CN117551890A - Method for recovering lithium from lithium manganate - Google Patents
Method for recovering lithium from lithium manganate Download PDFInfo
- Publication number
- CN117551890A CN117551890A CN202311416404.4A CN202311416404A CN117551890A CN 117551890 A CN117551890 A CN 117551890A CN 202311416404 A CN202311416404 A CN 202311416404A CN 117551890 A CN117551890 A CN 117551890A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- lithium manganate
- manganate
- carbonate
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 96
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 43
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 23
- 239000011572 manganese Substances 0.000 abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052748 manganese Inorganic materials 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 description 13
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for recovering lithium from lithium manganate. According to the method, lithium manganate, water and an oxidant are mixed, and after an oxidation leaching reaction, a lithium-containing solution and manganese dioxide are obtained through separation, wherein the pH value of the solution in the oxidation leaching reaction process is 1-2. Therefore, the method has simple process flow, can effectively reduce the cost, has the recovery rate of lithium up to more than 95 percent, and hardly leaches manganese.
Description
Technical Field
The invention relates to the technical field of lithium ion waste batteries, in particular to a method for recycling lithium from lithium manganate.
Background
The lithium manganate has higher oxidation potential, better thermal stability than lithium cobaltate and lithium nickelate, and overcharge resistance, and the spinel structure provides a good channel for the intercalation and deintercalation of lithium ions, thereby being beneficial to the charge and discharge of large current. Spinel structure LiMn 2 O 4 Is widely used because of the advantages of high working voltage, good safety, low price, environmental protection and the like. At present, the lithium manganate battery gradually enters the retirement period, the retired lithium manganate battery is rich in valuable metals such as lithium, manganese, copper and the like,meanwhile, the lithium battery contains various harmful substances such as electrolyte, and the lithium is used as a global strategic resource with limited reserves, and the lithium price is continuously increased in recent years, so that the cost of the lithium ion battery is increased. Therefore, from the viewpoints of sustainability and economy, it is of great importance to develop a method for cleanly and efficiently recovering lithium metal from waste lithium batteries.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to propose a method for recovering lithium from lithium manganate. The method has simple process flow, can effectively reduce the cost, has the recovery rate of lithium up to more than 95 percent, and hardly leaches manganese.
The invention provides a method for recovering lithium from lithium manganate, which comprises the following steps: mixing lithium manganate with water and an oxidant, and separating to obtain a lithium-containing solution and manganese dioxide after oxidation leaching reaction, wherein the pH value of the solution in the oxidation leaching reaction process is 1-2.
According to the method for recovering lithium from lithium manganate of the above embodiment of the present invention, lithium manganate (LiMn 2 O 4 ) Mixing with water and oxidant, stirring, oxidizing and leaching, oxidizing agent and LiMn 2 O 4 React to form manganese dioxide (MnO) 2 ) And LiMn 2 O 4 The lithium in (a) is extracted from the crystal lattice into solution. Controlling the pH value of the solution to be 1-2 in the oxidation leaching reaction process, wherein the too low pH value can cause manganese to be dissolved into the solution, so that the selectivity of extracting lithium is reduced; if the pH is too high, the oxidizing ability of the oxidizing agent decreases, and sufficient oxidation cannot be achieved. In addition, mnO generated by the oxidation leaching reaction 2 No lithium ion is adsorbed, so that the efficient selective leaching of lithium is realized. Therefore, the method has simple process flow, can effectively reduce the cost, has high recovery rate of lithium and hardly leaches manganese.
In addition, the method for recovering lithium from lithium manganate according to the above embodiment of the present invention may further have the following technical features:
in some embodiments of the invention, the oxidizing agent comprises at least one of persulfate, hypochlorite, hydrogen peroxide. Therefore, the cost can be effectively reduced, the recovery rate of lithium can be improved, and the leaching rate of manganese can be reduced.
In some embodiments of the invention, the molar ratio of the oxidizing agent to lithium manganate is (1.5-5) to 1. Therefore, the cost can be effectively reduced, the recovery rate of lithium can be improved, and the leaching rate of manganese can be reduced.
In some embodiments of the invention, the solid to liquid ratio of lithium manganate to water is 1kg to (1.5-10) L. Therefore, the cost can be effectively reduced, the recovery rate of lithium can be improved, and the leaching rate of manganese can be reduced.
In some embodiments of the invention, the temperature of the oxidative leach reaction is 50 ℃ to 95 ℃ for a period of 0.5h to 3h. Therefore, the reaction rate can be improved, the production efficiency is improved, the cost is reduced, the recovery rate of lithium is further improved, and the leaching rate of manganese is reduced.
