 1, it is characterised in that described in step C at screening
Reason selects high frequency shale shaker, and the vibration frequency of the high frequency shale shaker is 8000~10000Hz.
5. graphite cathode material purification process according to claim 1, it is characterised in that described in step a stirring be
Batch type, each mixing time are 10~20 minutes, and it is 30~60 minutes to stir interval time every time.
6. graphite cathode material purification process according to claim 1, it is characterised in that acid is sulphur described in step a
Acid, the sulphuric acid are the 3%~10% of material in reactor quality.
7. graphite cathode material purification process according to claim 1, it is characterised in that the reactor described in step a
Material is polytetrafluoroethylene (PTFE).
8. graphite cathode material purification process according to claim 1, it is characterised in that the dispersant described in step c
For at least one of CMC, PAC, SHMP, the addition of the dispersant is resulting material quality after press filtration depickling processing
0.1%~0.5%.
9. graphite cathode material purification process according to claim 1, it is characterised in that the water described in step c is pure
Water, the adding proportion of the pure water is in mass ratio resulting material after press filtration depickling processing：Water=1:1~5, the pure water
The μ S/cm of electrical conductivity≤1.
10. graphite cathode material purification process according to claim 1, it is characterised in that the sedimentation point described in step d
The time of layer is 1~5 hour.
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| CN201710792704.0A CN107601494A (en) | 2017-09-05 | 2017-09-05 | A kind of graphite cathode material purification process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108706582A (en) * | 2018-06-27 | 2018-10-26 | 河南易成新能源股份有限公司 | The preparation method of artificial plumbago negative pole material |
| CN109775700A (en) * | 2019-02-13 | 2019-05-21 | 山东天岳先进材料科技有限公司 | The recycling of waste and old graphite crucible and high-purity carbon dust |
| CN111252761A (en) * | 2020-04-07 | 2020-06-09 | 内蒙古凯金新能源科技有限公司 | Purification method of graphite negative electrode material |
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| CN105811040A (en) * | 2016-05-16 | 2016-07-27 | 哈尔滨巴特瑞资源再生科技有限公司 | Method for smashing, detaching and recycling lithium battery |
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| CN101209836A (en) * | 2006-12-28 | 2008-07-02 | 深圳市比克电池有限公司 | Classification method for graphite material |
| CN105197920A (en) * | 2015-10-20 | 2015-12-30 | 辽宁工程技术大学 | Microcrystal graphite separation and purification method |
| CN105811040A (en) * | 2016-05-16 | 2016-07-27 | 哈尔滨巴特瑞资源再生科技有限公司 | Method for smashing, detaching and recycling lithium battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108706582A (en) * | 2018-06-27 | 2018-10-26 | 河南易成新能源股份有限公司 | The preparation method of artificial plumbago negative pole material |
| CN109775700A (en) * | 2019-02-13 | 2019-05-21 | 山东天岳先进材料科技有限公司 | The recycling of waste and old graphite crucible and high-purity carbon dust |
| CN111252761A (en) * | 2020-04-07 | 2020-06-09 | 内蒙古凯金新能源科技有限公司 | Purification method of graphite negative electrode material |
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