CN116387668A - Selective leaching and recycling method for lithium in waste lithium iron phosphate battery - Google Patents
Selective leaching and recycling method for lithium in waste lithium iron phosphate battery Download PDFInfo
- Publication number
- CN116387668A CN116387668A CN202310338526.XA CN202310338526A CN116387668A CN 116387668 A CN116387668 A CN 116387668A CN 202310338526 A CN202310338526 A CN 202310338526A CN 116387668 A CN116387668 A CN 116387668A
- Authority
- CN
- China
- Prior art keywords
- lithium
- leaching
- iron phosphate
- lithium iron
- phosphate battery
- 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
- 238000002386 leaching Methods 0.000 title claims abstract description 104
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 24
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 24
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 8
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000006183 anode active material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hetero ions Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a selective leaching and recycling method of lithium in a waste lithium iron phosphate battery; the method comprises the following specific steps: uniformly mixing and reacting a positive and negative electrode mixture (black powder) obtained after disassembly, discharge, crushing and sorting of the waste lithium iron phosphate battery with a chlorine dioxide aqueous solution to obtain a lithium-containing leaching solution and filter residues; the lithium-containing leaching solution can be used for preparing lithium carbonate, and filter residues can be directly used for preparing lithium iron phosphate anode materials after impurity removal and drying. Based on the method, the invention provides a selective short-range recovery method of lithium in the waste lithium iron phosphate battery, and the method enables iron to be recovered in a form of ferric phosphate through solid-liquid separation, thereby avoiding the defect that the prior art needs to carry out complex separation and purification on leaching liquid, realizing the efficient selective recovery and closed-loop cyclic utilization of lithium in the waste lithium iron phosphate battery black powder, having the advantages of short flow, high lithium extraction efficiency, no secondary pollution and the like, and having excellent industrialized application and popularization prospects.
Description
Technical Field
The invention relates to the technical field of recycling of retired power batteries, in particular to a selective leaching and recycling method of lithium in waste lithium iron phosphate batteries.
Background
With the increasing importance of people on environmental protection, new energy automobiles using environment-friendly energy are continually moving into the lives of ordinary people. Among them, lithium ion batteries are widely used in the field of electric automobiles due to their high energy storage potential and environmental friendliness. The new energy automobile has a series of problems while the storage amount is greatly increased, and most directly, after the lithium ion batteries reach the service life, the waste lithium ion batteries can cause remarkable pollution to the environment. In addition, the great increase in demand for lithium ion batteries has also resulted in a great increase in demand for related metal resources, which has greatly increased the price of related metals, particularly lithium. Thus, recovery of lithium from spent lithium ion batteries is a fairly attractive option.
The positive electrode materials of lithium ion batteries in the current market mainly comprise lithium iron phosphate (LFP), lithium Cobalt Oxide (LCO), ternary lithium (NCM) and the like. Among them, lithium iron phosphate is used in a large amount in vehicles such as electric vehicles due to its characteristics of low cost, high chemical stability, high safety and long life. The service life of the lithium iron phosphate battery is 7-8 years, and the current lithium iron phosphate battery is facing a large-scale retirement tide, wherein the lithium content is far higher than the grade of lithium in primary lithium ore resources, and the lithium iron phosphate battery has higher recovery value.
Currently, the recovery processes of waste lithium iron phosphate batteries mainly include a fire method, a biological method, a wet method and the like. Fire refers to recovery of metals through a series of physicochemical processes at high temperatures, and there are generally two specific methods, direct regeneration and carbothermic reduction. For lithium iron phosphate, the flow of using direct regeneration is very short, but the purity of the raw materials is very high; while lithium remains in the slag for difficult recovery when carbothermic reduction is used. Biological methods are methods in which a metabolic process of microorganisms is used to act on a raw material, a target metal in the raw material is extracted into a solution, and the solution is separated and recovered by hydrometallurgical technology. The biological method has the advantages of lower cost compared with the traditional method, no generation of a large amount of waste water and waste gas, and longer culture period of microorganisms. Wet method refers to a method of recovering metal components by bringing a raw material into contact with water or other liquid, transferring metal in the raw material into a liquid phase through a chemical reaction, and separating the metal in the liquid phase. The wet method has the advantages of being capable of completely recycling metals in raw materials, and being convenient to operate, but high in strength of waste water and waste residue.