In some embodiments of the invention, the lithium manganate is derived from at least one of anode scraps generated in the production process of lithium manganate batteries and anode scraps obtained by disassembling and sorting waste lithium manganate batteries. Thus, the cost can be effectively reduced.
In some embodiments of the invention, the method further comprises: adding an alkaline solution into the lithium-containing solution to perform precipitation and impurity removal to obtain a pure lithium solution; adding carbonate into the pure lithium solution, and separating to obtain lithium carbonate. Thus, the impurity removal efficiency can be improved, and the recovery rate of lithium can be further improved.
In some embodiments of the invention, the pH of the solution during the precipitation and impurity removal process is controlled to be 9-10. Thus, the impurity removal efficiency can be improved, and the recovery rate of lithium can be further improved.
In some embodiments of the invention, the carbonate comprises saturated sodium carbonate. Thus, the production efficiency can be improved, and the recovery rate of lithium can be further improved.
In some embodiments of the invention, the alkaline solution comprises at least one of sodium hydroxide, ammonia, and potassium hydroxide. Therefore, the impurity removal efficiency can be effectively improved, and the recovery rate of lithium can be further improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention.
The invention provides a method for recovering lithium from lithium manganate. According to the embodiment of the invention, lithium manganate is mixed with water and an oxidant, and is separated to obtain a lithium-containing solution and manganese dioxide after oxidation leaching reaction, wherein the pH value of the solution in the oxidation leaching reaction process is 1-2.
According to the method for recovering lithium from lithium manganate of the above embodiment of the present invention, lithium manganate (LiMn 2 O 4 ) Mixing with water and oxidant, stirring, oxidizing and leaching, oxidizing agent and LiMn 2 O 4 React to form manganese dioxide (MnO) 2 ) And LiMn 2 O 4 The lithium in (a) is extracted from the crystal lattice into solution. Controlling the pH of the solution in the oxidation leaching reaction process to be 1-2, such as 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 and the like, wherein the too low pH can lead to dissolution of manganese into the solution, so that the selectivity of extracting lithium is reduced; if the pH is too high, the oxidizing ability of the oxidizing agent decreases, and sufficient oxidation cannot be achieved. In addition, mnO generated by the oxidation leaching reaction 2 No lithium ion is adsorbed, so that the efficient selective leaching of lithium is realized. Therefore, the method has simple process flow, can effectively reduce the cost, has high recovery rate of lithium and hardly leaches manganese.
MnO obtained by the above separation 2 The solid can be used as a manganese source to prepare battery materials again.
According to some embodiments of the invention, the oxidizing agent comprises at least one of persulfate, hypochlorite, hydrogen peroxide. Specifically, the persulfate may be sodium persulfate (Na 2 S 2 O 8 ) Ammonium persulfate ((NH) 4 ) 2 S 2 O 8 ) Or crossPotassium sulfate (K) 2 S 2 O 8 ) Etc., the hypochlorite may be sodium hypochlorite (NaClO), calcium hypochlorite (Ca (ClO) 2 ) Or potassium hypochlorite (KClO), etc. The oxidant can provide electrons in oxidation leaching reaction to enable LiMn 2 O 4 Oxidation to MnO 2 . Therefore, the cost can be effectively reduced, the recovery rate of lithium can be improved, and the leaching rate of manganese can be reduced.
According to some embodiments of the invention, the molar ratio of oxidizing agent to lithium manganate is (1.5-5) to 1, such as 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, etc. The inventor finds that when the molar ratio of the oxidant to the lithium manganate is too small, the oxidant is not enough to be beneficial to the efficient leaching of lithium in the lithium manganate, so that the recovery rate of the lithium is too low; when the molar ratio of the oxidizing agent to lithium manganate is too large, the oxidizing agent is excessive, resulting in waste, and the cost becomes high. Therefore, the molar ratio of the oxidant to the lithium manganate in the application is in the range, so that the cost can be effectively reduced, the recovery rate of lithium is improved, and the leaching rate of manganese is reduced.
