CN116646633A - Method for recycling active substances in lithium ion positive electrode material - Google Patents
Method for recycling active substances in lithium ion positive electrode material Download PDFInfo
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- CN116646633A CN116646633A CN202310632179.1A CN202310632179A CN116646633A CN 116646633 A CN116646633 A CN 116646633A CN 202310632179 A CN202310632179 A CN 202310632179A CN 116646633 A CN116646633 A CN 116646633A
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- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 239000013543 active substance Substances 0.000 title abstract description 12
- 238000004064 recycling Methods 0.000 title abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 129
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000010941 cobalt Substances 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 32
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 29
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 101
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000000706 filtrate Substances 0.000 claims description 48
- 239000002244 precipitate Substances 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000011149 active material Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000010926 waste battery Substances 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002912 waste gas 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
-
- 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
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
Abstract
The invention relates to a method for recycling active substances in a lithium ion positive electrode material, and belongs to the technical field of waste battery material recycling. According to the method, the cobalt, nickel, manganese and lithium materials in the positive electrode material are recovered by leaching the positive electrode material twice and then precipitating in a fractional manner, so that the leaching rate and the recovery rate are high, and the coprecipitation problem in the traditional fractional extraction of metal ions is relieved to a great extent; in the invention by NH 3 ·H 2 O solution and (NH) 4 ) 2 C 2 O 4 Alkaline leaching and H 2 SO 4 Solution and H 2 O 2 The acid leaching realizes the full leaching of the active substances of the positive electrode, and the leaching rates of cobalt, nickel, manganese and lithium are all above 98 percent; the invention uses the extractant P507, lix54 and Lix984 to effectively separate the positive electrode under the mutual synergistic effectCopper and aluminum impurities, and can control other positive electrode active substances carried out by the clamp at a lower level; the invention uses triethanolamine and thioglycollic acid, and can synergistically separate cobalt and nickel.
Description
Technical Field
The invention belongs to the technical field of waste battery material recovery, and particularly relates to a method for recovering active substances in a lithium ion anode material.
Background
Waste lithium ion batteries are classified as dangerous solid wastes, and if the waste lithium ion batteries are directly discarded or disposed of, the waste lithium ion batteries bring great potential safety hazards to the ecological environment and people. Meanwhile, the content of valuable metals such as lithium, cobalt, nickel, manganese and the like in the abundant waste lithium ion battery is higher than that of natural ores, and the valuable recycled metals are likely to be beneficial to the protection and utilization of resources and greatly relieve the problem of shortage of lithium, cobalt and nickel resources. The recycling of the positive electrode material can generate multiple benefits such as resources, environment and the like.
Currently, the methods for positive electrode active material recovery include wet recovery, pyrogenic recovery, biological recovery, and the like. Wherein, the pyrometallurgy recovery is to remove substances such as binder and the like through high-temperature roasting, and finally separate active substances, but the pyrometallurgy not only generates harmful waste gas, but also has lower recovery efficiency and larger energy consumption. Biological leaching has the advantages of environmental protection, high efficiency and low cost, has a certain development potential, but bacteria used for leaching are difficult to culture, and the recovery period is long, so that the method is not suitable for large-scale industrial application.
The wet leaching can effectively recycle valuable metal elements in the waste ternary cathode material, and the valuable metal elements are transferred into a solution through acid leaching, alkaline leaching or ammonia leaching and the like, and the product is obtained through subsequent separation and purification. Hydrometallurgy has the characteristics of low energy consumption, easy regulation and control of the reaction process, high recovery efficiency and the like, so that the waste lithium ion batteries are recovered by adopting a hydrometallurgy technology in a plurality of recovery schemes.
The chemical precipitation method is a method of adding a proper precipitant to a metal leaching solution to react and produce precipitation, thereby realizing metal ion separation. The chemical precipitation method has the advantages of low equipment requirement, low cost, simple operation and the like, and metal ions in the solution are subjected to fractional precipitation to obtain metal precipitates separated at all levels, so that separation is realized. However, since the leaching solution contains a plurality of metal ions, cobalt and nickel are easy to co-precipitate, and are difficult to separate.
