CN117737454A - Method for recycling lithium from waste lithium-containing cathode material - Google Patents
Method for recycling lithium from waste lithium-containing cathode material Download PDFInfo
- Publication number
- CN117737454A CN117737454A CN202311716534.XA CN202311716534A CN117737454A CN 117737454 A CN117737454 A CN 117737454A CN 202311716534 A CN202311716534 A CN 202311716534A CN 117737454 A CN117737454 A CN 117737454A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solvent
- sodium
- waste
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 239000010406 cathode material Substances 0.000 title claims description 31
- 238000004064 recycling Methods 0.000 title description 5
- 239000002904 solvent Substances 0.000 claims abstract description 72
- 238000001556 precipitation Methods 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 238000002386 leaching Methods 0.000 claims abstract description 38
- 239000011734 sodium Substances 0.000 claims abstract description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 238000011084 recovery Methods 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 86
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000011780 sodium chloride Substances 0.000 claims description 43
- 239000000706 filtrate Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000011045 prefiltration Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000001376 precipitating effect Effects 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011575 calcium Substances 0.000 abstract description 7
- 229910052791 calcium Inorganic materials 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000011777 magnesium Substances 0.000 abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910001415 sodium ion Inorganic materials 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering lithium from waste lithium-containing positive electrode materials, which utilizes hydrochloric acid and a reducing agent to carry out metal leaching treatment on the waste lithium-containing positive electrode materials, so that metal elements in the waste lithium-containing positive electrode materials are dissolved into leaching liquid in the form of ions, other metal components (such as nickel, cobalt, manganese, aluminum, iron, magnesium, calcium, zinc, copper and the like) except lithium and sodium are gradually converted into precipitate and removed by adding a precipitating agent, then a separating solvent is added to carry out precipitation treatment on sodium in the solution, the concentration of sodium in the solution is greatly reduced, the lithium-containing solution is concentrated as much as possible in the subsequent process, and lithium in the lithium-containing solution is maximally converted into lithium carbonate precipitate, so that a lithium product is recovered with high efficiency, high recovery rate and high purity.
Description
Technical Field
The invention relates to the field of waste battery recovery, in particular to a method for recovering lithium from waste lithium-containing positive electrode materials.
Background
Currently, new energy automobiles are increasingly favored by consumers by virtue of various advantages thereof, and lithium secondary batteries are continuously increasing in demand for lithium secondary batteries in the market as power batteries for new energy automobiles. With continuous scrapping of new energy automobiles, a large amount of scrapped lithium secondary batteries are generated. The waste lithium ion battery contains toxic and harmful heavy metals and electrolyte, if the waste lithium ion battery is improperly treated, the waste lithium ion battery can cause great harm to the environment, and meanwhile, the waste lithium ion battery also contains a plurality of noble and rare metal elements such as lithium, cobalt, nickel, manganese and the like. If the lithium element of the waste lithium ion battery can be recycled in the production process of enterprises, the problem of shortage of rare metal resources can be relieved, the production cost can be saved for the enterprises, and the pressure of the waste battery to the environment can be relieved. Therefore, it is highly desirable to develop a method that can recover lithium from the spent positive electrode material.
Currently, recovery techniques mainly include fire recovery, wet recovery, biological recovery, and the like. The fire recovery has strong applicability to raw materials, large treatment capacity, short flow and high efficiency, can realize the mixed treatment of anode and cathode and a shell, but has high requirements on the tail gas treatment and the performance of equipment and huge energy consumption. The bioleaching recovery technology has low cost, little pollution and recycling, but has low recovery rate, long recovery time and difficult microorganism selection and cultivation. Wet recovery is most widely used for recovering waste lithium batteries in industry due to mild conditions, low energy consumption and high recovery rate.
Wet recovery generally comprises the procedures of separating, leaching, chemical precipitation and the like of active substances in batteries, and the recovery of lithium elements in waste anode materials is realized. In the patent with publication number CN114606398A, sulfuric acid leaching treatment is used, pH is regulated by sodium hydroxide to separate ternary precipitate and lithium-containing refined treatment liquid, saturated sodium carbonate solution precipitant is added into the lithium-containing refined treatment liquid for precipitation reaction under the condition of ultrasonic oscillation, lithium carbonate precipitate is obtained, and the lithium carbonate precipitate is washed with water and dried to obtain a final product. The patent does not treat the high concentration sodium element introduced by sodium hydroxide in the lithium-containing finishing solution before precipitating lithium, so that the finally obtained lithium carbonate product contains a considerable amount of sodium impurities, so that the purity of the lithium carbonate product is not high.