The existing hydrometallurgical technology generally takes strong acid or strong alkali as a leaching agent to leach all valuable metals in the black powder, and then the method of adding a precipitant, adjusting the pH value and the like is adopted to recycle lithium in the black powder. For example, in chinese patent CN115504446a, after acid leaching waste lithium iron phosphate powder with an organic acid solution, solid-liquid separation is performed to obtain an acidic leaching solution, then an oxidant is added into the acidic leaching solution, an alkaline solution is added dropwise to adjust pH value, and after reaction, solid-liquid separation is performed to obtain a precipitate of iron phosphate and a filtrate containing lithium. And then the purified filtrate containing lithium is boiled, a carbonate solution is added to be saturated, the solution is continuously boiled, solid-liquid separation is carried out to obtain lithium carbonate sediment and acid-containing filtrate, and finally acid is recovered from the acid-containing filtrate. The method is complex in operation and high in cost, and the used waste lithium iron phosphate powder is easy to introduce aluminum, copper and other hetero ions, so that the product quality is affected. Chinese patent CN109554545A pulps lithium iron phosphate waste by adding water, adding acid, heating to 40-100 ℃, regulating the pH value of the system to 2-4, maintaining the temperature and the pH value range, reacting for 1-10 h, filtering and separating the reacted slurry to obtain lithium solution and ferrophosphorus slag. The method has longer process and is easy to cause secondary pollution to the environment.
In summary, the prior art has the defects of long flow, complex operation, high separation and purification cost, low recovery rate of lithium and the like, and a new process for selectively and efficiently extracting lithium from waste lithium iron phosphate batteries and further realizing short-range regeneration of the lithium iron phosphate batteries is urgently needed to be developed.
Disclosure of Invention
In view of the above problems, a primary object of the present invention is to provide a method for selectively leaching and recovering lithium from waste lithium iron phosphate batteries. The invention relates to a selective short-range recovery method of lithium in a waste lithium iron phosphate battery, which enables iron to be recovered in a form of ferric phosphate through solid-liquid separation, avoids the defect that the prior art needs to carry out complex separation and purification on leaching liquid, realizes high-efficiency selective recovery and closed-loop cyclic utilization of lithium in the waste lithium iron phosphate battery black powder, has the advantages of short flow, high lithium extraction efficiency, no secondary pollution and the like, and has excellent industrialized application and popularization prospects.
The invention solves the technical problems by the following technical proposal:
a selective leaching and recycling method of lithium in waste lithium iron phosphate batteries comprises the following steps:
(1) Disassembling the waste lithium iron phosphate battery into battery monomers, and discharging, crushing and sorting to obtain black powder rich in anode active materials;
(2) Adding the black powder obtained in the step (1) into 0.1-0.5 wt.% of chlorine dioxide aqueous solution for reaction, and after the reaction is finished, carrying out solid-liquid separation on a reaction system to obtain lithium-containing leaching solution and filter residues;
(3) Adding saturated sodium carbonate solution into the lithium-containing leaching solution obtained in the step (2), precipitating lithium carbonate, and washing and drying for multiple times to obtain battery-grade lithium carbonate with purity of more than 99.5%;
(4) Washing the filter residue obtained in the step (2) with pure water, drying, wherein the main component of the obtained powder is ferric phosphate, and preparing a positive electrode material precursor by utilizing the characteristic that graphite is easy to float upwards and purifying through a floatation method;
(5) And (3) mixing the battery grade lithium carbonate obtained in the step (3) with the positive electrode material precursor obtained in the step (4), and roasting at high temperature to prepare the lithium iron phosphate positive electrode material, so that closed loop recycling is realized.
In the invention, in the step (2), the mass ratio of the battery black powder to the chlorine dioxide is 1:0.5-1:10, the reaction temperature is 20-60 ℃, the leaching time is 5-180 min, and the pH value of the solution in the leaching process is 1-7.