Disclosure of Invention
The invention relates to a method for recycling active substances in a lithium ion positive electrode material, and belongs to the technical field of waste battery material recycling. According to the method, the cobalt, nickel, manganese and lithium materials in the positive electrode material are recovered by leaching the positive electrode material twice and then precipitating in a fractional manner, so that the leaching rate and the recovery rate are high, and the coprecipitation problem in the traditional fractional extraction of metal ions is relieved to a great extent; in the invention byNH 3 ·H 2 O solution and (NH) 4 ) 2 C 2 O 4 Alkaline leaching and H 2 SO 4 Solution and H 2 O 2 The acid leaching realizes the full leaching of the active substances of the positive electrode, and the leaching rates of cobalt, nickel, manganese and lithium are all above 98 percent; according to the invention, the extracting agents P507, lix54 and Lix984 are used, so that impurity copper and aluminum in the positive electrode can be effectively separated under the mutual synergistic effect, and other positive electrode active substances carried out by clamping can be controlled at a lower level; the invention uses triethanolamine and thioglycollic acid, and can synergistically separate cobalt and nickel.
The aim of the invention can be achieved by the following technical scheme:
a method for recovering active materials in a lithium ion positive electrode material, comprising the following steps of:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid;
step three: acid leaching is carried out on the residues after alkaline leaching to obtain acid leaching solution;
step four: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 1.95-2.05mol/L H 2 SO 4 Back extraction of the solution;
step five: adding H into alkali leaching solution 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate;
step six: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 The solution is prepared by mixing sulfuric acid with NH at 18-22deg.C 3 ·H 2 O adjusts the pH value of the solution to be more than 11, and the solution is stood and filtered to obtain filtrate B and oxides and hydroxides of manganese precipitate;
step seven: adding triethanolamine and thioglycollic acid into the filtrate B, standing, and adding Na 2 CO 3 Dripping with NaOH by parallel flow method, and filtering to obtainPrecipitating filtrate C and basic lithium carbonate;
step eight: adding triethanolamine and thioglycollic acid into the filtrate A, mixing with the filtrate C, and mixing until the molar ratio of NaOH to cobalt is 28-32:1; heating, recovering evaporated ammonia gas, and filtering to obtain filtrate D and cobalt oxide and hydroxide precipitate;
step nine: treating the filtrate D with Fenton method, and treating with NiFe 2 O 4 Nickel is recovered in the form.
As a preferable scheme of the invention, in the second step, the alkaline leaching reagent is NH 3 ·H 2 O and (NH) 4 ) 2 C 2 O 4 In which the NH is 3 ·H 2 The concentration of O is 3.8-4.2mol/L, the concentration of the (NH) 4 ) 2 C 2 O 4 The concentration of the alkaline leaching agent is 1.6-1.8mol/L, the liquid-solid ratio of the alkaline leaching agent to the separated positive electrode material is 180-220mL/g, the alkaline leaching temperature is 22-26 ℃, and the alkaline leaching time is 60-70min.
As a preferable mode of the invention, the reagent used for acid leaching in the third step is H 2 SO 4 Solution and H 2 O 2 The H is 2 SO 4 The concentration of the solution is 2.2-2.6mol/L, and the H 2 SO 4 The liquid-solid ratio of the solution to the residue after alkaline leaching is 16-20mL/g, the H 2 O 2 And H is 2 SO 4 The volume ratio of the solution is 4.8-5.2:1, the temperature of the acid leaching is 125-135 ℃, and the time of the acid leaching is 120-150min.
As a preferable scheme of the invention, in the fourth step, the compound extractant is extractant P507, lix54, lix984 and kerosene, and the volume ratio of the extractant P507, lix54, lix984 and kerosene is 1:1:1:17-18.
As a preferred embodiment of the present invention, the method of step five is as described in the above H 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) to (3) to (1) is controlled.
As a preferred embodiment of the present invention, the NH in the step six 4 The molar ratio of the addition amount of Cl to the total amount of cobalt and nickel is 3-4:1, and the NH is 3 ·H 2 Addition amount of OThe mol ratio of the cobalt and the nickel is 6-8:1; the H is 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) is controlled to be 0.4-0.6:1.
