CN109777957A - A kind of solvent compositions and leaching separation method suitable for discarding lithium battery material leaching separation - Google Patents
A kind of solvent compositions and leaching separation method suitable for discarding lithium battery material leaching separation Download PDFInfo
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- CN109777957A CN109777957A CN201811622709.XA CN201811622709A CN109777957A CN 109777957 A CN109777957 A CN 109777957A CN 201811622709 A CN201811622709 A CN 201811622709A CN 109777957 A CN109777957 A CN 109777957A
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The solvent that the present invention relates to a kind of suitable for discarding lithium battery material leaching separation forms and the method for solvent recovery, the main extracting solvent composition includes hydrocarbon R134a, R124a, R123a, R406a of single component, while the mixed solution formed after miscible in any proportion including the compound.Extracting solvent of the present invention suitable for discarding electrolyte recycling lithium battery, the method for being particularly suitable for leaching recycling lithium battery electrolytes.The method of the solvent composition of binder and recycling residual solvent in leaching separation lithium battery of the present invention, it is particularly suitable for adding any one composed mixed solvent in secondary solvent NMP, DMAC, DMF, DMSO, the method for being particularly suitable for separation and recovery secondary solvent in R134a, R124a, R123a, R406a solvent.Using nontoxic, the non-ignitable characteristic of extracting solvent, the situation that solvent loss is big, energy consumption is high, environmentally friendly, hidden fire-fighting danger is big is effectively relieved existing for conventional method.
Description
Technical field
The present invention relates to discarded lithium battery valuable material reclaiming fields, specifically, are related to a kind of suitable for discarded
The solvent compositions and leaching separation method of lithium battery material leaching separation.
Background technique
In recent years, with the fast development of electric car and extensive energy storage market, the yield of lithium-ion-power cell
The quantity of rapid growth therewith, the applying waste lithium ionic power battery of generation shows increasing for explosion type.Applying waste lithium ionic power
Containing non-ferrous metal elements in short supply such as a large amount of cobalt, lithium, nickel, manganese, copper, aluminium in battery, simultaneously containing electrolyte (DMC), electrolysis
Poisonous and harmful substances, the electrode materials of lithium battery such as matter lithium hexafluoro phosphate, binder Kynoar (PVDF) once enter ring
In border, heavy metal ion, organic matter, carbon dust, fluoride in battery etc. will likely cause serious environmental pollution.Wherein,
Positive electrode will cause heavy metal pollution, polluted-water and soil；Negative electrode material can cause dust pollution；Electrolyte can cause fluorine
Pollution and organic pollution；Diaphragm material will cause white pollution.Moreover, the loss of the valuable metals such as copper, nickel, cobalt, manganese, lithium
It also will cause the waste of resource, therefore, resource utilization carried out to it and harmless treatment is of great significance.
Currently, the recycling and reuse problem of lithium-ion-power cell has become whole society's focus of attention.Ensure to give up
Used batteries specification recycles and safe disposal, realizes that circular economy and sustainable development have far reaching significance to China.
Domestic applying waste lithium ionic power battery recycling, there are bottleneck, hinders back in all various aspects such as law, channel, technology
It closes the fast development of field, power battery recycling business is in planning and starting stage on the whole.
It is affected by this, the recovery process route of China's lithium-ion-power cell is many and diverse, existing theoretical research and industrialization
Application case, overview get up to be broadly divided into the following three steps: pre-processing, secondary treatment and advanced treating.Specific method is summarized
It is as follows: one, pre-treatment step: usually all to there is remaining electricity in applying waste lithium ionic power battery, therefore in recovery processing electricity
Before pond, need to carry out discharge treatment to battery.In addition, the electrolyte that contains in lithium-ion-power cell meet water can generate it is toxic
HF.In view of this, recycling lithium battery should be pre-processed suitably first, eliminate potential dangerous.Pre-treatment step is main
Inert gas shielding process including infusion method or electric-resistivity method deep discharge process and broken link.The above method is row
Well known to industry, used by prevailing technology.Secondary treatment step: the purpose of secondary treatment step is to realize that lithium battery is positive and negative
Pole active material is kept completely separate with copper aluminium pole piece, and currently used method has pyrogenic process thermal decomposition, organic solvent dissolution method, soda acid
Liquid dissolution method and electrolysis method.Wherein, pyrogenic process thermal decomposition is at a temperature of broken battery fragment is placed in 380 DEG C~500 DEG C,
Binder PVDF is promoted to volatilize or decompose, to realize the separation of positive and negative pole material Yu copper aluminium foil pole piece.Pyrogenic process thermal decomposition process
Simply, easy to operate, binder PVDF can be effectively removed.But thermal decomposition process necessarily leads to a large amount of toxic and harmful gas,
If absorption cleaning is improper, easily cause serious secondary pollution.Organic solvent dissolution method is that one kind efficiently separates positive and negative anodes material
The method of material and copper aluminium foil is subtracted by the interaction between organic solvent N-Methyl pyrrolidone (NMP) and binder PVDF
Cohesive force between weak material and paillon, promotes material to fall off from paillon.But due to such solvent incendivity and boiling point is equal
Greater than 200 DEG C, under usual conditions, the dissolvent residual of lithium battery positive and negative pole material, copper aluminium foil and frosting attachment can not be returned
It receives, inevitably forms hidden fire-fighting danger and secondary pollution.Acid & alkali liquid dissolution method is that broken battery is placed in NaOH solution first
In, wherein pole piece aluminium foil can be dissolved in lye, and copper foil does not react with alkali；Copper foil, carbon powder material after alkali is soaked exist
It calcines under high temperature or is dissolved in organic matter, so that PVDF is decomposed or is dissolved, acidleach then is carried out to residue, realize active material
Separation.This method cannot completely remove PVDF, unfavorable to subsequent leaching；The intervention of acid-base solution simultaneously, necessarily to production
Environment, water body environment, air environment pollute；In addition, this method needs to consume a large amount of acid, aqueous slkali, generated after dissolution
A large amount of AlO2-1, also it is unfavorable for the separating-purifying of consequent activities material.Electrolysis method refers to that, using stereotype as anode, anode is
Cathode, electrolyte is sulfuric acid solution, under the action of extra electric field, impacts anode using the hydrogen generated in electrolytic process, real
Existing positive electrode falls off, while recycling aluminium foil.This method can be realized the separation of positive electrode and aluminium foil, obtain pure aluminium
Foil, while can also promote part positive electrode converting and be present in electrolyte for ionic species, it is convenient for subsequent processing.But it lacks
Point is that power consumption is big, and electrolytic efficiency is low；Waste sulfate needs to carry out harmless treatment；The hydrogen that electrolytic process generates, makes to give birth to
Producing environment, there are hidden fire-fighting dangers.Advanced treating step: advanced treating step mainly includes the lithium battery active for obtaining preceding step
Material leaches by " hydrometallurgy " technique, separates the metal salt for being converted into nickel, cobalt, lithium, is Remanufacture lithium battery active
The presoma of material creates conditions.The process and the present invention do not have relevance, no longer illustrate.
