CN116397110B - Method for recycling lithium from waste lithium iron phosphate battery - Google Patents
Method for recycling lithium from waste lithium iron phosphate battery Download PDFInfo
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- CN116397110B CN116397110B CN202310607912.4A CN202310607912A CN116397110B CN 116397110 B CN116397110 B CN 116397110B CN 202310607912 A CN202310607912 A CN 202310607912A CN 116397110 B CN116397110 B CN 116397110B
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- iron phosphate
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 84
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000001914 filtration Methods 0.000 claims abstract description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011259 mixed solution Substances 0.000 claims abstract description 45
- 239000010413 mother solution Substances 0.000 claims abstract description 41
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012452 mother liquor Substances 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- 239000011888 foil Substances 0.000 claims abstract description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims description 80
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000005955 Ferric phosphate Substances 0.000 claims description 11
- 229940032958 ferric phosphate Drugs 0.000 claims description 11
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 68
- 229910052742 iron Inorganic materials 0.000 abstract description 34
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000002689 soil Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a method for recycling lithium from waste lithium iron phosphate batteries, and belongs to the technical field of lithium battery recycling. According to the invention, after the waste lithium iron phosphate battery is discharged, manual disassembly is carried out, electrolyte is evaporated, ultrasound is carried out in the mixed solution, after aluminum foil is separated, the mixed solution is filtered, filter residues are taken to react with hydrochloric acid in the presence of chlorine, leaching residues and leaching mother liquor are obtained after filtration, leaching mother liquor is added with alkali for reaction and filtration to obtain iron precipitation residues and iron precipitation mother liquor, the leaching residues are continuously subjected to hydrochloric acid reaction step and alkali adding reaction step successively, and finally, the iron phosphate is recovered by combining the two iron precipitation residues, and lithium carbonate is recovered by precipitating lithium of the iron precipitation mother liquor. The mixed solution contains dimethyl sulfoxide, dimethylformamide and polyethylene glycol, and the three components cooperate to promote the dissolution of the binder so as to promote the separation of aluminum foil and active substances and improve the recovery rate of lithium; and leaching the leaching residue A for the second time by using the iron-precipitating mother solution A, so that the concentration of lithium ions in the iron-precipitating mother solution B is increased, and the leaching rate of lithium is increased.
Description
Technical Field
The invention belongs to the technical field of lithium battery recycling, and relates to a method for recycling lithium from waste lithium iron phosphate batteries.
Background
In recent years, new energy automobiles and power storage batteries have been rapidly developed due to the increasing environmental pollution and energy crisis problems, and the power storage batteries include lead-acid storage batteries, nickel-hydrogen power batteries and lithium ion power batteries, wherein the lithium ion power batteries with high energy density and cycle characteristics are known as the best development direction of the power storage batteries in the future. At present, the lithium ion power battery is mainly divided into a ternary power battery and a lithium iron phosphate battery by taking a positive electrode material as a distinction, wherein the lithium iron phosphate battery has the advantages of high energy density, long cycle life, high safety and the like, and is widely applied to the fields of electric automobiles, energy storage systems and the like.
The lithium iron phosphate battery is scrapped after a service life of 8-10 years after a certain cycle times, and the random discarding of the battery can pollute soil, so that the pH value of the environment is increased, and meanwhile, the waste of lithium resources can be caused. The lithium iron phosphate battery material mainly comprises a positive electrode material, a negative electrode material, electrolyte and a diaphragm, wherein the positive electrode material is the most main raw material for effectively recycling lithium resources, a positive electrode plate mainly comprises aluminum foil, lithium iron phosphate positive electrode powder, namely active substances, a binder and a conductive agent, the binder is polyvinylidene fluoride, and the conductive agent is ultrafine carbon powder. The method for recovering lithium from the lithium iron phosphate battery generally comprises a solid-phase method, a liquid-phase method, an oxygen pressure leaching method, a liquid-solid-phase method, a supercritical extraction method and the like, but the existing recovery method has high energy consumption, serious secondary environmental pollution and the recovery rate of lithium is to be improved.
