A kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode sheet
Technical field
The present invention relates to lithium cell cathode material and reclaim field, be specifically related to the recoverying and utilizing method that the present invention relates to a kind of scrap lithium ion battery graphite cathode sheet.
Background technology
Lithium rechargeable battery is as good electric energy carrier, because of it, to have voltage high, specific capacity is large, cyclicity is good, the advantages such as memory-less effect, be widely used in the fields such as electronic product, electric motor car and Aero-Space, become the mankind and realize one of optimal selection from conventional fossil fuel to clean, environmental protection and regenerative resource transition.In recent years, along with the fast development of global lithium ion battery industry, its production capacity increases year by year, and according to State Statistics Bureau's statistics display, the total output of Chinese lithium ion battery in 2013 is about 47.68 hundred million, increases by 16.9% on a year-on-year basis.In the process of lithium ion battery industrialized mass production, because its packaging technology is very complicated with a strict technique, a lot of battery manufacture enterprise can because of slurry agitation, pole coating, cut and slip up with the operation such as tab welding and cap sealed and cause sub-standard product to occur, disqualification rate is about 10% ~ 20% of production, so while lithium battery production capacity constantly rises, also mean that corresponding a large amount of defective item needs process.At present, in lithium ion battery, the recovery of metal has formed the technological process of industrialization, with cobalt in positive electrode, nickel, the cycling and reutilization of the elements such as manganese and negative current collector copper sheet is main, comprise machinery to be separated, the technology such as hydrometallurgy and pyrometallurgy, and the recovery technology of negative material also imperfection, the lithium ion battery negative material of negative material Current commercial is mainly Delanium, native graphite and various modified graphite, usually can only go out of use or high temperature incineration process, but such way not only exacerbates dust pollution and the greenhouse effect of air, and cause a large amount of wastings of resources.
At present, the recovery for graphite negative material of lithium ion battery also has relevant report, as negative material regeneration method in the defective lithium ion battery of 201410331563.9 graphite systems, can only reclaim graphite material, and method is complicated, and cost recovery is high; Patent application CN102051484A discloses a kind of method reclaiming available substances on defective cathode piece of lithium battery, first pole piece is cleaned, then broken, and with the on-chip coated substance of pure water stirring and dissolving, make dispersion negative material in aqueous and Copper Foil carry out Separation of Solid and Liquid again, finally adopt the mode of feed supplement to obtain satisfactory coating cathode size.In the preparation process of lithium ion battery, each constituent content and proportioning are all what there are strict requirements, but adopt the negative material that this method obtains, wherein negative electrode active material, conductive agent, between binding agent and thickener, the content of each component and proportioning are all difficult to measure and control, thus the unsteadiness factor added in lithium ion battery production, have impact on the consistency of every batch products electrical property.And patent application CN101944644A discloses a kind of recovery method of lithium ion battery negative material, process to as if lithium ion battery production process in the leftover pieces that produce and non-compliant pole piece, or stir the non-compliant cathode size that link produces in lithium battery manufacture process, first the method for high-temperature baking is adopted to make binder decomposed and lose activity, then negative pole powder just naturally can come off from collector, finally sieves to obtain qualified negative material to mixture.The high-temperature baking of the method carries out under the atmosphere of neither anoxic also not oxygen enrichment, heating-up temperature is 400-600 DEG C, temperature retention time is 5-50min, in this baking process, although binding agent can lose activity because of oxidation Decomposition, thus realize the natural separation of negative pole powder and Copper Foil, but thickener CMC-Na and binding agent butadiene-styrene rubber do not decompose completely at above-mentioned temperature, also have small part to remain in and cause the purity of graphite material to decline among negative material.Therefore, the method does not consider the volatilization situation of each component all sidedly, thus causes its technological process to have certain limitation.As patent application CN101154757A discloses a kind of recovery method of battery negative pole carbon material, first with organic solvent negative material is dipped to Copper Foil and is separated, then anticathode material carries out high-temperature process, can obtain the material with carbon element meeting production requirement after cooling.High-temperature process in the method is carried out under non-oxidizing gas protection, heating-up temperature is 500-750 DEG C, temperature retention time is 1-24 hour, in this high-temperature processing technology, although organic substance, as CMC-Na, butadiene-styrene rubber etc., can cracking and volatilizing fully, but inevitably produce organic pyrolysis product-carbon residue, and the conductive agent-acetylene black in negative material is amorphous carbon, and coating layer hard carbon does not decompose in non-oxidizing atmosphere yet, so be actually the mixture of a kind of graphite and amorphous carbon with the material with carbon element that this method obtains, be not be applicable to high purity graphite prepared by lithium ion battery negative, if this raw material is used as battery material, the decline of material gram volume will inevitably be caused because of the existence of impurity.As patent application CN103346365A discloses a kind of method of anticathode material circulation regeneration from waste and old lithium ion battery, wherein the restorative procedure of negative electrode active material adopts graphitization processing technology, in inert atmosphere at 1400-2600 DEG C, anticathode material carries out purifying, temperature retention time is 5-24h, obtains the negative material of recoverable after cooling through screening.At graphited temperature, on the one hand, the organic substance in negative material can cracking fully, and their produce impalpable structure carbon residue at high temperature part also can be converted into the graphite with Patterns for Close-Packed Hexagonal Crystal structure.On the other hand, the crystal defect that graphite material causes after repeatedly discharge and recharge also can be repaired in this process.But, because the conductive agent acetylene black in negative material is difficult graphitized carbon, namely the material with carbon element of graphite may not be also converted under the high temperature more than 2500 DEG C, thoroughly can not solve in this way and reclaim the blended difficult problem of graphite and carbon in negative material, and graphitization technique harsh to the requirement of equipment, consume energy high, cost intensive, is unfavorable for application and the popularization of waste and old graphite recycling industry.