In conclusion industry Existing methods, can achieve separation impurity, the purpose of lithium battery active material is leached, but not
All have that energy consumption is high, soda acid loss is big, environmental pollution hidden danger is big, fires the big common problem of risk with degree, thus
Constrain the industrial application process of discarded lithium battery material recycling and reusing.
Summary of the invention
The present invention provides a kind of for discarded dynamic lithium battery for deficiency existing for traditional power lithium battery recovery process
The solvent composing method of leaching, separation, while solving leaching process or being separated after leaching, the method for recycling design.
The technical scheme to solve the above technical problems is that
The present invention provides a kind of solvent compositions suitable for discarding lithium battery material leaching separation, the solvent compositions
Including for leaching the extracting solvent of electrolyte in discarded lithium battery material and being used in the discarded lithium battery material of leaching separation glue
The secondary solvent of agent is tied, the boiling point of the extracting solvent is lower than the boiling point of secondary solvent.
Further, the extracting solvent is hydrocarbon, including tetrafluoroethane (R134a), a chloro-tetrafluoroethane (R-
124a), at least one of dichlorotrifluoroethane (R123a), R-406a；The secondary solvent includes N-Methyl pyrrolidone
(NMP), at least one of N- dimethyl acetamide (DMAC), dinethylformamide (DMF), dimethyl sulfoxide (DMSO).
The beneficial effects of the present invention are: a kind of solvent or solvent group suitable for discarding lithium battery material leaching, separation
Object is closed, mainly for the leaching of lithium battery electrolytes；Secondly, solvent combination meets the leaching of lithium battery binder, to recycle again
Raw valuable metal nickel, cobalt, lithium, manganese, copper, aluminium create conditions；In addition, repeat to leach and evaporate recycling by the combination solvent,
Lithium battery leaching object and electrolyte, binder and dissolvent residual in residue are sufficiently eliminated on the harm of environment and influence.
The hydrocarbon of the extracting solvent selected using nontoxic, non-ignitable, boiling point lower than 0 DEG C is object, including tetrafluoroethane
(R134a), at least one of a chloro-tetrafluoroethane (R-124a), dichlorotrifluoroethane (R123a), R-406a, wherein it is preferred that
Tetrafluoroethane (R134a).The selecting of secondary solvent normally produces the solvent necessarily referred to as object using lithium battery enterprise, general character
First is that boiling point is above 150 DEG C, including N-Methyl pyrrolidone (NMP), N- dimethyl acetamide (DMAC), N- dimethyl methyl
At least one of amide (DMF), dimethyl sulfoxide (DMSO), wherein it is preferred that N-Methyl pyrrolidone (NMP).
The extracting solvent can be mutually immiscible with secondary solvent, the variation of mixed proportion and order of addition, only influences this
The extraction velocity and cost of patent, it is uncorrelated to leaching effect.
It is gaseous state that wherein structure is the extracting solvent of hydrocarbon at normal temperatures and pressures, but in item of the present invention
In use, being for liquid under part.Secondary solvent is in a liquid state at normal temperatures and pressures, with hydrocarbon cosolvent it is miscible after, it is close
Vapour-liquid coexisting state is presented in the mixed solvent closed in container；The variation of temperature, pressure condition, solvent group are controlled according to this patent
Conjunction can convert between steam state and liquid.
The present invention also provides a kind of discarded lithium battery material leaching separation methods, are suitable for discarded lithium battery using above-mentioned
The solvent compositions of material leaching separation, comprising the following steps:
1) it will discharge, the appropriate closed container of broken discarded lithium battery material loading, vacuumize, then addition leaching is molten
Agent is leached under stirring, is separated by filtration later, respectively obtains the first insoluble solid and the first leaching mixed liquor；
2) the first leaching mixed solution heating fractionation for obtaining step 1), respectively obtains extracting solvent and electrolyte；
3) extracting solvent and secondary solvent, 20 DEG C~50 DEG C temperature are added into the first insoluble solid that step 1) obtains
Persistently stirring leaching in range；The second insoluble solid and the second mixing leaching liquid are respectively obtained after being separated by filtration；
4) the second insoluble solid addition extracting solvent obtained to step 3), leaches under lasting stirring；Filtering
Third insoluble solid and third leaching mixed liquor are obtained after separation；
5) step 4) is obtained into third insoluble solid heat drying, steam condensing reflux is obtained into extracting solvent；It will be complete
The further physical separation of third insoluble solid of white drying obtains lithium battery solid material；
6) the second obtained mixing leaching liquid of merging step 3) and the third mixing leaching liquid 4) obtained, lasting stirring add
Heat, fractionation, respectively obtains extracting solvent, secondary solvent and binder mixtures；
7) collection step 6) obtained secondary solvent is for being recycled；Collect and merge step 2), step 5) and step
6) extracting solvent obtained is for recycling.
Wherein, in above-mentioned steps, the step of step 2 and step 3 are after step 1, the two can not had simultaneously
There is a sequencing, the step of step 5 and step 6 are after step 4, the two can carry out no sequencing simultaneously.
Lithium battery solid material in the step 5 includes positive and negative anodes active material, copper, aluminium foil and the plastics of lithium battery.
Binder mixtures in the step 6 include PVDF plastics and dispersing agent.Second insoluble solid and leaching in the step 3
The solid, liquid volume ratio of solvent is 1:1 to 1:2, and leaching time is 20-60 minutes, and leaching temperature is 20 DEG C~50 DEG C.
Further, which is characterized in that in the step 1), discard the solid, liquid volume ratio of lithium battery material and extracting solvent
For 1:1 to 1:2, leaching time is 20~60 minutes, and leaching temperature is 20~50 DEG C；Operating pressure 0.8MPa to 1.35MPa, weight
Leaching number is 1-2 times again.