Disclosure of Invention
The invention provides a method for recycling lithium from waste lithium-containing positive electrode materials, which is characterized in that special precipitants and separation solvents are selected, impurity ions are selectively separated out from leaching liquid step by step orderly and efficiently, and finally separated from target lithium ions, so that a lithium-rich solution with extremely low impurity ion content is obtained, and the efficient recycling of lithium ions is facilitated.
The invention provides a method for recovering lithium from waste lithium-containing cathode materials, which comprises the following steps:
1) Hydrochloric acid and a reducing agent are added into the waste lithium-containing positive electrode material, and metal leaching treatment is carried out to obtain a leaching solution with pH value not higher than 1;
2) Adding a precipitant into the leaching solution to perform first precipitation treatment, filtering after the content of nickel, cobalt, manganese, iron and aluminum elements in the system is less than or equal to 500ppb, and collecting first filtrate;
3) Adjusting the pH value of the first filtrate to below 7 by utilizing hydrochloric acid, concentrating, and filtering and collecting to obtain a first lithium-containing concentrated solution when crystallization occurs;
4) Mixing the first lithium-containing concentrated solution with a separating solvent, performing second precipitation treatment, and filtering after the difference value of the content of the twice sampled sodium elements in the system is less than or equal to 10ppm to obtain second filtrate;
wherein the solubility S of NaCl and LiCl in 100g of the separating solvent is 25 DEG C NaCl 、S NaCl Satisfies the requirements of formulas 1 and 2:
S NaCl less than or equal to 0.2g of 1
S LiCl /S NaCl And more than or equal to 100 formula 2.
The method as described above, the first precipitation treatment in step 2) comprises the steps of:
adding a precipitant into the leaching solution until the pH value is 4-5, filtering after the content of iron and aluminum elements in the system is less than or equal to 500ppb, and collecting the pre-filtrate;
and continuously adding a precipitant into the prefilter until the pH value is 10-12, filtering after the content of nickel, cobalt and manganese elements in the system is less than or equal to 500ppb, and collecting the first filtrate.
The method comprises the steps of concentrating the second filtrate after the step 4) to obtain a second lithium-containing concentrated solution with the mass fraction of lithium elements not lower than 1.7%, and performing third precipitation treatment on the second lithium-containing concentrated solution to obtain lithium-containing precipitates.
In the method described above, the volume ratio of the separation solvent to the first lithium-containing concentrate is 6 to 10.
The method as described above, the separation solvent comprises at least one of methanol, ethanol, isopropanol, n-propanol, formic acid, acetic acid, ethanone, acetone, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and methyl chloride.
In the above method, the difference in boiling point between the separation solvent and water is 5 ℃ or higher.
The method as described above, the separation solvent comprises a first solvent and a second solvent, the first solvent is selected from one of methanol and ethanol, and the second solvent comprises one of isopropanol and ethanone;
wherein the mass ratio of the first solvent to the second solvent is (1-3): 1-2.
According to the method, the waste lithium-containing positive electrode material comprises at least one of ternary positive electrode material, lithium cobaltate positive electrode material and lithium manganate positive electrode material.
The method as described above, the precipitating agent comprises at least one of sodium carbonate, sodium hydroxide, and lithium hydroxide.
The recovery rate of lithium was not less than 70% by the method described above.
The invention relates to a method for recovering lithium from waste lithium-containing positive electrode materials, which comprises the steps of carrying out metal leaching treatment on the waste lithium-containing positive electrode materials by utilizing hydrochloric acid and a reducing agent, dissolving metal elements in the waste lithium-containing positive electrode materials into leaching liquid in an ionic form, gradually converting other metal components (such as nickel, cobalt, manganese, aluminum, iron, magnesium, calcium, zinc, copper and the like) except for lithium and sodium into precipitate by adding a precipitating agent, removing the precipitate, adding a separating solvent, carrying out precipitation treatment on sodium in the solution, greatly reducing the concentration of sodium in the solution, concentrating the lithium-containing solution in the subsequent process as much as possible, and converting lithium in the lithium-containing solution into lithium carbonate precipitate to the greatest extent, thereby recovering lithium products with high efficiency, high recovery rate and high purity.
Drawings
FIG. 1 is a flow chart of a method for recovering lithium from a spent lithium-containing positive electrode material in one embodiment;
fig. 2 is a flow chart of a method for recovering lithium from a spent lithium-containing cathode material in another embodiment.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but 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.