In the invention, in the step (2), the mass ratio of the battery black powder to the chlorine dioxide is 1:1-1:5, the reaction temperature is 20-60 ℃, the leaching time is 5-30 min, and the pH value of the solution in the leaching process is 1-3.
In the invention, in the step (3), the precipitation time of adding sodium carbonate is 60-180 min, and water with the temperature of 60-80 ℃ is adopted for washing lithium carbonate.
In the invention, in the step (4), the drying temperature is 80-105 ℃.
In the invention, in the step (5), the roasting temperature is 500-750 ℃ and the roasting time is 1-5 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the selective leaching and recycling method for lithium in the waste lithium iron phosphate battery, the chlorine dioxide aqueous solution is used as a leaching agent to selectively leach lithium in the waste lithium iron phosphate battery, the leaching rate of lithium is up to 99.76% under the optimal condition, the leaching rate of iron is only 4.56%, the main component of filter residues is ferric phosphate, the precursor of the lithium iron phosphate positive electrode material is prepared through separation, purification and impurity removal, the impurity removal method is mainly floatation, and the characteristic that graphite easily floats on water is utilized to separate graphite from ferric phosphate, so that selective leaching of lithium in the waste lithium iron phosphate battery and closed-loop recycling of the positive electrode material are realized.
(2) According to the selective leaching and recycling method for lithium in the waste lithium iron phosphate battery, provided by the invention, no additional reagent is required to be added after leaching to separate lithium and iron, so that the problem of short-range and efficient recycling of black powder is solved, and the method has the advantages of low reagent consumption, short flow, low cost and high lithium recovery rate.
(3) The selective leaching and recycling method for lithium in the waste lithium iron phosphate battery provided by the invention starts from the physical and chemical characteristics of the waste lithium iron phosphate battery black powder, has the advantages of clean whole recycling process, no secondary pollution, capability of effectively improving the recycling rate of the battery anode material, reduction of the material recycling cost and wide industrialization application prospect.
Drawings
Fig. 1 is a process flow diagram of the present invention for selectively leaching and recovering lithium from a spent lithium iron phosphate battery.
Fig. 2 is an XRD pattern of the residue obtained in example 1.
Figure 3 is an XRD pattern of the calcined product of example 1.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to the drawings and examples.
Fig. 1 is a process flow chart of selectively leaching and recovering lithium from waste lithium iron phosphate battery black powder, and the process for selectively leaching and recovering lithium from waste lithium iron phosphate battery black powder provided by the invention comprises the following specific steps:
(1) Disassembling the waste lithium iron phosphate battery into battery monomers, and discharging, crushing and sorting to obtain black powder rich in anode active materials;
(2) Adding chlorine dioxide water solution into the black powder obtained in the step (1), and reacting to obtain leaching solution;
(3) Filtering the leaching solution obtained in the step (2), and performing solid-liquid separation to obtain a lithium-containing filtrate and filter residues;
(4) Adding sodium carbonate into the lithium-containing leaching solution obtained in the step (2), precipitating lithium carbonate, and washing and drying for multiple times to obtain battery-grade lithium carbonate with the purity of more than 99.5%;
(5) Washing the filter residue obtained in the step (3) with pure water, drying, and carrying out flotation impurity removal and purification on the obtained powder to prepare a precursor of the anode material.
(6) And (3) sintering the lithium salt obtained in the step (4) and the positive electrode material precursor obtained in the step (5) to prepare the lithium iron phosphate positive electrode material.
The mass ratio of the battery black powder to the chlorine dioxide in the leaching process in the step (2) is 1 (0.5-10).
The leaching time in the step (2) is 5-180 min.
The reaction temperature in the step (2) is 20-60 ℃.
The pH value of the solution in the leaching process in the step (2) is 1-7.
The precipitation time of adding sodium carbonate in the step (4) is 60-180 min, and the water temperature of washing lithium carbonate is 60-80 ℃.
The main component of the filter residue obtained in the step (5) is ferric phosphate.
The temperature of the dried filter residue in the step (5) is 80-105 ℃.
The roasting temperature in the step (6) is 500-750 ℃ and the roasting time is 1-5 h.