Disclosure of Invention
The invention aims to provide a method for recycling lithium from waste lithium iron phosphate batteries, and belongs to the technical field of lithium battery recycling. According to the invention, the waste lithium iron phosphate battery is discharged and then is manually disassembled, a positive plate is taken to heat and evaporate residual electrolyte, then the electrolyte is placed into a mixed solution for ultrasonic treatment to remove a binder, so that aluminum foil and active substances are separated, the aluminum foil is taken out and washed and recycled, washing liquor is merged into the mixed solution containing the active substances, filter residues are taken to react with hydrochloric acid solution in the presence of chlorine and then filtered, leached slag A and leached mother liquor A are obtained, the leached mother liquor A is subjected to alkali reaction and filtered to obtain iron-precipitating slag A and iron-precipitating mother liquor A, hydrochloric acid solution is added into the iron-precipitating mother liquor A and reacts with the leached slag A under the condition of introducing chlorine, leached mother liquor B is subjected to alkali reaction and filtered to obtain iron-precipitating slag B and iron-precipitating mother liquor B, sodium carbonate is added into the iron-precipitating mother liquor B, and the iron-precipitating slag A and the iron-precipitating slag B are merged and the iron-precipitating slag B are recycled. The mixed solution contains dimethyl sulfoxide, dimethylformamide and polyethylene glycol, and the three components cooperate to promote the dissolution of the binder so as to promote the separation of aluminum foil and active substances and improve the recovery rate of lithium; and leaching the leaching residue A for the second time by using the iron-precipitating mother solution A, so that the concentration of lithium ions in the iron-precipitating mother solution B is increased, and the leaching rate of lithium is increased.
The aim of the invention can be achieved by the following technical scheme:
a method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Discharging the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to evaporate residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into the mixed solution, heating, performing ultrasonic treatment, and taking out the aluminum foil to obtain slurry;
(5) The aluminum foil is recycled after being washed by water, and the washing liquid is mixed with the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution into filter residues under the condition of introducing chlorine, stirring for reaction, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding sodium hydroxide aqueous solution into the leaching mother liquor A to adjust the pH value of the system to 3-4, stirring and reacting for 1-2h, and then filtering to obtain iron-precipitating slag A and iron-precipitating mother liquor A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, introducing chlorine, adding leaching slag A, stirring and reacting for 1-2h, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding sodium hydroxide aqueous solution into the leaching mother liquor B to adjust the pH value of the system to 3-4, stirring and reacting for 1-2h, and then filtering to obtain iron-precipitating slag B and iron-precipitating mother liquor B;
(10) And combining the iron-precipitating slag A and the iron-precipitating slag B, recovering iron phosphate, adding sodium carbonate into the iron-precipitating mother solution B, and filtering to obtain lithium carbonate.
As a preferred embodiment of the present invention, the discharging treatment in the step (1) means: immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 22-30%, completing discharging operation when the battery voltage is reduced to 0.2-0.3V, and taking out the waste lithium iron phosphate battery.
As a preferable technical scheme of the invention, the temperature of the heating in the step (3) is 90-110 ℃, and the evaporation time is controlled to be 2-5h.
As a preferable technical scheme of the invention, the mixed solution in the step (4) comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:0.8-1.8:1.2-2, and the dosage of the mixed solution is controlled to be just immersed into the positive plate.
As a preferable technical scheme of the invention, the temperature of the heating in the step (4) is 40-50 ℃, the ultrasonic frequency is 80-130kHz, and the ultrasonic time is 1-3h.
As a preferable technical scheme of the invention, the volume ratio of the washing liquid to the slurry in the step (5) is 0.8-2:1.
