CN116169388A - Method for recycling electrolyte of retired lithium battery and selectively extracting metal - Google Patents
Method for recycling electrolyte of retired lithium battery and selectively extracting metal Download PDFInfo
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- CN116169388A CN116169388A CN202310095012.6A CN202310095012A CN116169388A CN 116169388 A CN116169388 A CN 116169388A CN 202310095012 A CN202310095012 A CN 202310095012A CN 116169388 A CN116169388 A CN 116169388A
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- electrolyte
- lithium
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- lithium battery
- leaching
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 95
- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 238000001704 evaporation Methods 0.000 claims abstract description 33
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 20
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000010008 shearing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—Batteries
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling electrolyte and selectively extracting metal of a retired lithium battery, which relates to the field of comprehensive recycling of retired lithium batteries, and specifically comprises the following steps: and shearing and crushing the discharged retired lithium battery, performing low-temperature evaporation under the protection of inert gas, absorbing phosphorus and fluorine by the electrolyte escaped in the evaporation process through a calcium oxide solution, adding a carbonic acid solution into the absorption solution for neutralization treatment, and filtering and separating to obtain an aqueous solution of the electrolyte. And (3) putting the positive electrode material obtained from the retired lithium battery subjected to low-temperature evaporation treatment into an aqueous solution of electrolyte for leaching, and filtering to obtain a lithium-rich solution and leaching residues. According to the invention, the lithium element in the anode material is selectively extracted by using the retired lithium battery electrolyte as the leaching solvent, the electrolyte in the leaching solvent can be recycled, so that the harm to the environment caused by electrolyte components in the retired lithium battery is avoided, and the method is suitable for treating various retired lithium batteries such as nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium cobaltate, lithium manganate and the like, and has extremely high applicability.
Description
Technical Field
The invention relates to the field of comprehensive recycling of retired lithium batteries, in particular to a method for recycling electrolyte and selectively extracting metal of retired lithium batteries.
Background
The lithium battery has the advantages of high energy density, long service life, environmental friendliness and the like, and is a novel energy source which has the highest prospect for replacing the traditional energy source. At present, the lithium ion battery is widely applied to the fields of new energy automobiles, energy storage, medical treatment and the like, and particularly the power battery of the new energy automobiles is rapidly developed. However, the service life of the lithium ion battery is about 3-5 years, a large number of retired lithium batteries are generated, and the lithium batteries contain strategic metal resources such as lithium, cobalt and the like, and also contain harmful components such as lithium hexafluorophosphate, an organic electrolyte solvent and the like, so that the retired lithium batteries are recycled, thereby being beneficial to protecting the environment and saving the resources.
The weight ratio of the electrolyte in the lithium battery exceeds 10 percent, and the retired lithium battery electrolyte is difficult to recycle because the electrolyte components change in the battery operation process. The existing electrolyte treatment technology is mainly divided into two modes of wet treatment and heat treatment. The wet treatment process mainly comprises the steps of crushing, cleaning and the like, namely transferring the electrolyte into liquid, then recovering lithium element in the electrolyte in a precipitation mode, and further carrying out harmless treatment on the rest waste liquid. The heat treatment process is to directly pyrolyze or burn the retired lithium battery, wherein the pyrolysis process comprises a plurality of steps of pyrolysis, condensation collection, tail gas treatment and the like, and the burning process comprises steps of burning, tail gas treatment and the like. No matter the wet method or the heat treatment mode, the existing retired lithium battery electrolyte treatment mode has the problems of complex dioxin release and harmless treatment process, resource waste and the like.