According to some embodiments of the invention, the solid to liquid ratio of lithium manganate to water is 1 kg:1.5L, e.g., 1 kg:1.5L, 1 kg:2L, 1 kg:3L, 1 kg:4L, 1 kg:5L, 1 kg:6L, 1 kg:7L, 1 kg:8L, 1 kg:9L, 1 kg:10L, etc. The inventor finds that when the solid-to-liquid ratio of lithium manganate to water is too small, excessive water addition causes the reduction of the oxidizing capacity of the oxidant and insufficient oxidation; when the solid-to-liquid ratio of lithium manganate to water is too large, the shortage of the aqueous solution is unfavorable for efficient leaching of lithium in lithium manganate, and the recovery rate of lithium is too low. Therefore, the solid-liquid ratio of the lithium manganate to the water in the application is in the range, so that the cost can be effectively reduced, the recovery rate of the lithium is improved, and the leaching rate of the manganese is reduced.
According to some embodiments of the invention, the temperature of the oxidative leaching reaction is 50-95 ℃, e.g., 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃, etc., for a period of 0.5h-3h, e.g., 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, etc. The inventor finds that when the oxidation leaching reaction temperature is too low or the reaction time is too short, the oxidation leaching rate is too slow and lithium in lithium manganate is difficult to be extracted from crystal lattices; when the oxidation leaching reaction temperature is too high or the reaction time is too long, the oxidation leaching reaction is severely unsafe, and the energy consumption of the production process is increased. Therefore, the temperature and time of the oxidation leaching reaction are in the range, so that the reaction rate can be increased, the production efficiency can be improved, the cost can be reduced, the recovery rate of lithium can be further improved, and the leaching rate of manganese can be reduced.
According to some embodiments of the invention, the lithium manganate is derived from at least one of anode scraps generated in the production process of the lithium manganate battery and anode scraps obtained by disassembling and sorting waste lithium manganate batteries. Specifically, the above-mentioned positive electrode leftover materials refer to waste materials remained in the process of producing the positive electrode material of the lithium manganate battery, such as crushing, sieving, forming and the like. The process for disassembling and sorting the waste lithium manganate batteries comprises the following steps: disassembling the discharged waste lithium manganate batteries, collecting positive plates, and crushing by using a crusher to obtain positive plate fragments; carrying out low-temperature pyrolysis on the fragments of the positive plate, and removing electrolyte to obtain a preliminary pyrolysis positive plate; carrying out high-temperature pyrolysis on the preliminary pyrolysis positive plate to decompose the organic binder, so as to obtain a complete pyrolysis positive plate; further crushing the completely pyrolyzed positive plate to obtain a positive plate mixed material of spherical aluminum foil particles with uniform granularity and positive active powder; and screening the anode plate mixture to obtain coarse fraction current collector and fine fraction anode waste. Thus, the cost can be effectively reduced.
According to some embodiments of the invention, the method for recovering lithium from lithium manganate further comprises: adding an alkaline solution into the lithium-containing solution to perform precipitation and impurity removal to obtain a pure lithium solution; adding carbonate into pure lithium solution, separating to obtain lithium carbonate (Li 2 CO 3 ). Specifically, adding an alkaline solution to the lithium-containing solution, and controlling the pH of the solution to 9-10, for example, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, etc., using the alkaline solution can enable some impurity metals such as iron ions, aluminum ions, copper ions, etc., which may exist in the solution, to be totally precipitated in an alkaline environment, and the reaction principle is as follows:
Fe 3+ +3OH - →Fe(OH) 3 ↓；
Al 3+ +3OH - →Al(OH) 3 ↓；
Cu 2+ +2OH - →Cu(OH) 2 ↓。
removing the solid impurities through separation to obtain a pure lithium solution; and adding carbonate into the pure lithium solution to obtain lithium carbonate precipitate, and separating and drying to obtain lithium carbonate. Thus, the impurity removal efficiency can be improved, and the recovery rate of lithium can be further improved.
Further, the above carbonate includes saturated sodium carbonate, which can effectively suppress side reactions in the reaction and can reduce lithium loss. Thus, the production efficiency can be improved, and the recovery rate of lithium can be further improved.
According to some embodiments of the invention, the alkaline solution comprises sodium hydroxide (NaOH), ammonia (NH) 3 ·H 2 O) and potassium hydroxide (KOH). Therefore, the impurity removal efficiency can be effectively improved, and the recovery rate of lithium can be further improved.
The concentration of the above-mentioned alkaline solution and the amount to be added are not limited herein, and may be selected by those skilled in the art according to the actual circumstances, and eventually, the control of the pH of the solution may be satisfied within the above-mentioned range.