As a preferable technical scheme of the invention, the concentration of the hydrochloric acid aqueous solution in the step (6) is 6-9mol/L, the dosage of the hydrochloric acid aqueous solution is controlled to be just immersed in filter residues, the reaction time is 1.2-2.5h, and the stirring speed is 25-35rpm; the pressure of the reaction in the step (6) and the step (8) is 0.3-0.9MPa.
As a preferable technical scheme of the invention, the mass concentration of the sodium hydroxide aqueous solution in the step (7) and the step (9) is 30-45%, and the adding speed of the sodium hydroxide aqueous solution is controlled to be 8-12mL/min.
As a preferred embodiment of the present invention, the stirring speed in the steps (7), (8) and (9) is 25-35rpm.
As a preferable technical scheme of the invention, the adding amount of the sodium carbonate in the step (10) is controlled to be 10-11 of the pH value of the filtrate after filtering lithium carbonate.
The invention has the beneficial effects that:
(1) The positive plate of the lithium iron phosphate battery consists of aluminum foil, lithium iron phosphate active substances, adhesive polyvinylidene fluoride and conductive agent superfine carbon powder, wherein the adhesive polyvinylidene fluoride is used for bonding the lithium iron phosphate powder and the superfine carbon powder with the aluminum foil; simultaneously, the ultrasonic treatment not only promotes the mixed solution to be fully contacted with the polyvinylidene fluoride, but also promotes the separation of the lithium iron phosphate powder, the superfine carbon powder and the aluminum foil, and finally improves the recovery rate of lithium;
(2) The filter residue after the mixed solution is filtered is lithium iron phosphate containing superfine carbon powder, the filtrate is a mixed solution in which polyvinylidene fluoride is dissolved, the filter residue reacts with hydrochloric acid under the condition of introducing chlorine gas to decompose the lithium iron phosphate, the filtered leaching residue A is the superfine carbon powder and trace undegraded lithium iron phosphate, the leaching mother solution A is added with alkali to be adjusted to a corresponding pH range to precipitate ferric phosphate precipitate, the filtered iron precipitation residue A is the ferric phosphate residue, lithium ions enter the iron precipitation mother solution A, hydrochloric acid is added to the iron precipitation mother solution A to be adjusted to a corresponding pH range to introduce chlorine gas, and the leaching residue A is further added to decompose the residual lithium iron phosphate to continuously push the decomposition reaction to right, so that on one hand, the concentration of lithium ions in the iron precipitation mother solution B can be enriched and improved, the leaching rate of lithium is improved, and meanwhile, the recovery rate of ferric phosphate is also improved;
(3) The aluminum foil does not need to be crushed or smashed and does not need to be calcined, and the whole process can obviously reduce energy consumption; the aluminum foil can be directly recycled, the leaching slag B is used for recycling superfine carbon powder, the iron-precipitating slag A and the iron-precipitating slag B can be combined for recycling ferric phosphate, and finally the lithium carbonate is precipitated.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 25%, completing discharging operation when the battery voltage is reduced to 0.26V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 95 ℃ and keeping for 3 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 45 ℃, carrying out ultrasonic treatment for 2.5 hours at the frequency of 110kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:0.9:1.4;
(5) The aluminum foil is recycled after being washed, the volume ratio of the washed washing liquid to the slurry is controlled to be 0.9:1, and the washing liquid is mixed with the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 7mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2 hours under the condition of controlling the pressure to be 0.5MPa and the rotating speed of 30rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding 35% sodium hydroxide aqueous solution at a mass concentration of 10mL/min into the leaching mother liquor A to adjust the pH value of the system to 3-4, stirring at a rotating speed of 30rpm for reaction for 1h, and then filtering to obtain iron slag A and iron slag A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.5MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 30rpm for reaction for 1.5 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding 35% sodium hydroxide aqueous solution at a speed of 10mL/min into the leaching mother liquor B to adjust the pH value of the system to 3-4, stirring at a rotating speed of 30rpm for reaction for 1.8h, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The overall recovery rate of lithium in the positive electrode sheet of this example was 92.87%, and the purity of lithium carbonate was 99.25%.