At present, a method for recovering lithium in a positive electrode material of a retired lithium battery mainly comprises an acid leaching process. The basic process is that the anode material of the retired lithium battery is dissolved in inorganic acid, and then the leaching solution is regulated to be alkaline, so that lithium ions in the leaching solution form precipitate and are recovered. However, since the positive electrode material of the retired lithium battery contains elements such as nickel, cobalt, manganese, aluminum and the like in addition to lithium elements, and meanwhile, since the leaching selectivity of inorganic acid is weak, metals such as nickel, cobalt, manganese, aluminum and the like in the positive electrode material are leached synchronously, and before lithium ions are recovered in leaching liquid, the metal ions such as nickel, cobalt, manganese, aluminum and the like are separated through complex processes such as impurity removal, multistage extraction and the like, so that the problems of complex recovery process, low lithium recovery rate and the like are caused.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a method for recycling the electrolyte of a retired lithium battery and selectively extracting metals.
The technical scheme of the invention is as follows:
the method comprises the steps of shearing and crushing a discharged retired lithium battery, evaporating at a low temperature under the protection of inert gas, absorbing phosphorus and fluorine by a calcium oxide solution through gas matters escaped in the evaporation process, adding a carbonic acid solution into the absorption solution for neutralization treatment, and filtering and separating to obtain an aqueous solution of the electrolyte; and (3) putting the positive electrode material obtained from the retired lithium battery subjected to low-temperature evaporation treatment into an aqueous solution of electrolyte for leaching, and filtering to obtain a lithium-rich solution and leaching residues.
As a preferable scheme of the invention, the retired lithium battery is any one or the combination of at least two of nickel cobalt lithium manganate ternary, nickel cobalt lithium aluminate, lithium manganate or lithium cobaltate batteries.
As a preferable scheme of the invention, the evaporation temperature is 105-165 ℃ and the evaporation time is 0.5-3h.
As a preferable scheme of the invention, the positive electrode material is any one or a combination of at least two of nickel cobalt lithium manganate ternary positive electrode material, nickel cobalt lithium aluminate positive electrode material, lithium manganate positive electrode material and lithium cobaltate positive electrode material.
As a preferred scheme of the present invention, the method for obtaining the positive electrode material specifically includes: and disassembling the retired lithium battery subjected to low-temperature evaporation treatment to collect the positive plate, and crushing and sorting the positive plate to obtain the positive material.
As a preferred embodiment of the present invention, the leaching conditions are: the concentration of the electrolyte in the aqueous solution is 10-70wt%.
As a preferred embodiment of the present invention, the leaching conditions are: the solid-liquid ratio of the positive electrode material and the aqueous solution of the electrolyte is 5-125g/L.
As a preferred embodiment of the present invention, the leaching conditions are: the leaching temperature is 160-270 ℃ and the leaching time is 3-10h.
According to the invention, electrolyte in the retired lithium battery is recovered through low-temperature evaporation, and then an aqueous solution of the electrolyte after removing fluorine and phosphorus is taken as a leaching medium, so that the harmless conversion of the electrolyte and the metal leaching in the anode material can be realized in one step based on the principle that organic matters (carbonate solvents, organic additives and the like) in the electrolyte are firstly converted into weak acids and carbonates and then are converted into harmless substances (carbon dioxide, water and the like) in a subcritical water system, and the anode material is put into the subcritical aqueous solution of the electrolyte. In addition, except lithium element, cobalt, nickel, manganese, aluminum and other metal ions dissolved in the solution during leaching are synchronously combined with carbonate and hydroxide to generate water-insoluble compounds, so that when the leaching reaction is finished, metals except lithium in the positive electrode material exist in the leaching solution in a solid form.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method for recycling the electrolyte of the retired lithium battery and selectively extracting the metal, the electrolyte of the retired lithium battery can be safely and environmentally recycled, and meanwhile, the recycled electrolyte is used for selectively extracting the lithium element in the positive electrode material, so that the efficient utilization of the electrolyte is realized.
(2) The method for recycling the electrolyte of the retired lithium battery and selectively extracting the metal can treat different types of retired lithium batteries, and the provided method for selectively recycling the lithium in the anode material of the retired lithium battery has the advantages of short flow, easy realization of industrial process and strong technical applicability.
(3) According to the recycling and metal selective extraction method of the retired lithium battery electrolyte, the extraction rate of lithium is high (more than 97%), the impurity content is low (the leaching rate of metal elements such as nickel, cobalt, manganese and aluminum in the positive electrode material is lower than 0.5%), and the lithium-rich solution obtained by the method is easy to prepare battery grade lithium carbonate.