As a preferable scheme of the invention, in the seventh step, the mol ratio of triethanolamine, thioglycollic acid and nickel is 1.1:1.1:1, the concentration of sodium carbonate solution is 0.02mol/L, the concentration of sodium hydroxide solution is 0.01mol/L, the volume ratio of sodium carbonate solution to sodium hydroxide solution is 1:1, and the sodium carbonate solution and sodium hydroxide solution are added in parallel flow, wherein the pH is controlled to 9.3-9.6, the temperature is 62-66 ℃, the stirring time is 24-36h, and Na is controlled 2 CO 3 The molar ratio of the lithium to the magnetic stirrer is controlled to be 1.1-1.2:1, and the rotating speed of the magnetic stirrer is set to be 800-1000r/min.
As a preferable scheme of the invention, the heating temperature in the step eight is 98-100 ℃, and the heating time is 100-120min; the mol ratio of the triethanolamine, the thioglycollic acid and the nickel is 1.1:1.
The invention has the beneficial effects that:
1. the invention provides a method for recycling active substances in a lithium ion positive electrode material, which is characterized in that the positive electrode material is leached twice, cobalt, nickel, manganese and lithium materials in the positive electrode material are recycled through fractional precipitation, so that the leaching rate and the recycling rate are high, and the coprecipitation problem in the traditional fractional extraction of metal ions is relieved to a great extent;
2. in the invention by NH 3 ·H 2 O solution and (NH) 4 ) 2 C 2 O 4 Alkaline leaching and H 2 SO 4 Solution and H 2 O 2 Acid leaching realizes full leaching of the anode active material; after alkaline leaching, nickel and cobalt are well separated selectively, insufficiently leached substances are separated out by an acid leaching method, and leaching rates of cobalt, nickel, manganese and lithium are all above 98%;
3. according to the invention, the composite extractant is used for treating the acid leaching solution after secondary leaching, copper and aluminum impurities in the anode are effectively separated under the mutual synergistic effect of the extractants P507, lix54 and Li x984, and other anode active substances carried by the clamp can be controlled at a lower level;
4. the invention uses the triethanolamine and the thioglycollic acid, can cooperatively separate cobalt and nickel, the triethanolamine and the thioglycollic acid can be complexed with nickel, the existence of nickel can be effectively masked in a small amount of cobalt-nickel mixture, cobalt is firstly precipitated, and the thioglycollic acid can not realize good separation effect under the condition of no triethanolamine and alkaline environment;
5. according to the invention, the recovery is realized through the complexation realized by ammonia water and the subsequent ammonia distillation, so that the resource waste is greatly reduced, and the resource recovery and utilization are realized.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for recovering active materials in a lithium ion positive electrode material, comprising the following steps of:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid; the alkaline leaching reagent is NH 3 ·H 2 O and (NH) 4 ) 2 C 2 O 4 In (2) mixed solution of NH 3 ·H 2 The concentration of the O solution was 3.8mol/L, (NH) 4 ) 2 C 2 O 4 The concentration of the solution is 1.6mol/L, the liquid-solid ratio of the alkaline leaching reagent to the separated positive electrode material is 180mL/g, the alkaline leaching temperature is 22 ℃, and the alkaline leaching time is 60min.
Step three: the residue after alkaline leaching is treated with H 2 SO 4 Solution and H 2 O 2 Acid leaching is carried out to obtain acid leaching solution; h 2 SO 4 The concentration of the solution is 2.2mol/L, H 2 SO 4 The liquid-solid ratio of the solution to the residue after alkaline leaching was 16mL/g, H 2 O 2 And H is 2 SO 4 The volume ratio of the solution is 4.82:1, the acid leaching temperature is 125-135 ℃, and the acid leaching time is 120min.
Step four: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 1.95mol/L H 2 SO 4 Back extraction of the solution; the composite extractant is extractant P507, lix54, lix984 and kerosene, and the volume ratio of the extractant P507, lix54, lix984 and kerosene is 1:1:1:17.
Step five: adding H into alkali leaching solution 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate; h 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) to (3) to (1) is controlled.