The invention provides a method for recovering lithium from waste lithium-containing cathode materials, which comprises the following steps:
1) Hydrochloric acid and a reducing agent are added into the waste lithium-containing positive electrode material, and metal leaching treatment is carried out to obtain a leaching solution with pH value not higher than 1;
2) Adding a precipitant into the leaching solution to perform first precipitation treatment, filtering after the content of nickel, cobalt, manganese, iron and aluminum elements in the system is less than or equal to 500ppb, and collecting first filtrate;
3) Adjusting the pH value of the first filtrate to below 7 by utilizing hydrochloric acid, concentrating, and filtering and collecting to obtain a first lithium-containing concentrated solution when crystallization occurs;
4) Mixing the first lithium-containing concentrated solution with a separating solvent, performing second precipitation treatment, and filtering after the difference value of the content of the twice sampled sodium elements in the system is less than or equal to 10ppm to obtain second filtrate;
wherein the solubility S of NaCl and LiCl in 100g of the separating solvent is 25 DEG C NaCl 、S NaCl Satisfies the requirements of formulas 1 and 2:
S NaCl less than or equal to 0.2g of 1
S LiCl /S NaCl And more than or equal to 100 formula 2.
The lithium recovery method is mainly used for recovering and utilizing lithium elements in the waste lithium ion batteries. Generally, the waste lithium-containing positive electrode material to be recovered is obtained by disassembling a waste lithium ion battery, and crushing, grinding, screening and the like the positive electrode sheet obtained by disassembling.
The chemical composition of the waste lithium-containing positive electrode material is not particularly limited, and in a specific embodiment, the waste lithium-containing positive electrode material comprises at least one of ternary positive electrode material, lithium cobaltate positive electrode material and lithium manganate positive electrode material.
It can be appreciated that when different waste lithium-containing cathode materials are used, the leached metal ions are different, and the content of the metal ions in the leachate is also different. For example, when the waste lithium-containing cathode material is a ternary cathode material, the leachate includes a large amount of lithium ions, cobalt ions, nickel ions, and manganese ions, and other impurity ions such as iron, aluminum, sodium ions, and the like.
In one embodiment, fig. 1 is a flowchart of a method for recovering lithium from a waste lithium-containing cathode material according to one embodiment, as shown in fig. 1, and the method specifically includes the following steps:
and step 1, adding hydrochloric acid and a reducing agent into the waste lithium-containing positive electrode material, and performing metal leaching treatment to obtain a leaching solution with the pH value not higher than 1.
Firstly, hydrochloric acid and a reducing agent are utilized to carry out metal leaching treatment on the waste lithium-containing anode material. Specifically, the waste lithium-containing cathode material and water are added into a leaching container, and the mixture is stirred to uniformly disperse the waste lithium-containing cathode material in the water, so as to obtain an aqueous solution of the cathode material to be recycled. Adding hydrochloric acid and a reducing agent into an aqueous solution of the positive electrode material to be recovered at room temperature, carrying out metal leaching treatment, wherein the hydrochloric acid carries out oxidation leaching on metals in the waste lithium-containing positive electrode material, such as lithium, nickel, cobalt, manganese, aluminum, iron, sodium, magnesium, calcium, zinc, copper and the like, so that metal elements in the waste lithium-containing positive electrode material are dissolved into leaching liquid in the form of ions, and leaching liquid containing metal ions is obtained.
The purpose of the reducing agent is to reduce the insoluble or sparingly soluble metal ions in the higher valence state to the readily soluble lower valence state. For example, nickel (Ni) is usually present in solution only as +2 valent ions, and Ni may be added with a reducing agent 3+ Reduction to Ni 2+ Thereby dissolving as much nickel as possible in the waste lithium-containing cathode material.
Further, the reducing agent is added as hydrogen peroxide (H) 2 O 2 28 percent) of the leaching agent is added at the speed of 0.7mL/min, and other impurities are not introduced in the reaction process, so that the leaching efficiency can be obviously improved.
In order to ensure the dissolution of metals in the waste lithium-containing cathode material to the maximum extent, the pH of the leaching solution needs to be controlled to be not higher than 1.
In one embodiment, the pH of the leachate is no greater than 0.5.
And 2) adding a precipitant into the leaching solution to perform first precipitation treatment, filtering after the content of nickel, cobalt, manganese, iron and aluminum elements in the system is less than or equal to 500ppb, and collecting first filtrate.
Next, other metal components other than lithium, such as nickel, cobalt, manganese, aluminum, iron, magnesium, calcium, zinc, copper, and the like, are converted into precipitates by a precipitant for removal.
In one embodiment, the precipitating agent includes at least one of sodium carbonate, sodium hydroxide, and lithium hydroxide.
Further, the precipitant is sodium hydroxide due to the high cost of lithium hydroxide.
In a specific embodiment, the first precipitation treatment in step 2) comprises the steps of: adding a precipitant into the leaching solution until the pH value is 4-5, filtering after the content of iron and aluminum elements in the system is less than or equal to 500ppb, and collecting the pre-filtrate;
and continuously adding a precipitant into the prefilter until the pH value is 10-12, filtering after the content of nickel, cobalt and manganese elements in the system is less than or equal to 500ppb, and collecting the first filtrate.