Further, in the step 3), the mixed volume ratio of extracting solvent and secondary solvent is 1:1, mixed solvent with
The volume ratio of first insoluble solid is 1:2；Leaching condition are as follows: 20 DEG C~50 DEG C of leaching temperature, operating pressure 0.8MPa~
1.35MPa, leaching time are 20~60min, repeat to leach number to be 1~2 time.
Further, the leaching condition of step 4) are as follows: 20 DEG C to 50 DEG C of leaching temperature, operating pressure 0.8MPa to 1.35MPa,
Leaching time is 20-60min, repeats to leach number to be 1-2 times.
Further, the evaporation conditions of extracting solvent are recycled in the step 2), step 5) are as follows: gauge pressure -0.08MPa is extremely
1.4MPa, 30 DEG C -60 DEG C of temperature；Termination condition are as follows: vacuum degree gauge pressure reaches -0.08 to -0.09Mpa in closed container, continues
Pressure maintaining 5 minutes.
Further, the evaporation conditions of extracting solvent are recycled in step 6) are as follows: pressure -0.08MPa to 1.4MPa, temperature 30
℃-60℃；Termination condition are as follows: vacuum degree gauge pressure reaches -0.08 to -0.09Mpa in closed container, continues pressure maintaining 5 minutes；Recycling
The evaporating temperature of nmp solution is 120 DEG C to 180 DEG C, and continuous vacuum degree gauge pressure is -0.06 to -0.09MPa.
Further, the extracting solvent include hydrocarbon tetrafluoroethane, a chloro-tetrafluoroethane, dichlorotrifluoroethane and
At least one of R-406a；The secondary solvent includes N-Methyl pyrrolidone, N- dimethyl acetamide, N- dimethyl formyl
At least one of amine, dimethyl sulfoxide.
The beneficial effect of discarded lithium battery material leaching separation method of the invention is: being suitable for discarding using above-mentioned
The solvent compositions of lithium battery material leaching separation, to the binder and positive and negative pole material, copper foil, aluminium foil, plastics in lithium battery
Separation, while including recycling, cycling and reutilization extracting solvent, secondary solvent, the method for avoiding environmental hazard.
The main extracting solvent composition includes hydrocarbon R134a, R124a, R123a, R406a of single component, together
When include the mixed solution formed after the compound is miscible in any proportion.It is of the present invention suitable for discarded lithium battery
The extracting solvent of electrolyte recycling, the method for being particularly suitable for leaching recycling lithium battery electrolytes.Leaching point of the present invention
From in lithium battery binder solvent composition and recycling residual solvent method, be particularly suitable for R134a, R124a, R123a,
Any one composed mixed solvent in secondary solvent NMP, DMAC, DMF, DMSO is added in R406a solvent, it is especially suitable
Method for separating and recovering secondary solvent.Extracting solvent of the present invention is not only suitable for leaching and recycles in discarded lithium battery
Electrolyte, while be suitable for leaching separation lithium battery contained by binder, to make lithium battery positive and negative anodes active material and copper aluminium
Pole piece is removed.The present invention was both mutually melt and dissolved using different leaching solvents, and boiling point has the characteristic of larger difference again, in low consumption
Under the conditions of energy, realize mixed solvent efficiently separate and recycling and reusing.In addition, using nontoxic, the non-ignitable characteristic of leaching solvent,
The situation that solvent loss is big, energy consumption is high, environmentally friendly, hidden fire-fighting danger is big is effectively relieved existing for conventional method.
Detailed description of the invention
Fig. 1 is the flow chart of discarded lithium battery material leaching separation method of the invention；
Fig. 2 is the leaching of electrolyte and the partial process view of recycling design in discarded lithium battery of the invention；
Fig. 3 is that solvent compositions of the invention leach the partial process view of binder and recycling design in lithium battery；
Fig. 4 is the partial process view of dissolvent residual in recycling insoluble solid object of the invention；
Fig. 5 is the part details flow chart of recycling secondary solvent of the invention.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
The present invention provides a kind of solvent compositions suitable for discarding lithium battery material leaching separation, the solvent compositions
Including for leaching the extracting solvent of electrolyte in discarded lithium battery material and being used in the discarded lithium battery material of leaching separation glue
The secondary solvent of agent is tied, the boiling point of the extracting solvent is lower than the boiling point of secondary solvent.
Further, the extracting solvent be hydrocarbon tetrafluoroethane (R134a), a chloro-tetrafluoroethane (R-124a),
At least one of dichlorotrifluoroethane (R123a), R-406a；The secondary solvent includes N-Methyl pyrrolidone (NMP), N-
At least one of dimethyl acetamide (DMAC), dinethylformamide (DMF), dimethyl sulfoxide (DMSO).
A kind of discarded lithium battery material leaching separation method is suitable for discarded lithium battery material leaching separation using described
Solvent compositions, comprising the following steps:
1) it will discharge, the appropriate closed container of broken discarded lithium battery loading, and vacuumize exclusion on-condensible gas, then press
The solid, liquid volume ratio of 1:1 to 1:2 adds extracting solvent R134a, is warming up to 20 DEG C -50 DEG C, lasting to stir, and makes the electricity in raw material
Solution liquid be sufficiently diffused into R134a solvent, leaching 20-60 minute after, be separated by filtration solid, liquid, obtain the first insoluble solid with
First leaching mixed liquor；
2) in appropriate closed container, the first leaching solution heating that step 1) is obtained is kept for 30 DEG C -60 DEG C of temperature,
Wherein, R134a solvent can persistently be evaporated in gauge pressure -0.08MPa to 1.4Mpa range；When vacustat reaches in closed container
Gauge pressure -0.08 is continued above 5 minutes to -0.09Mpa range, illustrates that R134a has evaporated completely；Due to electrolyte carbonic acid diformazan
The boiling point of ester is 90.1 DEG C, and in 30 DEG C of -60 DEG C of temperature ranges, electrolyte remains unchanged to be separated and recovered；
R134a steam is converted into liquid after condensation, and cycle applications are in subsequent leaching process.