Step six: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 Solution, at 18℃with sulfuric acid and NH 3 ·H 2 O adjusts the pH value of the solution to be more than 11, and the solution is stood and filtered to obtain filtrate B and oxides and hydroxides of manganese precipitate; the NH is 4 C l to the total cobalt and nickel in a molar ratio of 3-4:1, NH being said 3 ·H 2 The molar ratio of the addition amount of O to the total amount of cobalt and nickel is 6-8:1; the H is 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) is controlled to be 0.4-0.6:1.
Step seven: adding triethanolamine and thioglycollic acid into the filtrate B, standing, and adding Na 2 CO 3 Dripping NaOH in parallel flow, filtering to obtain filtrate C and basic lithium carbonate precipitate; in the seventh step, the mol ratio of triethanolamine, thioglycollic acid and nickel is 1.1:1.1:1, the concentration of sodium carbonate solution is 0.02mol/L, the concentration of sodium hydroxide solution is 0.01mol/L, the volume ratio of sodium carbonate solution to sodium hydroxide solution is 1:1, pH is controlled to be 9.3-9.6, the temperature is 62 ℃, the stirring time is 24h, and Na is controlled in parallel flow adding 2 CO 3 The molar ratio of the lithium to the magnetic stirrer is controlled to be 1.1-1.2:1, and the rotating speed of the magnetic stirrer is set to be 800 r/min.
Step eight: adding triethanolamine and thioglycollic acid into the filtrate A, wherein the mol ratio of the triethanolamine to the thioglycollic acid to the nickel is 1.1:1, then mixing with the filtrate C, and the mol ratio of NaOH to the total cobalt is 28-32:1 after mixing; heating to 98deg.C for 100 min, recovering evaporated ammonia gas, and filtering to obtain filtrate D and cobalt oxide and hydroxide precipitate.
Step nine: treating filtrate D with Fenton method, and treating filtrate D with Ni Fe 2 O 4 Nickel is recovered in the form.
Example 2
A method for recovering active materials in a lithium ion positive electrode material, comprising the following steps of:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid; the alkaline leaching reagent is NH 3 ·H 2 O and (NH) 4 ) 2 C 2 O 4 In (2) mixed solution of NH 3 ·H 2 The concentration of the O solution was 4.0 mol/L, (NH) 4 ) 2 C 2 O 4 The concentration of the solution was 1.7 mol/L, the liquid-solid ratio of the alkaline leaching reagent to the separated positive electrode material was 200mL/g, the alkaline leaching temperature was 24℃and the alkaline leaching time was 65mi n.
Step three: the residue after alkaline leaching is treated with H 2 SO 4 Solution and H 2 O 2 Acid leaching is carried out to obtain acid leaching solution; h 2 SO 4 The concentration of the solution was 2.4 mol/L, H 2 SO 4 The liquid-solid ratio of the solution to the residue after alkaline leaching is 18mL/g, H 2 O 2 And H is 2 SO 4 The volume ratio of the solution is 5.0:1, the acid leaching temperature is 125-135 ℃, and the acid leaching time is 135min.
Step four: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 2.01mol/L H 2 SO 4 Back extraction of the solution; the compound extractant is extractant P507, lix54, lix984 and kerosene, wherein the extractant P507, lix54 and Lix9The volume ratio of 84 to kerosene was 1:1:1:17.4.
Step five: adding H into alkali leaching solution 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate; h 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) to (3) to (1) is controlled.
Step six: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 Solution, at 20 ℃, with sulfuric acid and NH 3 ·H 2 O adjusts the pH value of the solution to be more than 11, and the solution is stood and filtered to obtain filtrate B and oxides and hydroxides of manganese precipitate; the NH is 4 The molar ratio of the addition amount of Cl to the total amount of cobalt and nickel is 3-4:1, and the NH is 3 ·H 2 The molar ratio of the addition amount of O to the total amount of cobalt and nickel is 6-8:1; the H is 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) is controlled to be 0.4-0.6:1.