Li obtained as described above 2 CO 3 MnO which can be obtained by oxidation leaching reaction 2 The solid participates in the presynthesis of the lithium manganate anode material to finally generate LiMn 2 O 4 。
Li obtained as described above 2 CO 3 Can also be combined with ternary composite positive electrode material precursor FePO 4 /Ni x Co y Mn (1-x-y) (OH) 2 (wherein x is more than 0 and less than 1, y is more than 0 and less than 1) to participate in the pre-synthesis of the ternary composite positive electrode material, and finally LiFePO is generated 4 /LiNi x Co y Mn (1-x-y) O 2 。
The separation method is not particularly limited, and any device and method known to those skilled in the art for separation can be used, and the method can be adjusted according to the actual process, for example, filtration, centrifugation, sedimentation separation, and the like, or a combination of different methods.
According to the method, the pH value of the solution is controlled to be 1-2 by additionally adding the oxidant into the aqueous solution, the oxidant applies oxidation potential to oxidize lithium manganate into manganese dioxide, so that lithium is promoted to be separated out and enter the solution, and the recovery rate of the lithium is higher than that of other methods due to the fact that few lithium ions are adsorbed and entrained in manganese dioxide precipitate generated by the method, and the method can realize high-efficiency selective leaching of the lithium by only using the oxidant. Therefore, the method has simple process flow, can effectively reduce the cost, and has the recovery rate of lithium up to more than 95 percent.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
The method for recovering lithium from lithium manganate comprises the following steps:
(1) Mixing 1kg of lithium manganate (from positive electrode waste obtained by disassembling and sorting lithium manganate batteries, wherein the lithium content is 3.9%), 5L of water and 4kg of sodium persulfate, wherein the pH of the mixed solution is 1.5, oxidizing and leaching under the conditions of the reaction temperature of 80 ℃ and the reaction time of 2 hours, and filtering and separating to obtain a lithium-containing solution (the manganese content is 0.05 g/L) and manganese dioxide, wherein the leaching rate of lithium is 98.3%;
(2) Adding NaOH solution into the lithium-containing solution obtained in the step (1) to adjust the pH to 9.2, forming a precipitate by metal impurities in the solution, and obtaining a pure lithium solution by filtration and separation;
(3) And (3) adding 1.8L of saturated sodium carbonate solution into the pure lithium solution obtained in the step (2) to generate lithium carbonate precipitate, filtering, separating and drying to obtain a lithium carbonate product.
Example 2
(1) Mixing 1kg of lithium manganate (from anode scraps produced in the production process of the battery, wherein the content of lithium is 3.5%) with 3L of water and 1.5kg of sodium hypochlorite, oxidizing and leaching under the conditions that the reaction temperature is 85 ℃ and the reaction time is 2 hours, filtering and separating to obtain a lithium-containing solution (the content of manganese is 0.06 g/L) and manganese dioxide, wherein the leaching rate of lithium is 99.2%;
(2) Adding NaOH solution into the lithium-containing solution obtained in the step (1) to adjust the pH to 9.5, forming a precipitate by metal impurities in the solution, and obtaining pure lithium solution by filtration and separation;
(3) And (3) adding 1.6L of saturated sodium carbonate solution into the pure lithium solution obtained in the step (2) to generate lithium carbonate precipitate, filtering, separating and drying to obtain a lithium carbonate product.
Example 3
(1) Mixing 1kg of lithium manganate (from positive electrode waste obtained by disassembling and sorting lithium manganate batteries, wherein the lithium content is 4.2%) with 7L of water and 0.5kg of hydrogen peroxide, oxidizing and leaching under the conditions that the reaction temperature is 80 ℃ and the reaction time is 2 hours, filtering and separating to obtain a lithium-containing solution (the manganese content is 0.03 g/L) and manganese dioxide, wherein the leaching rate of lithium is 98.5%;
(2) Adding NH to the lithium-containing solution obtained in the step (1) 3 ·H 2 The pH value of the O solution is regulated to 9.4, metal impurities in the solution form precipitation, and pure lithium solution is obtained through filtration and separation;
(3) And (3) adding 1.9L of saturated sodium carbonate solution into the pure lithium solution obtained in the step (2) to generate lithium carbonate precipitate, filtering, separating and drying to obtain a lithium carbonate product.