The precipitant is sodium hydroxide.
Specifically, adding sodium hydroxide into the leaching solution, stopping adding the sodium hydroxide when the pH value of the solution is 4-5, continuing stirring, precipitating, filtering, collecting the pre-filtrate, and removing the component impurities such as aluminum, iron, magnesium, calcium, zinc, copper and the like and the residue mixture of the leaching reaction.
Then, continuously adding sodium hydroxide into the prefilter, stopping adding sodium hydroxide when the pH value of the solution is 10-12, continuously stirring, fully precipitating nickel (Ni), cobalt (Co) and manganese (Mn) components, and filtering to remove the components. Since lithium hydroxide has a large solubility, lithium remains in the first precipitation system in a metal ion state. Meanwhile, due to the addition of sodium hydroxide, a large amount of sodium ions are introduced into the mixed system, and after the first precipitation system is filtered, a first filtrate comprising lithium ions and sodium ions is obtained.
And 3, adjusting the pH value of the first filtrate to be below 7 by utilizing hydrochloric acid, concentrating, and filtering and collecting to obtain a first lithium-containing concentrated solution when crystallization occurs.
After the first precipitation treatment process, the first filtrate is alkaline, and in order to facilitate subsequent treatment, hydrochloric acid is needed to acidify the first filtrate, and the pH of the first filtrate is regulated to be below 7; in order to increase the efficiency of the second precipitation treatment in step 4), it is also necessary to concentrate the acidified first filtrate after the acidification treatment.
The method of the concentration treatment is not limited, and for example, evaporation concentration may be used.
When the concentration by evaporation is performed, the concentration is stopped when crystallization (sodium chloride crystals which are lithium chloride-entrained) occurs. The reason why lithium in the first filtrate after the acidification treatment cannot be concentrated to a higher concentration is that lithium is entrained when sodium chloride is precipitated, and in order to avoid lithium loss caused by concentration of sodium precipitation, concentration is ended when crystal precipitation occurs. And then filtered and collected to obtain a first lithium-containing concentrated solution.
In the step, the water content in the first filtrate after the acidification treatment is reduced through the concentration treatment, so that the precipitation efficiency of NaCl is higher when the second precipitation treatment is carried out, and the sodium ion content in the second filtrate is further reduced.
Step 4, mixing the first lithium-containing concentrated solution with a separating solvent, performing second precipitation treatment, and filtering after the difference value of the content of the sodium element sampled twice in the system is less than or equal to 10ppm to obtain second filtrate;
wherein the solubility S of NaCl and LiCl in 100g of the separating solvent is 25 DEG C NaCl 、S NaCl Satisfies the requirements of formulas 1 and 2:
S NaCl less than or equal to 0.2g of 1
S LiCl /S NaCl And more than or equal to 100 formula 2.
The hydrochloric acid added in the steps 1) and 3) introduces chloride ions, and more sodium ions are introduced in the step 2) during the first precipitation treatment, so that the first lithium-containing concentrated solution comprises lithium ions, sodium ions and chloride ions. Thus, step 4) separates lithium ions from sodium ions by the difference in solubility of NaCl and LiCl in the separation solvent.
Specifically, the inventors found that the separation solvent satisfying the requirements shown in formulas 1 to 2 can extrude sodium ions from the first lithium-containing concentrate in the form of NaCl to form a NaCl precipitate, while LiCl separation solvent still has a relatively large solubility, so that the NaCl precipitate is continuously separated out with the mixing of the first lithium-containing concentrate and the separation solvent and the stirring of the system, and finally the separation of sodium ions and lithium ions is completed.
Whether the current solvent meets the requirements of formulas 1 and 2 for separating the solvent can be evaluated by the following method.
The solvent to be evaluated was placed in a reaction vessel at 25℃with 100g, and anhydrous lithium chloride was added to dissolve until lithium chloride was no longer dissolved. At this time, 1g of anhydrous lithium chloride was further added to make undissolved lithium chloride exist in the solution. The reaction was further carried out in this state for 2 hours, and the completion was completed after the dynamic equilibrium of dissolution and crystallization was reached. Filtering the solution, performing ICP analysis on the lithium content in the filtrate, and calculating the solubility S of lithium chloride in the solvent to be detected LiCl . According to the sameCalculating S NaCl . When S is NaCl 、S LiCl And when the formula 1 and the formula 2 are met, the solvent to be detected is the separating solvent.
The present invention is not limited to the way of mixing the first lithium-containing concentrated solution and the separating solvent, and the first lithium-containing concentrated solution may be added to the separating solvent for mixing, or the separating solvent may be added to the first lithium-containing concentrated solution for mixing. The following description will be made in terms of a mixing manner in which the first lithium-containing concentrate is added to the separation solvent.