(4) According to the method for recycling the electrolyte and selectively extracting the metal of the retired lithium battery, provided by the invention, the process of the method for selectively recycling the lithium in the positive electrode material by taking the recycled electrolyte as a leaching medium is clean, no waste water and waste gas are discharged, lithium ions in the leaching solution can be recycled in a precipitation manner, and the leaching medium can be recycled, so that the harm of electrolyte components in the retired lithium battery to the environment is avoided.
Detailed Description
A method for recycling and selectively extracting metal from electrolyte of retired lithium battery comprises the following steps:
step 1: and shearing and crushing the discharged retired lithium battery, performing low-temperature evaporation under the protection of inert gas, absorbing phosphorus and fluorine by gas substances escaped in the evaporation process through a calcium oxide solution, adding a carbonic acid solution into the absorption solution for neutralization treatment, and filtering and separating to obtain an aqueous solution of the electrolyte, wherein the aqueous solution of the electrolyte is used as a selective extraction solvent of lithium in the anode material. Disassembling and collecting a positive plate of the retired lithium battery subjected to low-temperature evaporation treatment, and crushing and sorting to obtain a positive material;
step 2: and (3) putting the positive electrode material obtained in the step (1) into the obtained aqueous solution for leaching, and filtering to obtain a lithium-rich solution and leaching residues.
As a preferable technical scheme of the invention, the retired lithium battery in the step 1 is any one or a combination of at least two of nickel cobalt lithium manganate ternary, nickel cobalt lithium aluminate, lithium manganate or lithium cobaltate batteries.
As a preferred embodiment of the present invention, the evaporation temperature in step 1 is 105 to 165℃such as 105℃115℃130℃145℃165℃or the like, but is not limited to the values listed, and other values not listed in the range are applicable, preferably 110 to 160 ℃.
As a preferred embodiment of the present invention, the evaporation time in step 1 is 0.5 to 3 hours, for example, 0.5 hours, 1 hour, 2 hours, 2.5 hours or 3 hours, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable, preferably 1 to 2.5 hours.
As a preferable technical scheme of the invention, the positive electrode material of the retired lithium battery in the step 1 is any one or a combination of at least two of a nickel cobalt lithium manganate ternary material, a nickel cobalt lithium aluminate ternary material, a lithium manganate material and a lithium cobaltate material.
As a preferred embodiment of the present invention, the leaching temperature in the step 2 is 160 to 270 ℃, for example 160 to 180 to 210 to 230 to 270 ℃, etc., but not limited to the values listed, and other values not listed in the range are applicable, preferably 170 to 260 ℃.
As a preferred embodiment of the present invention, the leaching time in step 2 is 3 to 10 hours, for example, 3 hours, 5 hours, 7 hours, 9 hours or 10 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable, preferably 4 to 10 hours.
As a preferred embodiment of the present invention, the concentration of the electrolyte in the aqueous solution of the electrolyte in the leaching process of step 2 is 10 to 70wt%, for example, 10wt%, 25wt%, 35wt%, 50wt%, 60wt% or 70wt%, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably 15 to 65wt%.
As a preferred technical scheme of the invention, the solid-to-liquid ratio of the positive electrode material to the electrolyte in the leaching process in the step 2 is 5-125g/L, for example, 5g/L, 25g/L, 40g/L, 80g/L, 100g/L, 125g/L, etc., but the leaching process is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, preferably 10-100g/L.
The technical scheme of the invention is further described in the following specific examples.
The following formula for calculating the leaching rate is as follows:
leaching rate calculation formula = (concentration of certain element in leaching solution x volume of leaching solution)/total mass of certain element in raw material.