Step seven: adding triethanolamine and thioglycollic acid into the filtrate B, standing, and adding Na 2 CO 3 Dripping NaOH in parallel flow, filtering to obtain filtrate C and basic lithium carbonate precipitate; in the seventh step, the mol ratio of triethanolamine, thioglycollic acid and nickel is 1.1:1.1:1, the concentration of sodium carbonate solution is 0.02mol/L, the concentration of sodium hydroxide solution is 0.01mol/L, the volume ratio of sodium carbonate solution to sodium hydroxide solution is 1:1, and pH is controlled to 9.3-9.6, the temperature is 64 ℃ and the stirring time is 32h, na are added in parallel flow mode 2 CO 3 The molar ratio of the lithium to the magnetic stirrer is controlled to be 1.1-1.2:1, and the rotating speed of the magnetic stirrer is set to be 900r/min.
Step eight: adding triethanolamine and thioglycollic acid into the filtrate A, wherein the mol ratio of the triethanolamine to the thioglycollic acid to the nickel is 1.1:1, then mixing with the filtrate C, and the mol ratio of NaOH to the total cobalt is 28-32:1 after mixing; heating to 99deg.C for 110min, recovering evaporated ammonia gas, and filtering to obtain filtrate D and cobalt oxide and hydroxide precipitate.
Step nine: treating the filtrate D with Fenton method, and treating with NiFe 2 O 4 Nickel is recovered in the form.
Example 3
A method for recovering active materials in a lithium ion positive electrode material, comprising the following steps of:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid; the alkaline leaching reagent is NH 3 ·H 2 O and (NH) 4 ) 2 C 2 O 4 In (2) mixed solution of NH 3 ·H 2 The concentration of the O solution was 4.2mol/L, (NH) 4 ) 2 C 2 O 4 The concentration of the solution is 1.8mol/L, the liquid-solid ratio of the alkaline leaching reagent to the separated positive electrode material is 220mL/g, the alkaline leaching temperature is 26 ℃, and the alkaline leaching time is 70min.
Step three: the residue after alkaline leaching is treated with H 2 SO 4 Solution and H 2 O 2 Acid leaching is carried out to obtain acid leaching solution; h 2 SO 4 The concentration of the solution is 2.6mol/L, H 2 SO 4 The liquid-solid ratio of the solution to the residue after alkaline leaching is 20mL/g, H 2 O 2 And H is 2 SO 4 The volume ratio of the solution is 5.2:1, the acid leaching temperature is 125-135 ℃, and the acid leaching time is 150min.
Step four: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 2.04mol/L H 2 SO 4 Back extraction of the solution; the composite extractant is extractant P507, lix54, lix984 and kerosene, and the volume ratio of the extractant P507, lix54, lix984 and kerosene is 1:1:1:18.
Step five: adding H into alkali leaching solution 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate; h 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) to (3) to (1) is controlled.
Step six: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 Solution, at 22℃with sulfuric acid and NH 3 ·H 2 O regulationThe pH value of the solution is more than 11, and the solution is stood and filtered to obtain filtrate B and manganese oxide and hydroxide precipitate; the NH is 4 The molar ratio of the addition amount of Cl to the total amount of cobalt and nickel is 3-4:1, and the NH is 3 ·H 2 The molar ratio of the addition amount of O to the total amount of cobalt and nickel is 6-8:1; the H is 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) is controlled to be 0.4-0.6:1.
Step seven: adding triethanolamine and thioglycollic acid into the filtrate B, standing, and adding Na 2 CO 3 Dripping NaOH in parallel flow, filtering to obtain filtrate C and basic lithium carbonate precipitate; in the seventh step, the mol ratio of triethanolamine, thioglycollic acid and nickel is 1.1:1.1:1, the concentration of sodium carbonate solution is 0.02mol/L, the concentration of sodium hydroxide solution is 0.01mol/L, the volume ratio of sodium carbonate solution to sodium hydroxide solution is 1:1, pH is controlled to be 9.3-9.6, the temperature is 66 ℃, the stirring time is 36h, and Na is controlled in parallel flow addition 2 CO 3 The molar ratio of the lithium to the magnetic stirrer is controlled to be 1.1-1.2:1, and the rotating speed of the magnetic stirrer is set to be 1000r/min.