Example 4
(1) Mixing 1kg of lithium manganate (from positive electrode waste obtained by disassembling and sorting a lithium manganate battery, wherein the lithium content is 3.5%) with 4L of water and 4kg of sodium persulfate, oxidizing and leaching under the conditions of a reaction temperature of 90 ℃ and a reaction time of 2 hours, and filtering and separating to obtain a lithium-containing solution (the manganese content is 0.02 g/L) and manganese dioxide, wherein the leaching rate of lithium is 99.5%;
(2) Adding KOH solution into the lithium-containing solution obtained in the step (1) to adjust the pH to 9.5, forming a precipitate by metal impurities in the solution, and obtaining a pure lithium solution by filtration and separation;
(3) And (3) adding 1.6L of saturated sodium carbonate solution into the pure lithium solution obtained in the step (2) to generate lithium carbonate precipitate, filtering, separating and drying to obtain a lithium carbonate product.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method for recovering lithium from lithium manganate is characterized in that the lithium manganate is mixed with water and an oxidant, and is separated to obtain a lithium-containing solution and manganese dioxide after oxidation leaching reaction, wherein the pH value of the solution in the oxidation leaching reaction process is 1-2.
2. The method of claim 1, wherein the oxidizing agent comprises at least one of persulfate, hypochlorite, and hydrogen peroxide.
3. The method according to claim 1 or 2, wherein the molar ratio of the oxidizing agent to lithium manganate is (1.5-5) to 1.
4. The method of claim 1, wherein the solid to liquid ratio of lithium manganate to water is 1 kg:1.5-10L.
5. The method of claim 1, wherein the oxidative leach reaction is at a temperature of 50 ℃ to 95 ℃ for a time of 0.5h to 3h.
6. The method of claim 1, wherein the lithium manganate is derived from at least one of positive electrode scraps generated in the production process of lithium manganate batteries and positive electrode scraps obtained by disassembling and sorting waste lithium manganate batteries.
7. The method as recited in claim 6, further comprising:
adding an alkaline solution into the lithium-containing solution to perform precipitation and impurity removal to obtain a pure lithium solution;
adding carbonate into the pure lithium solution, and separating to obtain lithium carbonate.
8. The method of claim 7, wherein the pH of the solution during the precipitation and impurity removal is controlled to be 9-10.
9. The method of claim 7, wherein the carbonate comprises saturated sodium carbonate.
10. The method of claim 7, wherein the alkaline solution comprises at least one of sodium hydroxide, ammonia, and potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311416404.4A CN117551890A (en) | 2023-10-30 | 2023-10-30 | Method for recovering lithium from lithium manganate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311416404.4A CN117551890A (en) | 2023-10-30 | 2023-10-30 | Method for recovering lithium from lithium manganate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117551890A true CN117551890A (en) | 2024-02-13 |
Family
ID=89819419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311416404.4A Pending CN117551890A (en) | 2023-10-30 | 2023-10-30 | Method for recovering lithium from lithium manganate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117551890A (en) |
-
2023
- 2023-10-30 CN CN202311416404.4A patent/CN117551890A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110527835B (en) | Method for recycling soft package full components of waste ternary lithium battery | |
| Zou et al. | A novel method to recycle mixed cathode materials for lithium ion batteries | |
| KR101497041B1 (en) | Method for recovering valuable metals from cathodic active material of used lithium battery | |
| CA3105510A1 (en) | Process for the recycling of spent lithium ion cells | |
| US9023130B2 (en) | Method for separating positive-pole active substance and method for recovering valuable metals from lithium ion battery | |
| CN107017443A (en) | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery | |
| CN113443640B (en) | Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery | |
| CN109182732B (en) | Hierarchical recovery method for waste ternary lithium battery | |
| CN113802002B (en) | Method for recovering valuable metals in lithium battery by wet process | |
| CN110129571A (en) | A method of extracting valuable metal from waste and old lithium ion battery material | |
| CN111484044A (en) | Method for extracting lithium in lithium battery waste at front end | |
| CN109097581A (en) | The recovery method of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| Dobó et al. | A review on recycling of spent lithium-ion batteries | |
| US20240055684A1 (en) | Preparation method of heterosite iron phosphate and application thereof | |
| CN111994925A (en) | Comprehensive utilization method of valuable resources in waste lithium batteries | |
| CN114585756A (en) | Method for recycling lithium batteries | |
| CN110791668B (en) | Method for recovering manganese from lithium ion battery anode waste containing manganese element | |
| CN110498434B (en) | Recovery method and application of lithium ion battery positive electrode active material | |
| CN109004307A (en) | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| Yasa et al. | Recycling valuable materials from the cathodes of spent lithium-ion batteries: A comprehensive review | |
| JP2023516663A (en) | Disposal method of lithium iron phosphate battery | |
| CN112591806A (en) | Method for recovering and regenerating anode active material of waste lithium ion battery | |
| CN115321505B (en) | Method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater and application | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN115652077A (en) | Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery |
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 |