And (2) injecting the first lithium-containing concentrated solution into a separating solvent which is defined by the formulas 1 and 2, gradually precipitating in the system along with the injection of the first filtrate to perform second precipitation treatment, and filtering after the difference value of the content of the twice sampled sodium elements in the system is less than or equal to 10ppm to obtain the second filtrate.
In a specific embodiment, the first lithium-containing concentrated solution is added into the separating solvent, and the adding speed of the first lithium-containing concentrated solution is 10L/min, so that NaCl has a good removing effect.
In a specific embodiment, the solubility S of NaCl and LiCl in 100g of the separation solvent is at 25 DEG C NaCl 、S LiCl Satisfies the requirements of formulas 1 and 2:
S NaCl less than or equal to 0.2g of 1
S LiCl /S NaCl And no less than 600 formula 2.
In a specific embodiment, the volume ratio of the separation solvent to the first filtrate is 6 to 10. If the volume ratio of the separation solvent to the first filtrate is less than 6, the removal rate of sodium ions is reduced; if the concentration is more than 10, the cost of the subsequent concentration process increases. When the volume ratio of the separation solvent to the first filtrate is 6-10, the better removal rate of sodium ions can be ensured, the separation solvent is not wasted, the cost of the subsequent concentration process is increased, and the further preferable range is 7.5-8.5.
In one embodiment, the separation solvent used in the present invention includes at least one of methanol, ethanol, isopropanol, n-propanol, formic acid, acetic acid, ethanone, acetone, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, methyl chloride.
In a specific embodiment, the separation solvent comprises a first solvent and a second solvent, the first solvent is selected from one of methanol and ethanol, and the second solvent comprises one of isopropanol and ethanone; wherein the mass ratio of the first solvent to the second solvent is (1-3): 1-2. It may further be preferred that the first solvent is ethanol and the second solvent is isopropanol.
In a specific embodiment, to facilitate better removal of the separation solvent during concentration, the separation solvent and water have a boiling point difference of not less than 5 ℃.
After step 4), the invention is not limited to the subsequent treatment of the second filtrate. In a specific embodiment, fig. 2 is a flowchart of a method for recovering lithium from a waste lithium-containing cathode material in another specific embodiment, and as shown in fig. 2, after the second filtrate is obtained in step 4), the method further includes concentrating the second filtrate to obtain a second lithium-containing concentrated solution with a mass fraction of lithium elements not less than 1.7%, and performing a third precipitation treatment on the second lithium-containing concentrated solution to obtain a lithium-containing precipitate.
Firstly, concentrating the second filtrate to reduce the water content in the second filtrate to obtain second lithium-containing concentrated solution with the mass fraction of lithium elements not lower than 1.7%, thereby ensuring the efficient implementation of the third precipitation treatment.
Then, sodium carbonate or potassium carbonate and the like are added to carry out third precipitation treatment on the second lithium-containing concentrated solution, and lithium-containing precipitates are obtained.
When sodium carbonate is added, the following reaction occurs:
LiA(l)+Na 2 CO 3 (aq or powder)→Li 2 CO 3 (s)+NaA(l)
sodium carbonate can also be replaced by caustic soda and carbon dioxide, and the following reaction takes place:
LiA(l)+NaOH(aq)+CO 2 (g)→Li 2 CO 3 (s)+NaA(l)
when added as potassium carbonate, the following reaction occurs:
LiA(l)+K 2 CO 3 (aq or powder)→Li 2 CO 3 (s)+KA(l)
because the solubility of potassium carbonate in water is greater than that of sodium carbonate, the recovery rate of lithium can be further improved by adopting the method.
Based on the method for recovering lithium from the waste lithium-containing cathode material, the recovery rate of lithium is not lower than 70%.
The invention utilizes hydrochloric acid and a reducing agent to carry out metal leaching treatment on the waste lithium-containing positive electrode material, so that metal elements in the waste lithium-containing positive electrode material are dissolved into leaching liquid in the form of ions; then gradually converting other metal components (such as nickel, cobalt, manganese, aluminum, iron, magnesium, calcium, zinc, copper and the like) except lithium and sodium into precipitate by adding a precipitant; then acidizing and concentrating by using hydrochloric acid to obtain a first lithium-containing concentrated solution; and finally, mixing the first lithium-containing concentrated solution with a separation solvent, carrying out precipitation treatment on sodium impurities in the solution, greatly reducing the concentration of sodium in the solution, concentrating the lithium-containing solution as much as possible in a subsequent process, and converting lithium in the solution into lithium carbonate to the greatest extent for precipitation, thereby recovering lithium products with high efficiency, high recovery rate and high purity.
Hereinafter, the present invention will be described in further detail with reference to specific examples.