3) extracting solvent R134a is added into the first insoluble solid that step 1) obtains, while being added in claim 2
The secondary solvent NMP is persistently stirred in 20 DEG C of -50 DEG C of temperature ranges, and mixed solvent can leach the viscous of dissolved solid surface
Tie agent；It repeats this step 1-2 times, the binder PVDF in lithium battery, which can be immersed, to be taken entirely；It is separated by filtration consolidating in closed container
Body and liquid respectively obtain the second insoluble solid and the second mixing leaching liquid；
4) for the mixed solvent residue of the second insoluble solid surface attachment, step 3) is obtained second insoluble
Solid adds extracting solvent R134a by the solid, liquid volume ratio of 1:1 to 1:2, is warming up to 20 DEG C -50 DEG C, continues under stirring
Leaching 20-60 minutes；It is separated by filtration solid, liquid, obtains third insoluble solid and third leaching mixed liquor.
5) in closed container, step 4) is obtained into third insoluble solid continuous heating, evaporation, condensing recovery solid table
The remaining R134a solvent in face, makes its cycle applications in subsequent leaching process.
So far, third insoluble solid removes binder and extracting solvent completely, main composition be lithium battery just
Loose mixture form is presented in negative electrode active material, copper foil, aluminium foil, iron-clad, plastics, using the known method of industry
It is separated and is recycled.
6) second, third mixing leaching liquid for merging step 3), 4) obtaining, it is lasting to stir in appropriate closed container, it protects
30 DEG C of -60 DEG C of ranges of temperature are held, R134a solvent is made persistently to parse evaporation in gauge pressure -0.08Mpa to 1.4Mpa range；When closed
Vacustat reaches gauge pressure -0.08 to -0.09Mpa range in container, and the duration is more than 5 minutes, illustrates that R134a has evaporated
It is completely separated completely and with nmp solution；
Since the boiling point of secondary solvent NMP is 203 DEG C, in 30 DEG C of -60 DEG C of temperature ranges, nmp solvent keeps liquid condition
Constant, R134a the solvent analysis is that steam is separated both to make.
7) in closed container, gauge pressure -0.08 is evacuated to -0.09Mpa range, heating stepses 6) obtained NMP is mixed
Close solution, persistently overheating to 120 DEG C or more, preferred temperature is 150 DEG C, make liquid NMP parsing evaporation and with dissolve it is therein
Mixture is kept completely separate；Condensing recovery nmp solvent steam enables nmp solvent circulation for subsequent production；
Include mainly binder PVDF plastics and dispersing agent in mixture after removing solvent, passes through the known method of industry
It can carry out secondary use.
8) it collects, merge the R134a solvent that step 2), step 5), step 6) obtain, cycle applications were leached in subsequent
Journey.
Based on the above technical solution, the present invention can also be improved as follows:
Further, extracting solvent can be added in the step 1) by the solid, liquid volume ratio of 1:2 to 1:3, leaching number increases
It adds as 2-3 times.
Further, claim 2 can first be added into the first insoluble solid that step 1) obtains in the step 3)
Described in secondary solvent, persistently stir at room temperature, be then added extracting solvent, the bonding on collaboration leaching dissolved solid surface
Agent, and repeat this step 3-4 times；
Further, in the step 7), persistently overheating it can make liquid nmp solvent to 203 DEG C or more in closed container
Parsing evaporation is simultaneously kept completely separate with mixture therein is dissolved.
Embodiment 1
Extracting solvent chooses solvent R134a, and secondary solvent chooses NMP.
As shown in Fig. 2, electric discharge, broken lithium battery material being packed into appropriate closed container, vacuumized, gauge pressure is-
0.06 to -0.08Mpa, exclude the on-condensible gas inside container；
Solvent R134a is added in closed container, solvent adds 1 to 2 times that volume is lithium battery material volume, heating
To 20 DEG C -50 DEG C, 1.0 to 1.4Mpa are boosted to, stirring leaching 20-60 minutes, electrolyte is substantially dissolved in R134a solvent；
The filtration system inside container is opened, makes penetration by liquid strainer to separate with solid, respectively obtains lithium battery
The leaching mixed liquor and the first insoluble solid of liquid are solved, leaching, filtering 1-2 times is repeated, soaks the electrolyte in solid completely
It takes；
In closed container, by the leaching mixed liquor continuous heating of electrolyte to 30 DEG C -60 DEG C, R134a is from mixed liquor
Parsing evaporation, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa from 1.4Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is cooling to be turned
Liquid is turned to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches table
Pressing -0.08 to -0.09Mpa range is more than 5 minutes, shows that R134a has evaporated completely.Due to the boiling point of electrolyte dimethyl carbonate
It is 90.1 DEG C, cannot be evaporated in 30 DEG C of -60 DEG C of ranges, so that mixed liquor be made to be separated into electrolyte and R134a solvent, electrolyte is obtained
To abundant recycling.
As shown in Fig. 3, in closed container, R134a solvent and the nmp solvent injection the of about 50% volume ratio will respectively be accounted for
One insoluble solid material, the total volume of injected mixed solvent are about 1 to 2 times of solid material volume；It is warming up to 20 DEG C -50
DEG C, 0.8Mpa to 1.4Mpa is boosted to, stirring leaching 20-60 minutes is substantially dissolved in the binder PVDF in solid material
In the mixed solvent；
Filtration system is opened, makes the penetration by liquid strainer inside container to separate with insoluble solid, obtains the second leaching
Take mixed liquor and the second insoluble solid.Leaching, filtering 1-2 times is repeated, leaches binder completely；
In closed container, by the second leaching mixed liquor continuous heating to 30 DEG C -60 DEG C, R134a solvent is from mixed liquor
Parsing evaporation, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa from 1.4Mpa；
Start vacuum pump and compressor, the R134a steam of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that R134a has evaporated completely.Since the boiling point of nmp solvent is 203 DEG C, 30
DEG C -60 DEG C of ranges cannot evaporate, so that mixed liquor be made to be separated into nmp solution and R134a solvent.
As shown in Fig. 4, in closed container, solvent R134a is added to the second insoluble solid material, additive amount is about
1 to 2 times of insoluble solid material volume；Stirring 20-60 minutes, the residual nmp solvent for adhering to solids surface sufficiently expand
It is dispersed in R134a in the mixed solvent；
The filtration system inside container is opened, makes penetration by liquid strainer to separating with insoluble solid, respectively obtains the
Three mixed solutions and third insoluble solid object.Leaching, filtering 1-2 times is repeated, keeps solids nmp solvent remained on surface complete
Full leaching；
In closed container, by third insoluble solid material continuous heating to 30 DEG C -60 DEG C, R134a solvent is from solid
Surface parsing evaporation；With the continuity of evaporation process, the pressure inside container drops to 0.2Mpa from 1.4Mpa；
Start vacuum pump and compressor, the R134a steam of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that R134a has evaporated completely.Container bottom discharge valve is opened, is obtained completely
Remove the lithium battery material of electrolyte and binder.The material using the known method of industry it is available separation, recycling and again
It is raw.