Example 2
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 22%, completing discharging operation when the battery voltage is reduced to 0.3V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 110 ℃ and keeping for 2 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 40 ℃, carrying out ultrasonic treatment for 3 hours at the frequency of 130kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:1.5:2;
(5) The aluminum foil is recycled after being washed, the volume ratio of the washed washing liquid to the slurry is controlled to be 1.5:1, and the washing liquid is mixed with the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 6mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2.2 hours under the condition of controlling the pressure to be 0.8MPa and the rotating speed of 25rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding sodium hydroxide aqueous solution with mass concentration of 45% into the leaching mother liquor A at the speed of 8mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 35rpm for reaction for 1h, and then filtering to obtain iron precipitation slag A and iron precipitation mother liquor A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.8MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 30rpm for reaction for 2 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding a sodium hydroxide aqueous solution with the mass concentration of 30% into the leaching mother solution B at the speed of 12mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 25rpm for reaction for 2 hours, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The overall recovery rate of lithium in the positive electrode sheet of this example was 93.15%, and the purity of lithium carbonate was 99.37%.
Example 3
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 30%, completing discharging operation when the battery voltage is reduced to 0.2V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 90 ℃ and keeping for 5 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 50 ℃, performing ultrasonic treatment for 3 hours at the frequency of 80kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:1.8:1.2;
(5) The aluminum foil is recycled after being washed, the volume ratio of washing liquid to slurry after washing is controlled to be 2:1, and the washing liquid is mixed into the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 9mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2.5h under the condition of controlling the pressure to be 0.3MPa and the rotating speed of 35rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding a sodium hydroxide aqueous solution with the mass concentration of 30% into the leaching mother solution A at the speed of 12mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 25rpm for 2 hours, and then filtering to obtain iron slag A and iron slag A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.4MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 25rpm for reaction for 2 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding a sodium hydroxide aqueous solution with the mass concentration of 40% into the leaching mother solution B at the speed of 8mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 35rpm for reaction for 1.2h, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The overall recovery rate of lithium in the positive electrode sheet of this example was 92.24%, and the purity of lithium carbonate was 99.19%.
Comparative example 1
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 30%, completing discharging operation when the battery voltage is reduced to 0.2V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 90 ℃ and keeping for 5 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 50 ℃, performing ultrasonic treatment for 3 hours at the frequency of 80kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethyl sulfoxide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethyl sulfoxide to the polyethylene glycol is 2.8:1.2;
(5) The aluminum foil is recycled after being washed, the volume ratio of washing liquid to slurry after washing is controlled to be 2:1, and the washing liquid is mixed into the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 9mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2.5h under the condition of controlling the pressure to be 0.3MPa and the rotating speed of 35rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding a sodium hydroxide aqueous solution with the mass concentration of 30% into the leaching mother solution A at the speed of 12mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 25rpm for 2 hours, and then filtering to obtain iron slag A and iron slag A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.4MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 25rpm for reaction for 2 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding a sodium hydroxide aqueous solution with the mass concentration of 40% into the leaching mother solution B at the speed of 8mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 35rpm for reaction for 1.2h, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The overall recovery rate of lithium in the positive plate of this comparative example was 88.67%, and the purity of lithium carbonate was 98.37%.