Example 1
The method provided by the embodiment comprises the following steps:
the metal composition of the waste high nickel ternary positive electrode material used in this example is shown in table 1 below.
TABLE 1 Metal composition Table for waste high nickel ternary cathode material
1) Metal leaching treatment
100kg of the waste high-nickel ternary cathode material is added into 200L of deionized water at 85 ℃ to be stirred and pulped, and the heat preservation temperature is set at 85 ℃; 35wt.% hydrochloric acid (313.48L total, flow rate 313.48L/h) was added; after 30min, the hydrochloric acid flow rate was reduced to 70L/h, and 27.5wt.% hydrogen peroxide (71.91L, flow rate 30L/h) was started to be added; after 5 hours, the real-time detection was carried out to keep the pH at no higher than 0.5 (otherwise, the acid addition was continued, followed by the hydrogen peroxide addition) until the reaction was ended when the hydrogen peroxide addition no longer raised the pH, at which point the leachate pH was 0.25.
2) First precipitation treatment
Adding 16% sodium hydroxide solution as precipitant into the above leaching solution (flow rate 2L/min, pH value increased to 4.7, adding precipitant, stirring for 2 hr, filtering to remove impurities such as aluminum, iron, magnesium, calcium, zinc and copper, and residue mixture of the above leaching reaction to obtain prefilter.
And (3) adding a 16% sodium hydroxide solution (the flow rate is 3L/min, the pH value is raised to 11, the adding of the precipitant is finished, stirring is continued for 4 hours, and the nickel, cobalt and manganese components are fully precipitated.
3) Acidifying and concentrating
And adding 10% hydrochloric acid to adjust the pH of the lithium-containing filtrate to 7, performing rotary evaporation concentration, stopping heating when crystallization occurs in concentration, and filtering while the solution is hot to obtain a first lithium-containing concentrated solution, wherein the mass fraction of lithium elements in the solution is 0.73wt.% and the mass fraction of sodium elements in the solution is 6.5wt.%.
4) Second precipitation treatment
Adding the first lithium-containing concentrated solution into a separation solvent with the volume being 7.5 times of that of the first lithium-containing concentrated solution, and carrying out sodium precipitation treatment, wherein the separation solvent comprises ethanol and isopropanol in a mass ratio of 2:1, and S NaCl 0.019g, S LiCl /S NaCl 650, stirring for 1h at room temperature, filtering after the difference value of the content of the sodium element sampled twice in the system is less than or equal to 10ppm, wherein the sodium element removal rate is 79.026%, and the lithium loss rate is 3.525%. The obtained filtrate was heated to 83 ℃, ethanol and isopropanol were recovered by evaporation, condensation and reflux, and the remaining solution was concentrated to obtain a second lithium-containing concentrate, which could be concentrated to 3.38wt.% of lithium element.
5) Third precipitation treatment
Adding saturated sodium carbonate solution (prepared by heat preservation at 55 ℃) into the second lithium-containing concentrated solution obtained in the step 4), wherein the reaction temperature is 95 ℃, the input speed is about 1L/min, when the pH value reaches 10, stopping the input, continuously heating and reacting for 3 hours, then performing heat preservation and filtration (95 ℃), washing with boiling water to obtain lithium carbonate precipitate, and the comprehensive recovery rate of lithium is 91.33%.
Example 2
The method of recovering lithium from the spent cathode material of this example is substantially the same as in example 1, except that the separation solvent is ethanol, S NaCl 0.07g, S LiCl /S NaCl 336, sodium element removal rate 65.514%, lithium loss rate 2.84%, concentration to 1.93wt.% lithium element mass fraction, and final lithium comprehensive recovery 80.42%.
Example 3
The method of recovering lithium from the spent cathode material of this example is basically the same as in example 1, except that the separation solvent is ethanol and isopropanol in a mass ratio of 1:1, S NaCl 0.02g, S LiCl /S NaCl 680, the sodium element removal rate is 74.32%, the lithium loss rate is 3.54%, the concentration can be carried out until the mass fraction of the lithium element is 2.67wt.%, and the final comprehensive recovery rate of lithium is 84.68%.
Example 4
The method of recovering lithium from the waste cathode material of this example is basically the same as in example 1, except that the separation solvent is ethanol and ethanone in a mass ratio of 1:1, S NaCl 0.02g, S LiCl /S NaCl The sodium element removal rate was 625, the lithium loss rate was 7.54%, the concentration was 2.87wt.% of the lithium element mass fraction, and the final overall lithium recovery rate was 81.37%.
Example 5
The method of recovering lithium from the waste cathode material of this example is basically the same as in example 1, except that the separation solvent is methanol and ethanone in a mass ratio of 1:1, S NaCl 0.06g, S LiCl /S NaCl 367, the sodium element removal rate is 70.38%, the lithium loss rate is 3.96%, and the lithium element removal rate can be concentrated to 2.23wt.% of lithium element mass fraction, and finally lithium is obtainedThe comprehensive recovery rate is 78.98%.
