A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece
Technical field
The present invention relates to lithium cell cathode material recycling fields, and in particular to the present invention relates to a kind of scrap lithium ion batteries
The recoverying and utilizing method of graphite cathode piece.
Background technology
Lithium rechargeable battery is as good electric energy carrier, and because it has voltage high, specific capacity is big, and cyclicity is good, nothing
The advantages that memory effect, is widely used in the fields such as electronic product, electric vehicle and aerospace, becomes the mankind and realizes from biography
Fossil fuel unite to one of cleaning, environmental protection and optimal selection of regenerative resource transition.In recent years, with global lithium ion battery
The fast development of industry, production capacity increase year by year, and data are shown according to the statistics of State Statistics Bureau, Chinese lithium ion battery in 2013
Total output be about 47.68 hundred million, increase by 16.9% on a year-on-year basis.During lithium ion battery industrialized mass production, due to
Its package technique is one extremely complex with stringent technique, many battery manufacture enterprises can because slurry agitation, pole coating, point
It cuts and slips up with the processes such as tab welding and cap sealed and sub-standard product is caused to occur, disqualification rate is about production
10%~20%, so while lithium battery production capacity constantly rises, also imply that corresponding a large amount of defective work needs to locate
Reason.At present, the recycling of metal has formed the technological process of industrialization in lithium ion battery, with cobalt, nickel, manganese etc. in positive electrode
Based on the cycling and reutilization of element and negative current collector copper sheet, including the technologies such as mechanically decoupled, hydrometallurgy and pyrometallurgy, and
The recovery technology of negative material is still not perfect, and the lithium ion battery negative material of negative material Current commercial is mainly artificial stone
Ink, native graphite and various modified graphites, are typically only capable to be discarded or high temperature incineration is handled, but such way not only adds
The acute dust pollution and greenhouse effects of air, and cause a large amount of wasting of resources.
At present, also there is relevant report for the recycling of graphite negative material of lithium ion battery, such as 201410331563.9 stones
Negative material regeneration method in the unqualified lithium ion battery of black system can only recycle graphite material, and method is complicated,
Cost recovery is high;Patent application CN102051484A discloses a kind of recycling available substances on defective cathode piece of lithium battery
Method first cleans pole piece, then crushes, and with the coated substance on pure water stirring and dissolving substrate, then makes dispersion
Negative material in aqueous solution carries out separation of solid and liquid with copper foil, finally uses the mode of feed supplement to obtain satisfactory coating
Use negative electrode slurry.In the preparation process of lithium ion battery, each component content and proportioning are all what there are strict requirements, but are used
Between the negative material that this method is obtained, wherein negative electrode active material, conductive agent, binding agent and thickener, the content of each component
It is all difficult to measure and control with proportioning, so as to increase the unstability factor in lithium ion battery production, affect every
The consistency of batch products electrical property.And patent application CN101944644A discloses a kind of lithium ion battery negative material
Recovery method, the object of processing be the leftover pieces and non-compliant pole piece that are generated in lithium ion battery production process or
The non-compliant negative electrode slurry that link generates is stirred in lithium battery manufacturing process, makes to glue using the method for high-temperature baking first
Knot agent is decomposed and is lost activity, and then cathode powder can naturally come off from collector, and finally mixture is sieved
To obtain qualified negative material.The high-temperature baking of this method carries out under neither anoxic nor oxygen-enriched atmosphere, heating temperature
It is 400-600 DEG C, soaking time 5-50min, in this baking process, although binding agent can lose work due to oxygenolysis
Property, so as to fulfill the natural separation of cathode powder and copper foil, but thickener CMC-Na and binding agent butadiene-styrene rubber are above-mentioned
At a temperature of there is no completely decompose, also small part remains among negative material and the purity of graphite material is caused to decline.Cause
This, there is no the volatilization situations for comprehensively considering each component for this method, have certain limitation so as to cause its technological process.
It, first will be negative with organic solvent if patent application CN101154757A discloses a kind of recovery method of battery negative pole carbon material
Pole material is dipped to copper foil to be detached, and is then carried out high-temperature process to negative material, can be obtained after cooling and meet production requirement
Carbon material.High-temperature process in this method carries out under non-oxidizing gas protection, and heating temperature is 500-750 DEG C, heat preservation
Time is 1-24 hours, in this high-temperature processing technology, although organic matter, such as CMC-Na, butadiene-styrene rubber, it can be abundant
Ground is cracked and is volatilized, but is inevitably generated pyrolysis product-carbon residue of organic matter, and the conductive agent in negative material-
Acetylene black is that amorphous carbon and clad hard carbon are not decomposed in non-oxidizing atmosphere yet, so being obtained with the method
The carbon material obtained is actually the mixture of a kind of graphite and amorphous carbon, is not to be suitable for negative electrode of lithium ion battery to prepare use
High purity graphite, if this raw material used as battery material, will necessarily because impurity there are due to cause material gram volume
Decline.As patent application CN103346365A discloses one kind from waste and old lithium ion battery to negative material circular regeneration
The restorative procedure of the method utilized, wherein negative electrode active material is to use graphitization processing technology, lazy at 1400-2600 DEG C
Property atmosphere in negative material is purified, soaking time 5-24h, after cooling through screening obtain the cathode material of recoverable
Material.At graphited temperature, on the one hand, the organic matter in negative material can be cracked fully, and their generations are amorphous
Part can also be converted into the graphite with Patterns for Close-Packed Hexagonal Crystal structure to the carbon residue of structure at high temperature.On the other hand, graphite material
Crystal defect caused by after multiple charge and discharge can also be repaired in this process.But due in negative material
Conductive agent acetylene black be difficult graphitized carbon, i.e., the carbon materials of graphite may not can be also converted at a high temperature of 2500 DEG C or more
Material, institute can not thoroughly solve the problems, such as graphite and carbon blending in recycling negative material, and graphitization technique pair in this way
The requirement of equipment is harsh, energy consumption is high, expensive, is unfavorable for application and popularization that waste and old graphite recycles industry.