Comparative example 2
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 30%, completing discharging operation when the battery voltage is reduced to 0.2V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 90 ℃ and keeping for 5 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 50 ℃, performing ultrasonic treatment for 3 hours at the frequency of 80kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethylformamide to the polyethylene glycol is 2.8:1.2;
(5) The aluminum foil is recycled after being washed, the volume ratio of washing liquid to slurry after washing is controlled to be 2:1, and the washing liquid is mixed into the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 9mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2.5h under the condition of controlling the pressure to be 0.3MPa and the rotating speed of 35rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding a sodium hydroxide aqueous solution with the mass concentration of 30% into the leaching mother solution A at the speed of 12mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 25rpm for 2 hours, and then filtering to obtain iron slag A and iron slag A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.4MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 25rpm for reaction for 2 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding a sodium hydroxide aqueous solution with the mass concentration of 40% into the leaching mother solution B at the speed of 8mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 35rpm for reaction for 1.2h, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The comprehensive recovery rate of lithium in the positive plate of the comparative example is 87.83%, and the purity of lithium carbonate is 98.24%.
Comparative example 3
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 30%, completing discharging operation when the battery voltage is reduced to 0.2V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 90 ℃ and keeping for 5 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 50 ℃, performing ultrasonic treatment for 3 hours at the frequency of 80kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution contains dimethyl sulfoxide and dimethylformamide, and the volume ratio of the dimethyl sulfoxide to the dimethylformamide is 1:3;
(5) The aluminum foil is recycled after being washed, the volume ratio of washing liquid to slurry after washing is controlled to be 2:1, and the washing liquid is mixed into the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 9mol/L into filter residues under the condition of introducing chlorine, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, stirring and reacting for 2.5h under the condition of controlling the pressure to be 0.3MPa and the rotating speed of 35rpm, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding a sodium hydroxide aqueous solution with the mass concentration of 30% into the leaching mother solution A at the speed of 12mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 25rpm for 2 hours, and then filtering to obtain iron slag A and iron slag A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, controlling the pressure to be 0.4MPa, adding leaching slag A after introducing chlorine, stirring at a rotating speed of 25rpm for reaction for 2 hours, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding a sodium hydroxide aqueous solution with the mass concentration of 40% into the leaching mother solution B at the speed of 8mL/min to adjust the pH value of the system to 3-4, stirring at the rotating speed of 35rpm for reaction for 1.2h, and then filtering to obtain iron slag B and iron slag B;
(10) And (3) combining the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, filtering to obtain lithium carbonate, and controlling the pH value of the filtered filtrate to be 10-11.
The overall recovery rate of lithium in the positive plate of the comparative example was 85.07%, and the purity of lithium carbonate was 98.09%.
Comparative example 4
A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 30%, completing discharging operation when the battery voltage is reduced to 0.2V, and taking out the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to 90 ℃ and keeping for 5 hours, and evaporating residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into a mixed solution, enabling the mixed solution to just submerge the positive plate, heating to 50 ℃, performing ultrasonic treatment for 3 hours at the frequency of 80kHz, taking out the aluminum foil to obtain slurry, wherein the mixed solution comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, the molecular weight of the polyethylene glycol is 400-600, and the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:1.8:1.2;
(5) The aluminum foil is recycled after being washed, the volume ratio of washing liquid to slurry after washing is controlled to be 2:1, and the washing liquid is mixed into the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution with the concentration of 9mol/L into filter residues under the condition of introducing chlorine gas, enabling the hydrochloric acid aqueous solution to just submerge the filter residues, controlling the pressure to be 0.3MPa, stirring and reacting for 2.5h at the speed of 35rpm, and then filtering to obtain leaching residues and leaching mother liquor, wherein the leaching residues are used for recycling superfine carbon powder;
(7) Adding 30% sodium hydroxide aqueous solution at a mass concentration of 12mL/min into the leaching mother liquor, regulating the pH value of the system to 3-4, stirring at a rotating speed of 25rpm for reaction for 2 hours, and then filtering to obtain iron slag and iron slag mother liquor;
(8) The iron-precipitating slag is used for recovering ferric phosphate, sodium carbonate is added into the iron-precipitating mother liquor, lithium carbonate is obtained by filtering, and the pH value of the filtered filtrate is controlled to be 10-11.