As shown in Fig. 5, second, third leaching mixed solvent is merged in closed container, persistently overheating is to 30 DEG C -60
DEG C, R134a solvent parses evaporation from mixed liquor；With the continuity of evaporation process, the pressure inside container declines from 1.4Mpa
To 0.2Mpa；
Start vacuum pump and compressor, the R134a steam of parsing evaporation is delivered to condensing unit, the conversion of R134a steam
It is liquid to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches table
Pressing -0.08 to -0.09Mpa range is more than 5 minutes, shows that R134a has evaporated completely；
Keep vacuum degree gauge pressure -0.08 to -0.09Mpa, by residue NMP mixed solvent in container be heated to 120 DEG C -
150 DEG C, NMP is parsed from liquid surface to be evaporated, and the NMP steam of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.It with the continuity of evaporation process, is parsed completely in nmp solvent self-adhesive agent, it is molten to collect NMP
Liquid, cycle applications are in subsequent production.
In the present embodiment, on the basis of having efficiently separated discarded lithium battery material (wherein, the electrolyte rate of recovery >=
94%, the binder rate of recovery 92%, positive electrode rate of recovery 90%-93%, the negative electrode material rate of recovery 90%), can have simultaneously
The recycling extracting solvent R134a (rate of recovery 96%) and secondary solvent NMP (rate of recovery 88%) of effect, so as to avoid environmental pollution
With the waste of material, the energy has effectively been saved, has been reduced costs.
Embodiment 2
Extracting solvent chooses the mixture of R134a and R124a, and volume ratio is 1:1 or 2:1 or 1:2, is configured to extracting solvent
Ⅱ；Secondary solvent chooses the mixture of NMP and DMF, and volume ratio is 1:1 or 2:1 or 1:2, is configured to secondary solvent II.
As shown in Fig. 2, electric discharge, broken lithium battery material are packed into appropriate closed container, vacuumized, gauge pressure-
0.06 to -0.08Mpa, exclude on-condensible gas inside container；
Extracting solvent II is added in closed container, solvent adds 1 to 2 times that volume is lithium battery material volume, rises
Temperature boosts to 1.0 to 1.4Mpa, stirring leaching 20-60 minutes, electrolyte is substantially dissolved in extracting solvent II to 20 DEG C -50 DEG C
In；
Filtration system is opened, separates penetration by liquid strainer with solid, respectively obtains the leaching mixed liquor and the of electrolyte
One insoluble solid；Leaching, filtering 1-2 times is repeated, until electrolyte is leached completely；
In closed container, by the leaching mixed liquor continuous heating of electrolyte to 30 DEG C -60 DEG C, extracting solvent II mixes certainly
Evaporation is parsed in liquid.With the continuity of evaporation process, the pressure inside container gradually drops to 0.2Mpa or less；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent II has evaporated completely.Due to the boiling of electrolyte dimethyl carbonate
Point is 90.1 DEG C, cannot be evaporated in 30 DEG C of -60 DEG C of ranges, so that mixed liquor be made to be separated into electrolyte and extracting solvent II, is electrolysed
Liquid is separated and recovered.
As shown in Fig. 3, in closed container, II note of extracting solvent II and secondary solvent of about 50% volume ratio will respectively be accounted for
Enter the first insoluble solid material, the total volume for injecting mixed solvent is about 1 to 2 times of solid material volume；Be warming up to 20 DEG C-
50 DEG C, 0.8Mpa to 1.4Mpa is boosted to, stirring leaching 20-60 minutes dissolves the binder PVDF in solid material sufficiently
In in the mixed solvent；
Filtration system is opened, liquid and insoluble solid is separated, obtains the second leaching mixed liquor and the second insoluble solid.
Leaching, filtering 1-2 times is repeated, leaches binder completely；
In closed container, by the second leaching mixed liquor continuous heating to 30 DEG C -60 DEG C, extracting solvent II is from mixed liquor
Parsing evaporation, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, II steam of extracting solvent of parsing evaporation is delivered to condensing unit, steam conversion
It is liquid to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches table
Pressing -0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent II has evaporated completely.Due to the boiling point of secondary solvent II
For 153 DEG C (based on component DMF minimum by boiling point), cannot be evaporated in 30 DEG C of -60 DEG C of ranges, so that mixed liquor be made to be separated into auxiliary
II solution of solvent and extracting solvent II.
As shown in Fig. 4, in closed container, extracting solvent II is added to the second insoluble solid, additive amount is about not
1 to 2 times of soluble solids material volume；Stirring 20-60 minutes, the residual secondary solvent II for adhering to solids surface sufficiently expand
It is dispersed in extracting solvent II；
Filtration system is opened, liquid is separated with insoluble solid, respectively obtains third mixed solution and third is insoluble
Solids.Leaching, filtering 1-2 times is repeated, leaches solids secondary solvent II remained on surface completely；
In closed container, by third insoluble solid material continuous heating to 30 DEG C -60 DEG C, extracting solvent II is from solid
Surface parsing evaporation；With the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, II steam of extracting solvent of parsing evaporation is delivered to condensing unit, steam conversion
It is liquid to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches table
Pressing -0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent II has evaporated completely.Container bottom discharge valve is opened,
Obtain the lithium battery material for removing electrolyte and binder completely.
As shown in Fig. 5, second, third leaching mixed solvent is merged in closed container, persistently overheating is to 30 DEG C -60
DEG C, extracting solvent II parses evaporation from mixed liquor；With the continuity of evaporation process, the pressure inside container drops to
0.2Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, steam is converted into liquid
To obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure -0.08
It is more than 5 minutes to -0.09Mpa range, shows that extracting solvent II has evaporated completely；
Vacuum degree is kept, residual mixed liquor in container is heated to 120 DEG C -150 by gauge pressure -0.08 to -0.09Mpa
DEG C, secondary solvent II is parsed from liquid surface to be evaporated；The steam of parsing evaporation is delivered to condensing unit, steam is converted into liquid
To obtain reclaiming.It with the continuity of evaporation process, is parsed completely in II self-adhesive agent of secondary solvent, collects secondary solvent
II, cycle applications are in subsequent production.