Example 1
Shearing and crushing a discharged retired nickel cobalt lithium manganate battery, evaporating the battery at a low temperature of 110 ℃ for 2.5 hours under the protection of nitrogen, absorbing phosphorus and fluorine by a calcium oxide solution with the concentration of 20wt%, adding a carbonic acid solution with the concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 15wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the retired lithium manganate battery after the low temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into an aqueous solution with the concentration of 15wt% of the obtained electrolyte according to the solid-to-liquid ratio of 10g/L, leaching the solution and leaching residues after filtering at the temperature of 170 ℃ for 10 hours, and obtaining lithium-rich solution and leaching residues after detection calculation, wherein the leaching rate of the obtained lithium element reaches 98.3%, and the leaching rates of nickel, cobalt and manganese are respectively 0.15%, 0.02% and 0.18%.
Example 2
Shearing and crushing a discharged retired nickel cobalt lithium manganate battery, evaporating the battery for 1h at a low temperature of 160 ℃ under the protection of nitrogen gas, absorbing phosphorus and fluorine by a calcium oxide solution with the concentration of 20wt%, adding a carbonic acid solution with the concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 65wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the retired lithium manganate battery after the low temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into an aqueous solution with the concentration of 65wt% of the obtained electrolyte according to the solid-to-liquid ratio of 100g/L, filtering at the temperature of 260 ℃ for 4h, obtaining a lithium-rich solution and leaching residues, and detecting and calculating that the leaching rates of the obtained lithium elements in the embodiment reach 97.5%, and leaching rates of nickel, cobalt and manganese are 0.17%, 0.05% and 0.21% respectively.
Example 3
Cutting and crushing a discharged retired nickel cobalt lithium manganate battery, evaporating the battery for 1.5 hours at a low temperature of 150 ℃ under the protection of inert gas, absorbing phosphorus and fluorine by a calcium oxide solution with the concentration of 20wt%, adding a carbonic acid solution with the concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 50wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the positive electrode plate after the low-temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into an aqueous solution with the concentration of 50wt% of the obtained electrolyte according to the solid-to-liquid ratio of 40g/L, leaching the solution at the temperature of 200 ℃ for 5 hours, filtering to obtain a lithium-rich solution and leaching residues, and obtaining lithium element leaching rates of 98.9%, wherein the leaching rates of nickel, cobalt and manganese are respectively 0.13%, 0.01% and 0.16% through detection calculation.
Example 4
Cutting and crushing a discharged retired nickel cobalt lithium aluminate battery, evaporating the battery for 2.0 hours at a low temperature of 130 ℃ under the protection of inert gas, absorbing phosphorus and fluorine by a calcium oxide solution with the concentration of 20wt%, adding a carbonic acid solution with the concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 40wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the retired lithium battery after the low-temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into an aqueous solution with the concentration of 40wt% of the obtained electrolyte according to the solid-to-liquid ratio of 25g/L, leaching the solution at the temperature of 220 ℃ for 4.5 hours, filtering to obtain a lithium-rich solution and leaching residues, and detecting and calculating to obtain the leaching rates of 98.1 percent of lithium elements, wherein the leaching rates of nickel, cobalt and aluminum are 0.11 percent, 0.04 percent and 0.26 percent respectively.
Example 5
Cutting and crushing a discharged retired lithium cobalt oxide battery, evaporating the battery for 2.0 hours at a low temperature of 130 ℃ under the protection of inert gas, absorbing phosphorus and fluorine by a calcium oxide solution with the concentration of 20wt%, adding a carbonic acid solution with the concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 35wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the positive electrode plate by the retired lithium battery after the low-temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into the aqueous solution with the concentration of 35wt% of the obtained electrolyte according to the solid-to-liquid ratio of 30g/L, leaching the solution and leaching residues after filtering at the temperature of 190 ℃ for 8 hours, and obtaining the lithium-rich solution and the leaching residues after detection calculation, wherein the leaching rate of the obtained lithium element reaches 99.1% and the cobalt leaching rate is 0.13%.
Example 6
Shearing and crushing a discharged retired lithium manganate battery, evaporating the discharged retired lithium manganate battery at a low temperature for 2.5 hours at a temperature of 120 ℃ under the protection of inert gas, absorbing phosphorus and fluorine by a calcium oxide solution with a concentration of 20wt%, adding a carbonic acid solution with a concentration of 15wt% into the absorption solution for neutralization treatment, filtering and separating to obtain an aqueous solution of electrolyte, diluting the concentration of the electrolyte in the obtained aqueous solution to 45wt%, taking the aqueous solution as a selective extraction solvent of lithium in a positive electrode material, disassembling and collecting the retired lithium battery after the low-temperature evaporation treatment, crushing and sorting to obtain the positive electrode material, putting the obtained positive electrode material into an aqueous solution with a concentration of 20g/L of 45wt% of the obtained electrolyte at a solid-to-liquid ratio for 3 hours at a temperature of 230 ℃, filtering to obtain a lithium-rich solution and leaching residues, and detecting and calculating that the leaching rate of lithium element obtained in the embodiment reaches 99.3% and the leaching rate of manganese is 0.31%.
In summary, the extraction rate of lithium in the embodiment is high and is more than 97%, and the leaching rate of nickel and/or cobalt and/or manganese and/or aluminum and other metal elements in the positive electrode material is lower than 0.5%, which indicates that the impurities are low, and the lithium-rich solution obtained by the invention is easier to prepare battery-grade lithium carbonate.
The method for selectively recovering lithium in the positive electrode material by taking the recovered electrolyte as the leaching medium has the advantages of clean process, no wastewater and waste gas emission, precipitation recovery of lithium ions in the leaching solution, recycling of the leaching medium, and environmental hazard of electrolyte components in the retired lithium battery.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A method for recycling electrolyte of retired lithium battery and selectively extracting metal is characterized in that shearing and crushing the retired lithium battery after discharging, evaporating at low temperature under the protection of inert gas, absorbing phosphorus and fluorine by gas matters escaped in the evaporation process through calcium oxide solution, adding carbonic acid solution into the absorption solution for neutralization treatment, and filtering and separating to obtain aqueous solution of the electrolyte; and (3) putting the positive electrode material obtained from the retired lithium battery subjected to low-temperature evaporation treatment into an aqueous solution of electrolyte for leaching, and filtering to obtain a lithium-rich solution and leaching residues.
2. The method for recycling electrolyte and selectively extracting metal from a retired lithium battery according to claim 1, wherein the retired lithium battery is any one or a combination of at least two of a nickel cobalt lithium manganate ternary battery, a nickel cobalt lithium aluminate battery, a lithium manganate battery and a lithium cobaltate battery.
3. The method for recycling and selectively extracting metal from the electrolyte of the retired lithium battery according to claim 1, wherein the evaporating temperature is 105-165 ℃ and the evaporating time is 0.5-3h.
4. The method for recycling and selectively extracting metal from retired lithium battery electrolyte according to claim 1, wherein the positive electrode material is any one or a combination of at least two of nickel cobalt lithium manganate ternary positive electrode material, nickel cobalt lithium aluminate positive electrode material, lithium manganate positive electrode material and lithium cobaltate positive electrode material.
5. The method for recycling and selectively extracting metal from the electrolyte of the retired lithium battery according to claim 1, wherein the method for obtaining the positive electrode material is specifically as follows: and disassembling the retired lithium battery subjected to low-temperature evaporation treatment to collect the positive plate, and crushing and sorting the positive plate to obtain the positive material.
6. The method for recycling and selectively extracting metals from retired lithium battery electrolyte according to claim 1, wherein the leaching conditions are as follows: the concentration of the electrolyte in the aqueous solution is 10-70wt%.
7. The method for recycling and selectively extracting metals from retired lithium battery electrolyte according to claim 1, wherein the leaching conditions are as follows: the solid-liquid ratio of the positive electrode material and the aqueous solution of the electrolyte is 5-125g/L.
8. The method for recycling and selectively extracting metals from retired lithium battery electrolyte according to claim 1, wherein the leaching conditions are as follows: the leaching temperature is 160-270 ℃ and the leaching time is 3-10h.
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