Example 6
The method of recovering lithium from the waste positive electrode material of this example was basically the same as in example 1 except that the lithium concentrated solution was added to 10 volumes of the separation solvent for sodium precipitation treatment. The removal rate of sodium element is 80.03%, the loss rate of lithium is 4.01%, the concentration can be carried out until the mass fraction of lithium element is 3.504wt.%, and the final comprehensive recovery rate of lithium is 91.38%.
Example 7
The method of recovering lithium from the waste positive electrode material of this example was basically the same as in example 1 except that the lithium concentrated solution was added to 5-fold volume of the separation solvent for sodium precipitation treatment. The sodium element removal rate is 60.3%, the lithium loss rate is 3.23%, the concentration can be carried out until the mass fraction of the lithium element is 1.766wt.%, and the final comprehensive recovery rate of lithium is 72.89%.
Example 8
The method of recovering lithium from the waste positive electrode material of this example is basically the same as in example 1, except that the metal composition of the waste positive electrode material is different, see table 2 below.
Table 2 table of metal composition of spent cathode material in example 8
The final overall recovery of lithium was 92.12%.
Example 9
The method of recovering lithium from the waste positive electrode material of this example is basically the same as in example 1, except that the metal composition of the waste positive electrode material is different, see table 3 below.
Table 3 table of metal composition of spent cathode material in example 9
The final overall recovery of lithium was 91.13%.
Example 10
The method of recovering lithium from the waste positive electrode material of this example is basically the same as in example 1, except that the metal composition of the waste positive electrode material is different, as shown in table 4 below.
Table 4 table of metal composition of waste cathode material in example 10
The final overall recovery of lithium was 90.08%.
Comparative example 1
The comparative example method for recovering lithium from the waste positive electrode material was basically the same as in example 1, except that in step 3), the rotary evaporation concentration was directly performed without adjusting the pH, and when crystallization occurred, the heating was stopped and the solution was filtered while it was hot, to obtain a lithium-containing concentrated solution, in which the mass fraction of lithium element was only 0.27wt.%, and the mass fraction of sodium element was 2.40wt.%. The lithium content of the solution is too low to directly carry out the third precipitation treatment, so that lithium carbonate precipitation is obtained.
Comparative example 2
The method of recovering lithium from the waste cathode material of this comparative example is basically the same as in example 1 except that in step 4), the first lithium-containing concentrated solution is directly used for the third precipitation treatment without using a separation solvent for sodium precipitation treatment.
The comprehensive recovery rate of lithium is 62.306%.
As can be seen from comparative examples 1 and 2, comparative example 1, after step 2, could not be directly subjected to the third precipitation treatment to obtain lithium carbonate precipitate without the treatment of steps 3 and 4; in comparative example 2, the third precipitation treatment was directly performed without the treatment of step 4, and the comprehensive recovery rate of lithium was only about 60%. The reason why the recovery effect of lithium in comparative examples 1 and 2 is poor is that when the content of sodium element in the solution is high, sodium element is preferentially precipitated and entrained with lithium element during concentration of the solution, thereby causing loss of lithium element, and in order to avoid loss of lithium caused by concentration and precipitation of sodium in the solution, the solution cannot be concentrated as much as possible, and a higher concentration lithium-containing solution cannot be obtained. When the concentration of lithium element in the solution is low, the effect becomes poor when the lithium carbonate product is obtained by the third precipitation treatment. At the same time, the treatment process of steps 3 and 4 in the method for recovering lithium of the present application was proved to be indispensable.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The method for recovering lithium from the waste lithium-containing cathode material is characterized by comprising the following steps of:
1) Hydrochloric acid and a reducing agent are added into the waste lithium-containing positive electrode material, and metal leaching treatment is carried out to obtain a leaching solution with pH value not higher than 1;
2) Adding a precipitant into the leaching solution to perform first precipitation treatment, filtering after the content of nickel, cobalt, manganese, iron and aluminum elements in the system is less than or equal to 500ppb, and collecting first filtrate;
3) Adjusting the pH value of the first filtrate to below 7 by utilizing hydrochloric acid, concentrating, and filtering and collecting to obtain a first lithium-containing concentrated solution when crystallization occurs;
4) Mixing the first lithium-containing concentrated solution with a separating solvent, performing second precipitation treatment, and filtering after the difference value of the content of the twice sampled sodium elements in the system is less than or equal to 10ppm to obtain second filtrate;
wherein the solubility S of NaCl and LiCl in 100g of the separating solvent is 25 DEG C NaCl 、S LiCl Satisfies the requirements of formulas 1 and 2:
S NaCl less than or equal to 0.2g of 1
S LiCl /S NaCl And more than or equal to 100 formula 2.