The comprehensive recovery rate of lithium in the positive plate of the comparative example is 82.35%, and the purity of lithium carbonate is 99.08%.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. A method for recovering lithium from a spent lithium iron phosphate battery, the method comprising the steps of:
(1) Discharging the waste lithium iron phosphate battery;
(2) Manually disassembling the discharged waste lithium iron phosphate battery and taking out the positive plate;
(3) Heating the positive plate to evaporate residual electrolyte;
(4) Putting the positive plate from which the electrolyte is evaporated into the mixed solution, heating, performing ultrasonic treatment, and taking out the aluminum foil to obtain slurry;
(5) The aluminum foil is recycled after being washed by water, and the washing liquid is mixed with the slurry to obtain mixed liquid;
(6) Filtering the mixed solution, adding a hydrochloric acid aqueous solution into filter residues under the condition of introducing chlorine, stirring for reaction, and then filtering to obtain leaching residue A and leaching mother liquor A;
(7) Adding sodium hydroxide aqueous solution into the leaching mother liquor A to adjust the pH value of the system to 3-4, stirring and reacting for 1-2h, and then filtering to obtain iron-precipitating slag A and iron-precipitating mother liquor A;
(8) Adding an aqueous hydrochloric acid solution into the iron-precipitating mother solution A until the pH value of the system is 1-2, introducing chlorine, adding leaching slag A, stirring and reacting for 1-2h, and filtering to obtain leaching slag B and leaching mother solution B, wherein the leaching slag B is used for recycling superfine carbon powder;
(9) Adding sodium hydroxide aqueous solution into the leaching mother liquor B to adjust the pH value of the system to 3-4, stirring and reacting for 1-2h, and then filtering to obtain iron-precipitating slag B and iron-precipitating mother liquor B;
(10) Mixing the iron-precipitating slag A and the iron-precipitating slag B to recover ferric phosphate, adding sodium carbonate into the iron-precipitating mother solution B, and filtering to obtain lithium carbonate;
the mixed solution in the step (4) comprises dimethyl sulfoxide, dimethylformamide and polyethylene glycol, wherein the molecular weight of the polyethylene glycol is 400-600, the volume ratio of the dimethyl sulfoxide to the dimethylformamide to the polyethylene glycol is 1:0.8-1.8:1.2-2, the dosage of the mixed solution is controlled to be just immersed into a positive plate, the temperature for heating is 40-50 ℃, the ultrasonic frequency is 80-130kHz, and the ultrasonic time is 1-3h;
the concentration of the hydrochloric acid aqueous solution in the step (6) is 6-9mol/L, the dosage of the hydrochloric acid aqueous solution is controlled to be just immersed into filter residues, the reaction time is 1.2-2.5h, and the stirring speed is 25-35rpm; the pressure of the reaction in the step (6) and the step (8) is 0.3-0.9MPa;
the mass concentration of the sodium hydroxide aqueous solution in the step (7) and the step (9) is 30-45%, and the adding speed of the sodium hydroxide aqueous solution is controlled to be 8-12mL/min.
2. The method for recovering lithium from a waste lithium iron phosphate battery according to claim 1, wherein the discharging treatment in the step (1) is: immersing the waste lithium iron phosphate battery in a sodium chloride aqueous solution with the mass concentration of 22-30%, completing discharging operation when the battery voltage is reduced to 0.2-0.3V, and taking out the waste lithium iron phosphate battery.
3. The method for recovering lithium from waste lithium iron phosphate battery according to claim 1, wherein the temperature of the temperature rise in the step (3) is 90-110 ℃, and the evaporation time is controlled to be 2-5h.
4. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the volume ratio of the washing liquid to the slurry in the step (5) is 0.8-2:1.
5. The method for recovering lithium from waste lithium iron phosphate battery according to claim 1, wherein the stirring speed in step (7), step (8) and step (9) is 25-35rpm.
6. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the addition amount of sodium carbonate in the step (10) is controlled to be 10-11 of the pH value of the filtrate after filtering lithium carbonate.
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