Existing technical disadvantages in a word:
1st, the recycling purity of copper is low in graphite negative electrode of lithium ion battery piece;
2nd, treatment process is cumbersome, and processing speed is slow, low production efficiency.
Invention content
The purpose of the present invention is to provide a kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece, by with
Lower scheme is realized:
A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece, including step:A is crushed, and passes through superfine powder
Broken machine crushes raw material, the material particular diameter after crushing<20μm;B, it detaches, the powder after crushing is passed through into the whirlwind on pulverizer
Separator obtains the different blister copper powder of density and rubble ink powder;C, blister copper powder is handled, and will be passed through containing the copper powder of 2% graphite powder impurity
2-8 cyclonic separation is crossed, obtains 99.9% copper powder;D, rubble ink powder is handled, and rubble ink powder is dissolved in the solution containing acid, is led to
It crosses centrifuge and obtains graphite wet feed, then dried by baker, obtain cathode of lithium battery graphite powder.
The raw material be leftover pieces in lithium cell cathode material production process, the lithium battery graphite cathode piece scrapped and
Graphite cathode piece any that is disassembled after waste lithium cell recycling and more than.
The blister copper powder 98% copper powder+2% graphite powder big for density, rubble ink powder 99% graphite powder small for density+
1% copper powder.
The acid-containing solution is 1%-30% hydrochloric acid, sulfuric acid solution.
The temperature of the baker is 100-200 DEG C.
Graphite wet feed gets final cathode of lithium battery graphite powder by nixing sieve after drying.
The advantage of the invention is that:
It 1st, can be thick by copper powder and graphite with cyclonic separation by crushing using the not high characteristic of graphite and copper foil attachment degree
Powder separates, and then can be increased to 99.9% the recycling purity of copper from 80%, substantially increase copper by simple thin processing
Economic value;
2nd, processing procedure is simple, and processing speed is fast, is 5-6 times of conventional method.
Description of the drawings
Fig. 1 is flow chart of the method for the present invention.
Specific embodiment
Following embodiment is further details of to illustrate the present invention, but the invention is not limited in this embodiments.
Embodiment 1
A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece, including step:A is crushed, and passes through superfine powder
Broken machine crushes the lithium battery graphite cathode piece scrapped, the material particular diameter after crushing<20μm;B, it detaches, by the powder after crushing
The different blister copper powder of density and rubble ink powder are obtained by the cyclone separator on pulverizer;Wherein blister copper powder is that density is big
98%+2% graphite powder of copper powder, rubble ink powder 99% graphite powder+1% copper powder small for density;C, blister copper powder is handled, and will contain 2%
The copper powder of graphite powder impurity passes through 5 cyclonic separations, obtains 99.9% copper powder;D, rubble ink powder is handled, and rubble ink powder is dissolved in
Solution containing acid, obtains graphite wet feed by centrifuge, is then dried by baker, then mixes and sieves, and obtains lithium electricity
Pond negative pole graphite powder.
Embodiment 2
A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece, including step:A is crushed, and passes through superfine powder
Broken machine crushes the leftover pieces in lithium cell cathode material production process, the material particular diameter after crushing<20μm;B, it detaches, by powder
Powder after broken obtains the different blister copper powder of density and rubble ink powder by the cyclone separator on pulverizer;Wherein blister copper powder is
98% big+2% graphite powder of copper powder of density, rubble ink powder 99% graphite powder+1% copper powder small for density;C, blister copper powder is handled,
By the copper powder containing 2% graphite powder impurity by 8 cyclonic separations, 99.9% copper powder is obtained;D, rubble ink powder is handled, by rubble
Ink powder is dissolved in the solution containing acid, obtains graphite wet feed by centrifuge, is then dried by baker, then mixes and sieves,
Obtain cathode of lithium battery graphite powder.
Embodiment 3
A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode piece, including step:A is crushed, and passes through superfine powder
The graphite cathode piece that broken machine is disassembled after waste lithium cell is recycled crushes, the material particular diameter after crushing<20μm;B, it detaches, by powder
Powder after broken obtains the different blister copper powder of density and rubble ink powder by the cyclone separator on pulverizer;Wherein blister copper powder is
98% big+2% graphite powder of copper powder of density, rubble ink powder 99% graphite powder+1% copper powder small for density;C, blister copper powder is handled,
By the copper powder containing 2% graphite powder impurity by 3 cyclonic separations, 99.9% copper powder is obtained;D, rubble ink powder is handled, by rubble
Ink powder is dissolved in the solution containing acid, obtains graphite wet feed by centrifuge, is then dried by baker, then mixes and sieves,
Obtain cathode of lithium battery graphite powder.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.