In the present embodiment, (wherein, the electrolyte rate of recovery 93% is glued on the basis of efficiently separating discarded lithium battery material
Tie the agent rate of recovery 92%, the positive electrode rate of recovery 90%, the negative electrode material rate of recovery 92%), it being capable of effectively recycling leaching simultaneously
Solvent II (rate of recovery 96%) and secondary solvent II (rate of recovery 86%).
Embodiment 3
Extracting solvent chooses the mixture of solvent R134a, R124a, R123a and R406a, and volume ratio is 1:1:1:1 or 2:
1:1:1 or 1:1:1:2 is configured to extracting solvent III, and secondary solvent chooses the mixture of NMP, DMAC and DMF, volume ratio 2:
1:1 or 3:1:1 is configured to secondary solvent III.
As shown in Fig. 2, electric discharge, broken lithium battery material are packed into appropriate closed container, vacuumized, gauge pressure-
0.06 to -0.08Mpa, exclude the on-condensible gas inside container；
Extracting solvent III is added in closed container, solvent adds 1 to 2 times that volume is lithium battery material volume, rises
Temperature boosts to 1.0 to 1.4Mpa, stirring leaching 20-60 minutes, electrolyte is substantially dissolved in extracting solvent III to 20 DEG C -50 DEG C
In；
The filtration system inside container is opened, makes penetration by liquid strainer to separate with solid, respectively obtains lithium battery
The leaching mixed liquor and the first insoluble solid of liquid are solved, leaching, filtering 1-2 times is repeated, soaks the electrolyte in solid completely
It takes；
In closed container, by the leaching mixed liquor continuous heating of electrolyte to 30 DEG C -60 DEG C, extracting solvent III mixes certainly
Evaporation is parsed in liquid, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent III has evaporated completely.Due to the boiling of electrolyte dimethyl carbonate
Point is 90.1 DEG C, cannot be evaporated in 30 DEG C of -60 DEG C of ranges, so that mixed liquor be made to be separated into electrolyte and extracting solvent III, is electrolysed
Liquid is separated and recovered.
As shown in Fig. 3, in closed container, III note of extracting solvent III and secondary solvent of about 50% volume ratio will respectively be accounted for
Enter the first insoluble solid material, the total volume of injected mixed solvent is about 1 to 2 times of solid material volume；It is warming up to 20
DEG C -50 DEG C, 0.8Mpa to 1.4Mpa is boosted to, stirring leaching 20-60 minutes keeps the binder PVDF in solid material sufficiently molten
Solution is in the mixed solvent；
Filtration system is opened, liquid and insoluble solid is separated, obtains the second leaching mixed liquor and the second insoluble solid.
Leaching, filtering 1-2 times is repeated, leaches binder completely；
In closed container, by the second leaching mixed liquor continuous heating to 30 DEG C -60 DEG C, extracting solvent III is from mixed liquor
Parsing evaporation, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, III steam of extracting solvent of parsing evaporation is delivered to condensing unit, solvent vapo(u)r
Liquid is converted into obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches
Gauge pressure -0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent III has evaporated completely.Due to the boiling of secondary solvent III
Point is 153 DEG C (based on the component DMF minimum by boiling point), cannot be evaporated in 30 DEG C of -60 DEG C of ranges, to make supplemented by mixed liquor separation
Cosolvent III and extracting solvent III.
As shown in Fig. 4, in closed container, extracting solvent III is added to the second insoluble solid material, additive amount is about
It is 1 to 2 times of insoluble solid material volume；Stirring 20-60 minutes, the residual secondary solvent III for adhering to solids surface fill
Divide and is diffused in extracting solvent III；
Open container inside filtration system, separate liquid with insoluble solid, respectively obtain third mixed solution with
Third insoluble solid object.Leaching, filtering 1-2 times is repeated, leaches solids secondary solvent III remained on surface completely；
In closed container, by third insoluble solid material continuous heating to 30 DEG C -60 DEG C, extracting solvent III is from solid
Surface parsing evaporation；With the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, the steam of extracting solvent III is delivered to condensing unit, solvent vapo(u)r is converted into liquid
Body is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent III has evaporated completely.Container bottom discharge valve is opened, is obtained
To the lithium battery material of complete removing electrolyte and binder.
As shown in Fig. 5, second, third leaching mixed solvent is merged in closed container, persistently overheating is to 30 DEG C -60
DEG C, extracting solvent III parses evaporation from mixed liquor；With the continuity of evaporation process, the pressure inside container drops to
0.2Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, steam is converted into liquid
To obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure -0.08
It is more than 5 minutes to -0.09Mpa range, shows that extracting solvent III has evaporated completely；
Keep vacuum degree, gauge pressure -0.08 to -0.09Mpa, by mixed solvent remaining in container be heated to 120 DEG C -
150 DEG C, secondary solvent III is parsed from liquid surface to be evaporated, and the steam of parsing evaporation is delivered to condensing unit, solvent vapo(u)r turns
Liquid is turned to obtain reclaiming.It with the continuity of evaporation process, parses, collects completely in III self-adhesive agent of secondary solvent
Secondary solvent III, cycle applications are in subsequent production.
In the present embodiment, on the basis of having efficiently separated discarded lithium battery material (wherein, the electrolyte rate of recovery 93%,
The binder rate of recovery 92%, positive electrode rate of recovery 90%-92%, the negative electrode material rate of recovery 90%), it can effectively return simultaneously
Receive extracting solvent III (rate of recovery 95%) and secondary solvent III (rate of recovery 85%).
Embodiment 4
Extracting solvent chooses the mixture of solvent R134a and R406a, and volume ratio is that 1:1 or 1:2 or 2:1 is configured to leach
Solvent IV, secondary solvent choose the mixture of NMP, DMAC, DMF and DMSO, and volume ratio is that 2:1:1:1 or 3:1:1:1 is configured to
Secondary solvent IV.
As shown in Fig. 1, electric discharge, broken lithium battery material are packed into appropriate closed container, vacuumized, gauge pressure-
0.06 to -0.08Mpa, exclude the on-condensible gas inside container；
Extracting solvent IV is added in closed container, solvent adds 1 to 2 times that volume is lithium battery material volume, rises
Temperature boosts to 1.0 to 1.4Mpa, stirring leaching 20-60 minutes, electrolyte is substantially dissolved in extracting solvent IV to 20 DEG C -50 DEG C
In；
Filtration system is opened, makes penetration by liquid strainer to separate with solid, respectively obtains the leaching of lithium battery electrolytes
Mixed liquor and the first insoluble solid repeat leaching, filtering 1-2 times, leach the electrolyte in solid completely；
In closed container, by the leaching mixed liquor continuous heating of electrolyte to 30 DEG C -60 DEG C, extracting solvent IV mixes certainly
Evaporation is parsed in liquid, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, solvent vapo(u)r is converted into
Liquid is to obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure-
0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent IV has evaporated completely.Due to the boiling of electrolyte dimethyl carbonate
Point is 90.1 DEG C, cannot be evaporated in 30 DEG C of -60 DEG C of ranges, so that mixed liquor be made to be separated into electrolyte and extracting solvent IV, is electrolysed
Liquid is separated and recovered.
As shown in Fig. 3, in closed container, IV note of extracting solvent IV and secondary solvent of about 50% volume ratio will respectively be accounted for
Enter the first insoluble solid material, the total volume of injected mixed solvent is about 1 to 2 times of solid material volume；It is warming up to 20
DEG C -50 DEG C, 0.8Mpa to 1.4Mpa is boosted to, stirring leaching 20-60 minutes keeps the binder PVDF in solid material sufficiently molten
Solution is in the mixed solvent；
Filtration system is opened, makes the penetration by liquid strainer inside container to separate with insoluble solid, obtains the second leaching
Take mixed liquor and the second insoluble solid.Leaching, filtering 1-2 times is repeated, leaches binder completely；
In closed container, by the second leaching mixed liquor continuous heating to 30 DEG C -60 DEG C, extracting solvent IV is from mixed liquor
Parsing evaporation, with the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, IV steam of extracting solvent of parsing evaporation is delivered to condensing unit, solvent vapo(u)r
Liquid is converted into obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches
Gauge pressure -0.08 to -0.09Mpa range is more than 5 minutes, shows that extracting solvent IV has evaporated completely.Due to the boiling of secondary solvent IV
Point is 153 DEG C (based on the component DMF minimum by boiling point), cannot be evaporated in 30 DEG C of -60 DEG C of ranges, to make supplemented by mixed liquor separation
Cosolvent IV and extracting solvent IV.
As shown in Fig. 4, in closed container, extracting solvent IV is added to the second insoluble solid material, additive amount is about
It is 1 to 2 times of insoluble solid material volume；Stirring 20-60 minutes, the residual secondary solvent IV for adhering to solids surface fill
Divide and is diffused in extracting solvent IV；
Filtration system is opened, liquid and insoluble solid is separated, respectively obtains third mixed solution and third is insoluble solid
Body object.Leaching, filtering 1-2 times is repeated, leaches solids secondary solvent IV remained on surface completely；
In closed container, by third insoluble solid material continuous heating to 30 DEG C -60 DEG C, extracting solvent IV is from solid
Surface parsing evaporation；With the continuity of evaporation process, the pressure inside container drops to 0.2Mpa；
Start vacuum pump and compressor, IV steam of extracting solvent of parsing evaporation is delivered to condensing unit, solvent vapo(u)r
Liquid is converted into obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches
Gauge pressure -0.08 to -0.09Mpa range is more than 5 minutes, shows that solvent has evaporated completely.Container bottom discharge valve is opened, is obtained
Remove the lithium battery material of electrolyte and binder.
As shown in Fig. 5, second, third leaching mixed solvent is merged in closed container, persistently overheating is to 30 DEG C -60
DEG C, extracting solvent IV parses evaporation from mixed liquor；With the continuity of evaporation process, the pressure inside container gradually drops to
0.2Mpa；
Start vacuum pump and compressor, the solvent vapo(u)r of parsing evaporation is delivered to condensing unit, steam is converted into liquid
To obtain reclaiming.Continue this process, until becoming vacuum from positive pressure inside container, and stably reaches gauge pressure -0.08
It is more than 5 minutes to -0.09Mpa range, shows that extracting solvent IV has evaporated completely；
Keep vacuum degree, gauge pressure -0.08 to -0.09Mpa, by mixed solvent remaining in container be heated to 120 DEG C -
150 DEG C, secondary solvent IV is parsed from liquid surface to be evaporated, and the steam of parsing evaporation is delivered to condensing unit, solvent vapo(u)r turns
Liquid is turned to obtain reclaiming.It with the continuity of evaporation process, parses, collects completely in IV self-adhesive agent of secondary solvent
Secondary solvent IV, cycle applications are in subsequent production.
In the present embodiment, (wherein, the electrolyte rate of recovery 93% is glued on the basis of efficiently separating discarded lithium battery material
Tie the agent rate of recovery 90%, positive electrode rate of recovery 90%-92%, the negative electrode material rate of recovery 88%), it can effectively recycle simultaneously
Extracting solvent IV (rate of recovery 95%) and secondary solvent IV (rate of recovery 85%).
It for the discarded lithium battery for losing use value, is formed using suitable solvent, lithium battery is recycled in leaching first
Electrolyte, secondly leaching, separation binder, make to be combined into whole positive and negative pole material, copper foil, aluminium foil, plastics, iron shell originally
Separation, while high efficiente callback, recycling extracting solvent so that this method is with other existing production technologies compared with, with
Lower advantage:
The electrolyte in lithium battery is directly leached using solvent method, is reduced electrolyte and is contacted generation harmfulness object with air
The probability of matter and time are effectively relieved lithium battery electrolytes and import the possible environmental pollution of surrounding enviroment and hidden fire-fighting danger.
Meanwhile leaching, separation process carry out inside the container of totally-enclosed, whole process does not have pollution gas, liquid discharge.
By hydrocarbon extracting solvent and the known N-Methyl pyrrolidone of industry (NMP) solvent complex, can assign
Mixed solvent functional characteristic: firstly, the viscosity of mixed liquid in leaching process reduces, mobility is improved, and is conducive to leaching process
It goes on smoothly；Secondly, the intervention of low-boiling hydrocarbon cosolvent, can be such that dissolvent residual accompanying by solid material surface obtains
Sufficiently to recycle；Again, nontoxic, the non-ignitable hydrocarbon of use considerably reduces lithium battery as main extracting solvent
The combustibility for solving liquid, enables production process to carry out in a safe environment.
Selected hydrocarbon organic solvent, boiling point are respectively less than 0 DEG C, solvent can be realized in a mild condition
Evaporation and condensing recovery, avoid energy waste present in conventional recovery method.
After electrolyte in discarded lithium battery, binder leaching are removed, battery material is in completely loose mixing shape
State, to lay a good foundation for the materials such as regeneration nickel, cobalt, lithium, manganese, copper, aluminium, iron are further purified.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of solvent compositions suitable for discarding lithium battery material leaching separation, which is characterized in that the solvent compositions
Including for leaching the extracting solvent of electrolyte in discarded lithium battery material and being used in the discarded lithium battery material of leaching separation glue
The secondary solvent of agent is tied, the boiling point of the extracting solvent is lower than the boiling point of secondary solvent.
2. being suitable for the solvent compositions of discarded lithium battery material leaching separation according to claim 1, which is characterized in that institute
State extracting solvent be hydrocarbon, including in tetrafluoroethane, a chloro-tetrafluoroethane, dichlorotrifluoroethane, R-406a at least
It is a kind of；The secondary solvent includes N-Methyl pyrrolidone, N- dimethyl acetamide, dinethylformamide, dimethyl sulfoxide
At least one of.
3. a kind of discarded lithium battery material leaching separation method, which is characterized in that useless using being suitable for as described in claim 1
The solvent compositions for abandoning lithium battery material leaching separation carry out leaching separation to discarded lithium battery material, comprising the following steps:
1) it will discharge, the appropriate closed container of broken discarded lithium battery material loading, and vacuumize, then add extracting solvent,
It leaches under stirring, is separated by filtration later, respectively obtain the first insoluble solid and the first leaching mixed liquor；
2) the first leaching mixed solution heating fractionation for obtaining step 1), respectively obtains extracting solvent and electrolyte；
3) extracting solvent and secondary solvent, 20 DEG C to 50 DEG C temperature ranges are added into the first insoluble solid that step 1) obtains
Lasting stirring leaching respectively obtains the second insoluble solid and the second mixing leaching liquid after being separated by filtration；
4) the second insoluble solid addition extracting solvent obtained to step 3), leaches under lasting stirring；It is separated by filtration
After obtain third insoluble solid and third leaching mixed liquor；
5) step 4) is obtained into third insoluble solid heat drying, steam condensing reflux is obtained into extracting solvent；It will be completely dry
The dry further physical separation of third insoluble solid obtains lithium battery solid material；
6) the third mixing leaching liquid for merging the second obtained mixing leaching liquid of step 3) and 4) obtaining, continues agitating and heating, point
It evaporates, respectively obtains extracting solvent, secondary solvent and binder mixtures；
7) collection step 6) obtained secondary solvent is for being recycled；Step 2), step 5) and step 6) is collected and merges to obtain
The extracting solvent arrived is for recycling.
4. a kind of discarded lithium battery material leaching separation method according to claim 3, which is characterized in that the step 1)
In, the solid, liquid volume ratio for discarding lithium battery material and extracting solvent is 1:1 to 1:2, and leaching time is 20~60 minutes, leaching
Temperature is 20 DEG C~50 DEG C；Operating pressure 0.8MPa to 1.35MPa, repeating leaching number is 1 to 2 time.
5. a kind of discarded lithium battery material leaching separation method according to claim 3, which is characterized in that the step 3)
In, the mixed volume ratio of extracting solvent and secondary solvent is 1:1, and the volume ratio of mixed solvent and the first insoluble solid is 1:
2；Leaching condition are as follows: 20 DEG C~50 DEG C of leaching temperature, operating pressure 0.8MPa~1.35MPa, leaching time is 20~60min,
Repeating leaching number is 1~2 time.
6. a kind of discarded lithium battery material leaching separation method according to claim 3, which is characterized in that the leaching of step 4)
Condition are as follows: 20 DEG C to 50 DEG C of leaching temperature, operating pressure 0.8MPa to 1.35MPa, leaching time 20-60min, repeat to leach
Number is 1-2 times.
7. a kind of discarded lithium battery material leaching separation method according to claim 3, which is characterized in that the step 2),
The evaporation conditions of recycling extracting solvent in step 5) are as follows: gauge pressure -0.08MPa to 1.4MPa, 30 DEG C -60 DEG C of temperature；Termination condition
Are as follows: vacuum degree reaches -0.08 to -0.09Mpa in closed container, continues pressure maintaining 5 minutes.
8. a kind of discarded lithium battery material leaching separation method according to claim 3, which is characterized in that recycling in step 6)
The evaporation conditions of extracting solvent are as follows: gauge pressure -0.08MPa to 1.4MPa, 30 DEG C -60 DEG C of temperature；Termination condition are as follows: in closed container
Vacuum degree reaches -0.08 to -0.09Mpa, continues pressure maintaining 5 minutes；The evaporating temperature for recycling nmp solution is 120 DEG C to 180 DEG C,
Continuous vacuum degree gauge pressure is -0.06 to -0.09MPa.
9. according to a kind of any discarded lithium battery material leaching separation method of claim 3-8, which is characterized in that the leaching
Taking solvent includes at least one of hydrocarbon tetrafluoroethane, a chloro-tetrafluoroethane, dichlorotrifluoroethane and R-406a；Institute
State secondary solvent include N-Methyl pyrrolidone, N- dimethyl acetamide, dinethylformamide, in dimethyl sulfoxide at least
It is a kind of.
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| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
| WO2023240334A1 (en) * | 2022-05-02 | 2023-12-21 | Technologies Lithion Inc. | Improved lithium batteries recycling process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1819326A (en) * | 2006-01-10 | 2006-08-16 | 东南大学 | Resource separation of waste lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1819326A (en) * | 2006-01-10 | 2006-08-16 | 东南大学 | Resource separation of waste lithium ion battery |
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| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
| WO2022041327A1 (en) * | 2020-08-28 | 2022-03-03 | 甘肃电气装备集团生物科技工程有限公司 | Extraction solvent applied to electrolyte in decommissioned lithium battery and method for separating and recovering electrolyte from decommissioned lithium battery by using same |
| WO2023240334A1 (en) * | 2022-05-02 | 2023-12-21 | Technologies Lithion Inc. | Improved lithium batteries recycling process |
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