Existing technical disadvantages in a word:
1, in graphite negative electrode of lithium ion battery sheet, the recovery purity of copper is low;
2, treatment process is loaded down with trivial details, and processing speed is slow, and production efficiency is low.
Summary of the invention
The object of the present invention is to provide a kind of recoverying and utilizing method of scrap lithium ion battery graphite cathode sheet, realized by following scheme:
A recoverying and utilizing method for scrap lithium ion battery graphite cathode sheet, comprises step: a pulverizes, and is pulverized by raw material, the material particular diameter <20 μm after pulverizing by ultrafine crusher; B, separation, obtain the different blister copper powder of density and rubble ink powder by the powder after pulverizing by the cyclone separator on pulverizer; C, the process of blister copper powder, by the copper powder containing 2% graphite powder impurity through 2-8 cyclonic separation, obtain the copper powder of 99.9%; D, the process of rubble ink powder, be dissolved in the solution containing acid, obtain graphite wet feed, then dried by baker, obtain cathode of lithium battery graphite powder by centrifuge by rubble ink powder.
Described raw material be the leftover pieces in lithium cell cathode material production process, the lithium battery graphite cathode sheet scrapped and waste lithium cell reclaim after disassemble graphite cathode sheet any one and more than.
Described blister copper powder be density large 98% copper powder+2% graphite powder, rubble ink powder be density little 99% graphite powder+1% copper powder.
Described acid-containing solution is 1%-30% hydrochloric acid, sulfuric acid solution.
The temperature of described baker is 100-200 DEG C.
Graphite wet feed is divided obtained final cathode of lithium battery graphite powder by nixing sieve after drying.
The invention has the advantages that:
1, graphite and the not high characteristic of Copper Foil attachment degree is utilized, by pulverize and cyclonic separation by copper powder and graphite meal separately, then the recovery purity of copper from 80%, can be brought up to 99.9%, substantially increase the economic worth of copper through simple carefully process;
2, processing procedure is simple, and processing speed is fast, is 5-6 times of conventional method.
Accompanying drawing explanation
Fig. 1 is method flow diagram of the present invention.
Embodiment
The further detailed description the present invention of following examples, but the present invention is not limited to this embodiment.
Embodiment 1
A recoverying and utilizing method for scrap lithium ion battery graphite cathode sheet, comprises step: a pulverizes, and is pulverized by the lithium battery graphite cathode sheet scrapped, the material particular diameter <20 μm after pulverizing by ultrafine crusher; B, separation, obtain the different blister copper powder of density and rubble ink powder by the powder after pulverizing by the cyclone separator on pulverizer; Wherein blister copper powder be density large 98% copper powder+2% graphite powder, rubble ink powder be density little 99% graphite powder+1% copper powder; C, the process of blister copper powder, by the copper powder containing 2% graphite powder impurity through 5 cyclonic separation, obtain the copper powder of 99.9%; D, the process of rubble ink powder, be dissolved in the solution containing acid, obtain graphite wet feed, then dried by baker, then mix and sieve, obtain cathode of lithium battery graphite powder by centrifuge by rubble ink powder.
Embodiment 2
A recoverying and utilizing method for scrap lithium ion battery graphite cathode sheet, comprises step: a pulverizes, and is pulverized by the leftover pieces in lithium cell cathode material production process, the material particular diameter <20 μm after pulverizing by ultrafine crusher; B, separation, obtain the different blister copper powder of density and rubble ink powder by the powder after pulverizing by the cyclone separator on pulverizer; Wherein blister copper powder be density large 98% copper powder+2% graphite powder, rubble ink powder be density little 99% graphite powder+1% copper powder; C, the process of blister copper powder, by the copper powder containing 2% graphite powder impurity through 8 cyclonic separation, obtain the copper powder of 99.9%; D, the process of rubble ink powder, be dissolved in the solution containing acid, obtain graphite wet feed, then dried by baker, then mix and sieve, obtain cathode of lithium battery graphite powder by centrifuge by rubble ink powder.
Embodiment 3
A recoverying and utilizing method for scrap lithium ion battery graphite cathode sheet, comprises step: a pulverizes, and the graphite cathode sheet disassembled after being reclaimed by waste lithium cell by ultrafine crusher is pulverized, the material particular diameter <20 μm after pulverizing; B, separation, obtain the different blister copper powder of density and rubble ink powder by the powder after pulverizing by the cyclone separator on pulverizer; Wherein blister copper powder be density large 98% copper powder+2% graphite powder, rubble ink powder be density little 99% graphite powder+1% copper powder; C, the process of blister copper powder, by the copper powder containing 2% graphite powder impurity through 3 cyclonic separation, obtain the copper powder of 99.9%; D, the process of rubble ink powder, be dissolved in the solution containing acid, obtain graphite wet feed, then dried by baker, then mix and sieve, obtain cathode of lithium battery graphite powder by centrifuge by rubble ink powder.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.