Step eight: adding triethanolamine and thioglycollic acid into the filtrate A, wherein the mol ratio of the triethanolamine to the thioglycollic acid to the nickel is 1.1:1, then mixing with the filtrate C, and the mol ratio of NaOH to the total cobalt is 28-32:1 after mixing; heating to 99.9 deg.c for 120min, recovering evaporated ammonia gas, and filtering to obtain filtrate D and cobalt oxide and hydroxide precipitate.
Step nine: treating filtrate D with Fenton method, and treating filtrate D with Ni Fe 2 O 4 Nickel is recovered in the form.
Comparative example 1
In contrast to example 1, the method for recovering the active material in the lithium ion cathode material only performs one alkaline leaching of the active material in the cathode material, specifically comprises the following operations:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid;
step three: adding compound extractant into alkali leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 1.95mol/L H 2 SO 4 Back extraction of the solution;
step four: adding H into the mixture after extraction 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate;
the rest of the procedure was the same as in example 1.
Comparative example 2
In comparison with example 1, the method for recovering the active material in the lithium ion cathode material only performs one-time acid leaching of the active material in the cathode material, specifically comprises the following operations:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: acid leaching is carried out on the separated anode material to obtain acid leaching solution;
step three: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 1.95mol/L H 2 SO 4 Back extraction of the solution;
step four: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 Solution, at 18℃with sulfuric acid and NH 3 ·H 2 O adjusts the pH value of the solution to be more than 11, and the solution is stood and filtered to obtain filtrate A and manganese oxide and hydroxide precipitate;
step five: adding triethanolamine and thioglycollic acid into the filtrate A, standing, and adding Na 2 CO 3 Dripping NaOH by adopting a parallel flow method, filtering to obtain filtrate B and basic lithium carbonate precipitate;
step six: controlling the molar ratio of NaOH to cobalt in the filtrate B to be 28:1; heating, recovering evaporated ammonia gas, and filtering to obtain filtrate C and cobalt oxide and hydroxide precipitate;
the rest of the procedure was the same as in example 1.
Comparative example 3
In comparison with example 1, in the method for recovering active material in lithium ion positive electrode material, lix54 was used instead of Lix984 in the composite extractant, and the rest of the operations were the same as in example 1.
Comparative example 4
In the method for recovering the active material in the lithium ion cathode material, compared with the example 1, lix984 is used for replacing Lix54 in the composite extractant, and the rest of the operations are the same as the example 1.
Comparative example 5
In comparison with example 1, the method for recovering active materials in lithium ion cathode materials uses P507 instead of Lix54 and Lix984 in the composite extractant, and the rest of the operations are the same as in example 1.
Comparative example 6
In the method for recovering the active material in the lithium ion cathode material, thioglycollic acid was used instead of triethanolamine as in example 1, and the other operations were the same as in example 1.
The leaching rates and recovery rates of cobalt nickel manganese lithium of the positive electrode materials in examples 1 to 3 and comparative examples 1 to 6 were respectively tested, and the obtained results are shown in table 1.
TABLE 1
As can be seen from table 1, in the examples provided in the present invention, the method for recovering the active material in the lithium ion positive electrode material has a good leaching rate, and the leaching rate of the positive electrode active material is above 98%, and has a good recovery rate. Whereas comparative example 1 leached out the active material by the alkaline leaching method, although having good selectivity to cobalt and nickel, recovery was not substantially achieved for manganese and lithium; the acid leaching method in comparative example 2 is more remarkable in precipitation rate of lithium, but is inferior in recovery effect to other three elements as the recovery method provided by the invention; in comparative examples 3 to 5, the impurity elements are leached by using different extractants, and although the leaching of the positive electrode active material is not affected, more elements to be recovered are entrained in the extraction process, so that the loss is caused; comparative example 6 uses thioglycollic acid instead of triethanolamine and thioglycollic acid, and has a great influence on the combination of cobalt and nickel, and the loss increases.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. A method for recovering an active material in a lithium ion positive electrode material, characterized by: the method comprises the following operation steps:
step one: carrying out discharge pretreatment on the waste ternary lithium battery, and disassembling and separating a steel shell, a positive electrode material, a negative electrode material and a diaphragm;
step two: alkaline leaching is carried out on the separated anode material by an alkaline leaching reagent, and residues after alkaline leaching are filtered out to obtain alkaline leaching liquid;
step three: acid leaching is carried out on the residues after alkaline leaching to obtain acid leaching solution;
step four: adding compound extractant into acid leaching solution for extraction, centrifuging to obtain mixed solution and loaded oil phase, wherein the loaded oil phase is 1.95-2.05mol/L H 2 SO 4 Back extraction of the solution;
step five: adding H into alkali leaching solution 2 O 2 Standing and filtering to obtain filtrate A and manganese oxide and hydroxide precipitate;
step six: adding NH into the mixed solution 4 Cl、NH 3 ·H 2 O and H 2 O 2 The solution is prepared by mixing sulfuric acid with NH at 18-22deg.C 3 ·H 2 O adjusts the pH value of the solution to be more than 11, and the solution is stood and filtered to obtain filtrate B and oxides and hydroxides of manganese precipitate;
step seven: adding triethanolamine and thioglycollic acid into the filtrate B, standing, and adding Na 2 CO 3 Dripping NaOH in parallel flow, filtering to obtain filtrate C and basic lithium carbonate precipitate;
step eight: adding triethanolamine and thioglycollic acid into the filtrate A, mixing with the filtrate C, and mixing until the molar ratio of NaOH to cobalt is 28-32:1; heating, recovering evaporated ammonia gas, and filtering to obtain filtrate D and cobalt oxide and hydroxide precipitate;
step nine: treating the filtrate D with Fenton method, and treating with NiFe 2 O 4 Nickel is recovered in the form.
2. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: in the second step, the alkaline leaching reagent is NH 3 ·H 2 O and (NH) 4 ) 2 C 2 O 4 In which the NH is 3 ·H 2 The concentration of O is 3.8-4.2mol/L, the concentration of the (NH) 4 ) 2 C 2 O 4 The concentration of the alkaline leaching agent is 1.6-1.8mol/L, the liquid-solid ratio of the alkaline leaching agent to the separated positive electrode material is 180-220mL/g, the alkaline leaching temperature is 22-26 ℃, and the alkaline leaching time is 60-70min.
3. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: the reagent used for acid leaching in the third step is H 2 SO 4 Solution and H 2 O 2 The H is 2 SO 4 The concentration of the solution is 2.2-2.6mol/L, and the H 2 SO 4 The liquid-solid ratio of the solution to the residue after alkaline leaching is 16-20mL/g, the H 2 O 2 And H is 2 SO 4 The volume ratio of the solution is 4.8-5.2:1, the temperature of the acid leaching is 125-135 ℃, and the time of the acid leaching is 120-150min.
4. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: in the fourth step, the composite extractant is extractant P507, lix54, lix984 and kerosene, wherein the volume ratio of the extractant P507, lix54, lix984 and kerosene is 1:1:1:17-18.
5. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: step five, the H 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) to (3) to (1) is controlled.
6. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: NH described in step six 4 The molar ratio of the addition amount of Cl to the total amount of cobalt and nickel is 3-4:1, and the NH is 3 ·H 2 The molar ratio of the addition amount of O to the total amount of cobalt and nickel is 6-8:1; the H is 2 O 2 And Mn in the positive electrode material 2+ The molar ratio of (2) is controlled to be 0.4-0.6:1.
7. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: in the seventh step, the mol ratio of triethanolamine, thioglycollic acid and nickel is 1.1:1.1:1, the concentration of sodium carbonate solution is 0.02mol/L, the concentration of sodium hydroxide solution is 0.01mol/L, the volume ratio of sodium carbonate solution to sodium hydroxide solution is 1:1, pH is controlled to be 9.3-9.6, the temperature is 62-66 ℃, the stirring time is 24-36h, and Na is controlled in parallel flow addition 2 CO 3 The molar ratio of the lithium to the magnetic stirrer is controlled to be 1.1-1.2:1, and the rotating speed of the magnetic stirrer is set to be 800-1000r/min.
8. The method for recovering an active material from a lithium ion positive electrode material according to claim 1, wherein: the heating temperature in the step eight is 98-100 ℃, and the heating time is 100-120min; the mol ratio of the triethanolamine, the thioglycollic acid and the nickel is 1.1:1.
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