2. The method according to claim 1, wherein the first precipitation treatment in step 2) comprises the steps of:
adding a precipitant into the leaching solution until the pH value is 4-5, filtering after the content of iron and aluminum elements in the system is less than or equal to 500ppb, and collecting the pre-filtrate;
and continuously adding a precipitant into the prefilter until the pH value is 10-12, filtering after the content of nickel, cobalt and manganese elements in the system is less than or equal to 500ppb, and collecting the first filtrate.
3. The method according to claim 1 or 2, further comprising concentrating the second filtrate after the step 4) to obtain a second lithium-containing concentrated solution with a mass fraction of lithium elements of not less than 1.7%, and performing a third precipitation treatment on the second lithium-containing concentrated solution to obtain a lithium-containing precipitate.
4. A method according to any one of claims 1 to 3, wherein the volume ratio of the separation solvent to the first lithium-containing concentrate is 6 to 10.
5. The method according to any one of claims 1 to 4, wherein the separation solvent comprises at least one of methanol, ethanol, isopropanol, n-propanol, formic acid, acetic acid, ethanone, acetone, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and methyl chloride.
6. The method according to any one of claims 1 to 5, wherein the difference in boiling point between the separation solvent and water is not less than 5 ℃.
7. The method according to claim 5 or 6, wherein the separation solvent comprises a first solvent selected from one of methanol and ethanol and a second solvent comprising one of isopropanol and ethanone;
wherein the mass ratio of the first solvent to the second solvent is (1-3): 1-2.
8. The method of claim 1, wherein the waste lithium-containing cathode material comprises at least one of a ternary cathode material, a lithium cobaltate cathode material, and a lithium manganate cathode material.
9. The method of claim 1, wherein the precipitation agent comprises at least one of sodium carbonate, sodium hydroxide, lithium hydroxide.
10. The method according to any one of claims 1 to 9, wherein the recovery rate of lithium is not less than 70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311716534.XA CN117737454A (en) | 2023-12-13 | 2023-12-13 | Method for recycling lithium from waste lithium-containing cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311716534.XA CN117737454A (en) | 2023-12-13 | 2023-12-13 | Method for recycling lithium from waste lithium-containing cathode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117737454A true CN117737454A (en) | 2024-03-22 |
Family
ID=90255618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311716534.XA Pending CN117737454A (en) | 2023-12-13 | 2023-12-13 | Method for recycling lithium from waste lithium-containing cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117737454A (en) |
-
2023
- 2023-12-13 CN CN202311716534.XA patent/CN117737454A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112142077B (en) | Method for preparing battery-grade lithium carbonate and iron phosphate by recycling lithium iron phosphate positive electrode waste | |
| WO2021047352A1 (en) | Manganese-lithium separation and pre-extraction liquid preparation processes in comprehensive recovery of ternary battery waste, and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste | |
| CN113061723B (en) | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate | |
| CN112374511B (en) | Method for preparing lithium carbonate and ternary precursor by recycling waste ternary lithium battery | |
| CN108963371B (en) | Method for recovering valuable metals from waste lithium ion batteries | |
| CN110669933B (en) | Method for removing fluorine in nickel-cobalt-manganese solution | |
| CN106340692B (en) | A method of lithium in cleaning recycling positive electrode | |
| CN110835683B (en) | Method for selectively extracting lithium from waste lithium ion battery material | |
| CN109097581A (en) | The recovery method of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN112375910A (en) | Recovery processing method of waste power battery powder | |
| CN111118311B (en) | Manganese-lithium separation method in comprehensive recovery of ternary battery waste | |
| CN111254276A (en) | Method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of sodium reduction roasting | |
| CN114477240A (en) | Preparation method of battery-grade lithium hydroxide | |
| CN109004307A (en) | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN113862476B (en) | Method for pre-extracting lithium from waste lithium ion battery | |
| CN111549229A (en) | Method for extracting lithium from positive electrode material of waste lithium ion battery through pre-reduction preferential dissolution | |
| CN116411182A (en) | Method for selectively recovering lithium from lithium battery | |
| CN111321298A (en) | Method for leaching waste ternary LNCM lithium ion battery and recovering valuable metal | |
| CN117737454A (en) | Method for recycling lithium from waste lithium-containing cathode material | |
| CN111129634B (en) | Method for separating and recovering anode material of failed ternary lithium ion battery | |
| CN113981230A (en) | Method for leaching nickel cobalt slag | |
| CN115491497B (en) | Method for recycling valuable metal elements in iron slag and application of method | |
| CN115571925B (en) | Method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries | |
| CA3211531C (en) | Method for producing secondary battery material from black mass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |