CN107275700A - A kind of waste and old lithium ion battery recovery and treatment method crushed based on wet type - Google Patents
A kind of waste and old lithium ion battery recovery and treatment method crushed based on wet type Download PDFInfo
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- CN107275700A CN107275700A CN201610214115.XA CN201610214115A CN107275700A CN 107275700 A CN107275700 A CN 107275700A CN 201610214115 A CN201610214115 A CN 201610214115A CN 107275700 A CN107275700 A CN 107275700A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
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Abstract
The present invention provides a kind of waste and old lithium ion battery recovery method crushed based on wet type, and methods described comprises the following steps：Waste and old lithium ion battery carries out discharge process；Wet type is carried out to the waste and old lithium ion battery after electric discharge to crush, the broken solvent used of the wet type is organic solvent；Separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, organic solvent is separated and recovered from liquid phase, the organic solvent is recycled；Isolated electrolyte and binding agent from the remaining liquid phase after organic solvent is reclaimed；Isolated active principle aluminium, iron, copper and positive powder from the solid phase after separation of solid and liquid.The inventive method simplifies the complicated pre-selection process in Battery disposal process, and disposable efficient process waste and old lithium ion battery improves organic efficiency, with cost is low, efficient, non-secondary pollution the features such as.
Description
Technical field
The invention belongs to recycling of WEEE utilize and recycling economy technical field, be related to a kind of waste and old lithium from
The recovery method of sub- battery, more particularly to a kind of waste and old lithium ion battery recycling side crushed based on wet type
Method.
Background technology
With becoming increasingly conspicuous the problems such as energy crisis and environmental pollution, Sustainable Development new energy is built
If environmental protection low-carbon type society turns into the task of top priority.Lithium ion battery, solar cell, fuel cell and
The clean reproducible energies such as wind-power electricity generation turn into the developing direction of future source of energy, and with electric automobile industry
High speed development, lithium ion battery is by uniquenesses such as its specific energy height, small volume, light weight, wide temperature ranges
Advantage, production and demand are growing day by day in recent years.
The extensive utilization of lithium ion battery, has not only brought facility, the discarded amount of the thing followed also by
Year increase.The mineral resources of China are relatively fewer, and have in waste and old lithium ion battery lithium, cobalt, manganese, nickel,
Many valuable metal resources such as aluminium, copper, main component includes cobaltosic oxide, nickel, cobalt and manganese oxide, nickel cobalt
Manganese hydroxide, cobalt acid lithium, LiMn2O4, lithium cobalt manganic acid lithium.Compared to mineral resources, waste and old lithium-ion electric
Pond metals resources content is of a relatively high, and species and content are determined, if can high efficiente callback waste and old lithium ion battery
And its metal in production waste material, the consumption of mineral resources can not only be reduced, additionally it is possible to reduce it to environment
With the harm of the mankind, promote the industrial upgrading of lithium ion battery.
At present, for lithium ion battery resource recycle method mainly include hydrometallurgy, pyrometallurgy and
Biological metallurgy.Due to lithium ion battery structure include plastics package, metal shell, positive plate, negative plate and
Electrolyte, general burn off electrolyte and plastic casing, binding agent etc. by the way of pyrogenic process calcining in industry,
Cause processing procedure exhaust emission serious.For the recovery of metals resources in battery, although wet process can profit
With the chemical reagent such as sodium hydroxide, sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide by the aluminium in lithium ion battery, nickel,
The metal ions such as cobalt, manganese, iron, copper, lithium are leached, and are purified, separated by modes such as precipitation, extractions
Each metal, but typically can because of strong acid, highly basic presence, cause secondary environmental pollution.
CN104577249A discloses a kind of method of resource of waste and old cobalt acid lithium battery, and this method uses punch press
The techniques such as broken, vibrosieve, magnetic separation, vortex electric separation, the roasting of anaerobic normal pressure, alternating temperature filtering are combined reality
The complete resource of valuable component in existing waste and old lithium ion battery, and obtain the thick cobalt of simple substance with high added value,
The products such as lithium carbonate, graphite, copper, aluminium, iron, plastics.However, to the electrolysis in battery in this mode
The processing mode of liquid is only the roasting of anaerobic normal pressure, it is thus possible to cause exhaust emission.
CN102009054A discloses a kind of waste and old lithium ion battery efficient pulverizing new technology, and the technique is by releasing
Put that remaining electricity, wet type be broken, sieving technology composition, realize efficient pulverizing and the selection of waste and old lithium ion battery
Property crush and reduce the cost recovery of cobalt acid lithium.However, this processing mode is just for cobalt acid lithium secondary cell,
Nickle cobalt lithium manganate battery, ferric phosphate lithium cell to gradually putting into application now etc. are not simultaneously applied to, and adding
In the wet type shattering process of water, positive pole and negative electrode active material and collector can not be efficiently separated, is made follow-up
Metal separation process there is certain difficulty.
Therefore, need badly at present and develop a kind of clean technologies that can be reclaimed and mix lithium ion battery.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of waste and old lithium ion battery recovery side
Method, is provided in particular in a kind of waste and old lithium ion battery recovery method crushed based on wet type.
To reach this goal of the invention, the present invention uses following technical scheme：
The present invention provides a kind of waste and old lithium ion battery recovery method, and methods described comprises the following steps：
(1) waste and old lithium ion battery carries out discharge process；
(2) carry out wet type to the waste and old lithium ion battery after electric discharge to crush, the broken solvent used of the wet type
For organic solvent；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, being separated and recovered from liquid phase has
Machine solvent, the organic solvent return to step (2) is recycled；
(4) isolated electrolyte and binding agent in the remaining liquid phase reclaimed from step (3) after organic solvent；
(5) isolated active principle aluminium, iron, copper and just from the solid phase after step (3) separation of solid and liquid
The mixture of pole powder.
In the method for the invention, carry out what is used when wet type is broken to the waste and old lithium ion battery after electric discharge
It is organic solvent, the wet type carried out using organic solvent is crushed, actually one dissolving, broken integration
Coupling chemistry-physical process, and the broken physics shattering process of traditional dry-type pulverizing, the wet type that adds water is complete
It is different.Compared to the solvent for crushing water as wet type, organic solvent can be broken while, by molten
Organic binder bond is solved, so as to accelerate separation positive pole, negative electrode active material and corresponding collector, is shortened brokenly
The broken time, improve the separative efficiency of positive and negative electrode material.In particle after broken, most positive pole material
The various materials such as material, negative material, aluminium foil are separated to be opened, and is disperseed in organic solvent.Conventional dry, with
Water fragmentates for broken simply battery physics is crushed of wet type of solvent, the various electricity such as most of positive pole, negative pole
Pond material sticks together still through binding agent.Meanwhile, electrolyte, binding agent in shattering process etc. are organic
Volatile matter can form vapor phase contaminants, caused by after especially fluorine-containing electrolyte, broken blade frictional heat
The toxicity of organic matter degradation accessory substance is larger.Crushed by the wet type of organic solvent, organic vapors can be absorbed
Pollutant, reduces secondary pollution in processing procedure.Separative efficiency, reduction broken time are improved, can also be dropped
To the damage of equipment in low shattering process, the service life of extension device.
In the present invention, the active material in the positive electrode of lithium ion battery is LiFePO4, Ni-based oxidation
One or more of combinations in thing, cobalt base oxide or manganese-base oxide.
Preferably, the active material in the positive electrode of the waste and old lithium ion battery be cobalt acid lithium, lithium nickelate,
LiMn2O4, binary composite positive pole or one kind in ternary composite cathode material or at least two combination.
Preferably, the binary composite positive pole is LiNixCo1–xO2、LiNixMn1–xO2Or
LiCo1–xMnxO2In one kind or at least two combination, wherein, 0≤x≤1.
Preferably, the ternary composite cathode material is LiNixCoyMnl–x–yO2And/or
LiNixCoyAll–x–yO2, wherein, 0≤x≤1,0≤y≤1, and 0≤x+y≤1.
In the present invention, step (1) described discharge process is that waste and old lithium ion battery is dipped in salting liquid
Carry out discharge process.
Preferably, the concentration of the salting liquid be 0.1-20%, such as 0.1%, 1%, 3%, 5%, 7%,
8%th, 9%, 10%, 12%, 14%, 16%, 18% or 20%, preferably 1-8% salting liquid.
Preferably, the salting liquid is NaCl, KCl, NH4Cl、Na2SO4、(NH4)2SO4In one kind
Or two kinds of combination.
Preferably, the soaking temperature be 10-60 DEG C, such as 10 DEG C, 13 DEG C, 15 DEG C, 18 DEG C,
20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C.
Preferably, the soak time is 1-72h, such as 1h, 3h, 5h, 8h, 10h, 15h, 18
h、20h、24h、28h、30h、33h、36h、38h、40h、45h、48h、50h、55
H, 58h, 60h, 64h, 68h, 70h or 72h, preferably 1-10h.
Preferably, by waste and old lithium ion battery be dipped in salting liquid carry out discharge process when liquid-solid ratio be
0.1-100L/kg, 0.1L/kg, 1L/kg, 5L/kg, 8L/kg, 10L/kg, 15L/kg, 18L/kg,
20L/kg、25L/kg、30L/kg、35L/kg、40L/kg、50L/kg、60L/kg、70L/kg、80
L/kg, 90L/kg or 100L/kg.
Preferably, step (2) described organic solvent is ketone, arene, fat hydrocarbon, alicyclic
In class, alcohols, ethers, esters, diol, derivatives or halogenated carboxylic acid any one or at least two group
Close.
Preferably, step (2) described wet type it is broken used in equipment be that shear crusher, circular cone type are broken
In broken machine, jaw crusher, hammer mill or impact crusher any one or at least two group
Close.
Preferably, step (2) described wet type broken time is 0.5-100h, such as 0.5h, 1h, 3h,
5h、10h、15h、20h、24h、28h、30h、32h、36h、40h、45h、48h、52
H, 58h, 60h, 64h, 72h, 80h, 84h, 90h, 96h or 100h, preferably 1-20h.
Preferably, solid-to-liquid ratio when step (2) described wet type is broken is more than or equal to 0.1kg/L, such as 0.1
L/kg、1L/kg、5L/kg、8L/kg、10L/kg、15L/kg、18L/kg、20L/kg、25
L/kg、30L/kg、35L/kg、40L/kg、50L/kg、60L/kg、70L/kg、80L/kg、90
L/kg or 100L/kg, preferably 0.5-50kg/L.
Preferably, the granularity of the broken gained solid of step (2) described wet type is 10-200 mesh, such as 10 mesh,
20 mesh, 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 120 mesh, 140
Mesh, 160 mesh, 180 mesh or 200 mesh, preferably 50-100 mesh.
Preferably, step (3) it is described reclaim organic solvent method for rectifying, extraction, stripping, absorption,
Crystallization or UF membrane in any one or at least two combination.
Preferably, the method for step (4) the isolated electrolyte and binding agent be distillation, UF membrane,
Absorption, extraction or centrifuge in any one or at least two combination.
Preferably, the mixture of step (5) the isolated active principle aluminium, iron, copper and positive powder
Method is for any one in gravity separating method, magnetic method, floatation, sieve method or cyclonic separation or at least
Two kinds of combination.
Preferably, the waste gas return to step (2) produced after step (5) described separation, is used as regenerated solvent
Recycle.The waste gas is the liquid component evaporated when carrying out separation of solid and liquid, and it contains organic solvent
With micro electrolyte and conductive agent, therefore, it return to step (2) can be followed as regenerated solvent
Ring is used.
It is used as optimal technical scheme, the waste and old lithium ion battery recovery method of the present invention crushed based on wet type
Specifically include following steps：
(1) waste and old lithium ion battery is soaked into 1-72h, immersion temperature in concentration is 0.1-20% salting liquid
Spend for 10-60 DEG C, carry out discharge process, liquid-solid ratio when carrying out discharge process is 0.1-100L/kg；
(2) carry out wet type to the waste and old lithium ion battery after electric discharge to crush, the broken solvent used of the wet type
For organic solvent, the wet type broken time is 0.5-100h, and solid-to-liquid ratio when wet type is broken is more than or equal to
0.1kg/L, the granularity of the broken gained solid of wet type is 10-200 mesh；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, being separated and recovered from liquid phase has
Machine solvent, the organic solvent return to step (2) is recycled；
(4) isolated electrolyte and binding agent in the remaining liquid phase reclaimed from step (3) after organic solvent；
(5) isolated active principle aluminium, iron, copper and just from the solid phase after step (3) separation of solid and liquid
The mixture of pole powder, the waste gas return to step (2) produced after step (5) described separation is molten as regenerating
Agent is recycled.
Relative to prior art, the invention has the advantages that：
The present invention using organic matter as wet type crush solvent, can by dissolve binding agent separation positive pole,
Negative electrode active material and corresponding collector, shorten technological process；At waste and old lithium ion battery collaboration
Reason, simplifies the complicated pre-selection process in Battery disposal process, disposable efficient process applying waste lithium ionic electricity
Pond, improves organic efficiency；The solvent crushed by the use of organic matter as wet type, can be reduced in shattering process
Damage to equipment, the service life of extension device.In addition, the present invention coordinates other points using wet type is broken
Being combined from mode mode such as rectifying separation, solid sorting realizes valuable group of waste and old lithium ion battery
The separation divided so that the wherein rate of recovery of metal is more than 98%, and organic solvent can be utilized with closed cycle,
Compared with the separation methods such as inorganic Ore Leaching, extract and separate, chemical precipitation, with cost is low, efficient, nothing
The features such as secondary pollution.
Brief description of the drawings
The process chart that Fig. 1 reclaims for the present invention for waste and old lithium ion battery.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art
It will be clearly understood that the embodiment is only to aid in understanding the present invention, the specific limit to the present invention is not construed as
System.
Embodiment 1
In the present embodiment, waste and old lithium ion battery recovery is carried out by the following method, specifically includes following step
Suddenly (its technological process is as shown in Figure 1)：
(1) pending waste and old lithium ion battery is soaked in 5% sodium chloride solution in 2h, positive electrode
Active material be nickel-based oxide, cobalt base oxide, manganese-base oxide, soaking temperature be 25 DEG C, liquid is solid
Than for 2L/kg, the remaining electric Spontaneous release of waste and old lithium ion battery；
(2) it is the waste and old lithium ion battery after electric discharge and organic solvent 1-METHYLPYRROLIDONE (NMP) is mixed
Close, wet type is carried out in shear crusher and is crushed, it is 2h to crush the time, and solid-to-liquid ratio is 3kg/L, institute is crushed
The particle size range for obtaining solid is 50-100 mesh；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, obtained liquid phase is with rectifying side
Formula Separation of Organic, the organic solvent return to step (2) is recycled；
(4) residual solution for reclaiming step (3) after organic solvent is efficiently separated by distilling, point
From the mixture for obtaining electrolyte and binding agent；
(5) by the solid phase after step (3) separation of solid and liquid after drying, using gravity separation separation wherein
Aluminium, iron, copper, the mixture of positive powder, the waste gas return to step (2) produced after step (5) described separation,
Recycled as regenerated solvent.
The rate of recovery that each obtained metal is reclaimed from waste and old sub- battery by the present embodiment is shown in Table 1.
Table 1
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.31% | 99.85% | 99.82% |
Embodiment 2
In the present embodiment, waste and old lithium ion battery recovery is carried out by the following method, specifically includes following step
Suddenly (its technological process is as shown in Figure 1)：
(1) pending waste and old lithium ion battery is soaked into 72h in the solution of 0.1% ammonium chloride and potassium chloride,
Active material in positive electrode is LiFePO4, and soaking temperature is 60 DEG C, and liquid-solid ratio is 0.1L/kg, waste and old
The remaining electric Spontaneous release of lithium ion battery.
(2) waste and old lithium ion battery after electric discharge is mixed with the mixture of trifluoroacetic acid and dimethylbenzene, successively
Carry out wet type in impact crusher and jaw crusher to crush, it is 0.5h to crush the time, and solid-to-liquid ratio is
0.1kg/L, the particle size range for crushing gained solid is 50-100 mesh.
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, obtained liquid phase is with rectifying side
Formula Separation of Organic, the organic solvent return to step (2) is recycled；
(4) residual solution for reclaiming step (3) after organic solvent is efficiently separated by distilling, point
From the mixture for obtaining electrolyte and binding agent；
(5) by the solid phase after step (3) separation of solid and liquid after drying, using gravity separation separation wherein
Aluminium, iron, copper, the mixture of positive powder, the waste gas return to step (2) produced after step (5) described separation,
Recycled as regenerated solvent.
The rate of recovery that each obtained metal is reclaimed from waste and old sub- battery by the present embodiment is shown in Table 2.
Table 2
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.23% | 99.96% | 98.39% |
Embodiment 3
In the present embodiment, waste and old lithium ion battery recovery is carried out by the following method, specifically includes following step
Suddenly (its technological process is as shown in Figure 1)：
(1) pending waste and old lithium ion battery is soaked into 1h in the solution of 20% sodium sulphate and ammonium sulfate,
Active material in positive electrode is LiFePO4, and soaking temperature is 10 DEG C, and liquid-solid ratio is 100L/kg, waste and old
The remaining electric Spontaneous release of lithium ion battery；
(2) by hexamethylene, ethyl acetate and ethylene glycol with volume fraction 1:1:After 1 mixing, electric discharge is put into
Waste and old lithium ion battery afterwards, successively carries out wet type in cone crusher and hammer mill and crushes, break
The broken time is 20h, and solid-to-liquid ratio is 50kg/L, and the particle size range for crushing gained solid is 50-100 mesh；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, obtained liquid phase is with rectifying side
Formula Separation of Organic, the organic solvent return to step (2) is recycled；
(4) residual solution for reclaiming step (3) after organic solvent is efficiently separated by distilling, point
From the mixture for obtaining electrolyte and binding agent；
(5) by the solid phase after step (3) separation of solid and liquid after drying, using gravity separation separation wherein
Aluminium, iron, copper, the mixture of positive powder, the waste gas return to step (2) produced after step (5) described separation,
Recycled as regenerated solvent.
The rate of recovery that each obtained metal is reclaimed from waste and old sub- battery by the present embodiment is shown in Table 3.
Table 3
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.56% | 99.79% | 98.22% |
Embodiment 4
In the present embodiment, waste and old lithium ion battery recovery is carried out by the following method, specifically includes following step
Suddenly (its technological process is as shown in Figure 1)：
(1) pending waste and old lithium ion battery is soaked into 1h, positive electrode in the solution of 10% sodium sulphate
In active material be nickle cobalt lithium manganate (LiNi1/3Co1/3Mn1/3O2) and LiFePO4, soaking temperature is 10 DEG C,
Liquid-solid ratio is 100L/kg, the remaining electric Spontaneous release of waste and old lithium ion battery；
(2) by dimethyl ether, propyl alcohol and 2- glycol chlorohydrins with volume fraction 1:1:After 1 mixing, electric discharge is put into
Waste and old lithium ion battery afterwards, successively carries out wet type in cone crusher and shear crusher and crushes,
The broken time is 1h, and solid-to-liquid ratio is 20kg/L；The particle size range of broken gained solid is 50-100 mesh；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, obtained liquid phase is with rectifying side
Formula Separation of Organic, the organic solvent return to step (2) is recycled；
(4) residual solution for reclaiming step (3) after organic solvent is efficiently separated by distilling, point
From the mixture for obtaining electrolyte and binding agent；
(5) by the solid phase after step (3) separation of solid and liquid after drying, using gravity separation separation wherein
Aluminium, iron, copper, the mixture of positive powder, the waste gas return to step (2) produced after step (5) described separation,
Recycled as regenerated solvent.
The rate of recovery that each obtained metal is reclaimed from waste and old sub- battery by the present embodiment is shown in Table 4.
Table 4
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.45% | 99.26% | 99.80% |
It is the solvent that wet type is crushed by using organic matter, waste and old mixing lithium ion battery is recycled,
Isolated aluminium, iron, the rate of recovery of copper have exceeded 99%, and the organic solvent cycling rate of processing procedure surpasses
97% is crossed, secondary pollution of the organic solvent to environment is efficiently avoid, while also reducing production cost.
Applicant states that the present invention illustrates the process of the present invention, but the present invention by above-described embodiment
Above-mentioned processing step is not limited to, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to former selected by the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc., all fall within the protection model of the present invention
Within the scope of enclosing and disclosing.
Claims (10)
1. a kind of waste and old lithium ion battery recovery method, it is characterised in that methods described includes following step
Suddenly：
(1) waste and old lithium ion battery carries out discharge process；
(2) carry out wet type to the waste and old lithium ion battery after electric discharge to crush, the broken solvent used of the wet type
For organic solvent；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, being separated and recovered from liquid phase has
Machine solvent, the organic solvent return to step (2) is recycled；
(4) isolated electrolyte and binding agent in the remaining liquid phase reclaimed from step (3) after organic solvent；
(5) isolated active principle aluminium, iron, copper and just from the solid phase after step (3) separation of solid and liquid
The mixture of pole powder.
2. according to the method described in claim 1, it is characterised in that the positive pole of the waste and old lithium ion battery
Active material in material is cobalt acid lithium, lithium nickelate, LiMn2O4, binary composite positive pole or tri compound
One kind or at least two combination in positive electrode；
Preferably, the binary composite positive pole is LiNixCo1–xO2、LiNixMn1–xO2Or
LiCo1–xMnxO2In one kind or at least two combination, wherein, 0≤x≤1；
Preferably, the ternary composite cathode material is LiNixCoyMnl–x–yO2And/or
LiNixCoyAll–x–yO2, wherein, 0≤x≤1,0≤y≤1, and 0≤x+y≤1.
3. method according to claim 1 or 2, it is characterised in that at step (1) described electric discharge
Manage and carry out discharge process for waste and old lithium ion battery is dipped in salting liquid；
Preferably, the concentration of the salting liquid is 0.1-20%, preferably 1-8%；
Preferably, the salting liquid is NaCl, KCl, NH4Cl、Na2SO4、(NH4)2SO4In it is any
It is a kind of or at least two combination；
Preferably, the soaking temperature is 10-60 DEG C；
Preferably, the soak time is 1-72h；
Preferably, by waste and old lithium ion battery be dipped in salting liquid carry out discharge process when liquid-solid ratio be
0.1-100L/kg。
4. the method according to any one of claim 1-3, it is characterised in that step (2) is described
Organic solvent is ketone, arene, fat hydrocarbon, alicyclic hydrocarbon type, alcohols, ethers, esters, glycol
In derivative or halogenated carboxylic acid any one or at least two combination；
Preferably, step (2) described wet type it is broken used in equipment be that shear crusher, circular cone type are broken
In broken machine, jaw crusher, hammer mill or impact crusher any one or at least two group
Close.
5. the method according to any one of claim 1-4, it is characterised in that step (2) is described
The wet type broken time is 0.5-100h, preferably 1-20h；
Preferably, solid-to-liquid ratio when step (2) described wet type is broken is more than or equal to 0.1kg/L, preferably
0.5-50kg/L；
Preferably, the granularity of the broken gained solid of step (2) described wet type is 10-200 mesh.
6. the method according to any one of claim 1-5, it is characterised in that step (3) is described
The method for reclaiming organic solvent is any one in rectifying, extraction, stripping, absorption, crystallization or UF membrane
Or at least two combination.
7. the method according to any one of claim 1-6, it is characterised in that step (4) is described
The method of isolated electrolyte and binding agent be distillation, UF membrane, absorption, extraction or centrifugation in
Any one or at least two combination.
8. the method according to any one of claim 1-7, it is characterised in that step (5) is described
Isolated active principle aluminium, iron, the method for the mixture of copper and positive powder are gravity separating method, magnetic method,
In floatation, sieve method or cyclonic separation any one or at least two combination.
9. the method according to any one of claim 1-8, it is characterised in that step (5) is described
The waste gas return to step (2) produced after separation, is recycled as regenerated solvent.
10. the method according to any one of claim 1-9, it is characterised in that methods described includes
Following steps：
(1) waste and old lithium ion battery is soaked into 1-72h, immersion temperature in concentration is 0.1-20% salting liquid
Spend for 10-60 DEG C, carry out discharge process, liquid-solid ratio when carrying out discharge process is 0.1-100L/kg；
(2) carry out wet type to the waste and old lithium ion battery after electric discharge to crush, the broken solvent used of the wet type
For organic solvent, the wet type broken time is 0.5-100h, and solid-to-liquid ratio when wet type is broken is more than or equal to
0.1kg/L, the granularity of the broken gained solid of wet type is 10-200 mesh；
(3) separation of solid and liquid is carried out to the solidliquid mixture that wet type is obtained after broken, being separated and recovered from liquid phase has
Machine solvent, the organic solvent return to step (2) is recycled；
(4) isolated electrolyte and binding agent in the remaining liquid phase reclaimed from step (3) after organic solvent；
(5) isolated active principle aluminium, iron, copper and just from the solid phase after step (3) separation of solid and liquid
The mixture of pole powder, the waste gas return to step (2) produced after step (5) described separation, is used as regenerated solvent
Recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610214115.XA CN107275700B (en) | 2016-04-07 | 2016-04-07 | A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type |
Applications Claiming Priority (1)
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| CN108110356A (en) * | 2017-12-08 | 2018-06-01 | 天齐锂业股份有限公司 | A kind of full-automatic waste and old lithium ion battery recovery process and system |
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| CN111203172A (en) * | 2020-01-08 | 2020-05-29 | 山东建筑大学 | Method for preparing heavy metal adsorbent by recycling waste lithium ion battery anode material |
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