Example 1
The method for selectively leaching and recycling lithium in the waste lithium iron phosphate battery black powder comprises the following specific steps:
(1) Determination of the Metal content in a sample
Taking 0.1g of dry waste lithium iron phosphate battery black powder sample, placing the dry waste lithium iron phosphate battery black powder sample in a digestion tank, adding 6mL of concentrated hydrochloric acid, 2mL of concentrated nitric acid and 2mL of deionized water, and placing the digestion tank in a microwave digestion instrument. After digestion, the volume was set to 100mL and the solutions were diluted 10-fold and 100-fold, respectively. The content of the metal component was then quantitatively determined using ICP-OES (ICAP 700) from thermoelectric (ThermoFisher Scientific) corporation in America, and the results are shown in Table 1.
TABLE 1 Main ingredients of waste lithium iron phosphate battery black powder
| Element(s) | Li | Fe |
| Content (wt.) | 4.18 | 39.46 |
(2) Chlorine dioxide system selective leaching lithium
Taking 1g of black powder, placing the black powder into a beaker, adding 0.5wt.% of chlorine dioxide aqueous solution, uniformly stirring, controlling the mass ratio of the black powder to the chlorine dioxide to be 1:5, and controlling the reaction temperature to be 20 ℃ and the pH value in the leaching process to be 2. And standing the beaker with the mixed sample for 30min, and separating the lithium-containing filtrate and filter residues by using a vacuum suction filtration device. The filter residue was washed with ultrapure water, the washing solution was added to the filtrate, and the content of metal ions in the filtrate was measured by ICP-OES. The washed filter residue is put into an oven at 105 ℃ to be dried for 24 hours, then is weighed, the phase composition of the filter residue is detected by XRD, 0.1g of the filter residue is taken out, and the content of metal ions in the digestion liquid is measured by ICP-OES. The leaching rates of lithium and iron were calculated using the following formula.
In the formula, LE M Leaching rate (%) for metal M;
C L is the concentration of metal in the leachate (measured by ICP, g/L);
V L is the volume (L) of the leaching solution;
m Z the mass of the filter residue (weighing, g after drying at 105 ℃ for 24 hours);
w is the mass fraction (%) of metal in the filter residue;
C Z concentration of metals in the digestion solution (measured by ICP, g/L);
m is the weighing number (g) of the filter residue.
The leaching rate of lithium in the system using chlorine dioxide as a leaching agent is up to 99.76%, the leaching rate of iron is 4.56%, and XRD (Bruker D8 ADVANCE) of Bruker (Bruker) of Germany is adopted for detection, and the result is shown in figure 2, wherein the main phase of filter residues is ferric phosphate. The method realizes the efficient and selective leaching of lithium in the waste lithium iron phosphate battery black powder.
(3) Lithium carbonate recovery
And collecting the leached lithium-containing filtrate and washing liquid, adding sodium carbonate, precipitating lithium carbonate, filtering, washing and drying to obtain the lithium carbonate. And washing the leached filter residues by pure water, drying, and removing impurities by floatation by utilizing the characteristic that graphite is easy to float on water to obtain the precursor of the anode material.
(4) Synthesis of lithium iron phosphate
And taking a certain amount of lithium carbonate and a positive electrode material precursor, ensuring the molar ratio of lithium to iron to be 1:1, mixing the lithium carbonate and the positive electrode material precursor, roasting the mixture under nitrogen atmosphere at the roasting temperature of 650 ℃ for 3 hours, and obtaining the lithium iron phosphate after roasting. Figure 3 is an XRD pattern of the calcined product of example 1.
Example 2
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder in the embodiment is the same as that in embodiment 1, except that: the mass ratio of the battery black powder to the chlorine dioxide in the leaching experiment in the step (2) is 1:3, and the reaction temperature is 40 ℃. The leaching rate of lithium under the chlorine dioxide system is 96.13 percent, and the leaching rate of iron is 3.57 percent, thus realizing the efficient and selective leaching of lithium in the waste lithium iron phosphate battery black powder.
Example 3
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder in the embodiment is the same as that in embodiment 1, except that: the mass ratio of the battery black powder to the chlorine dioxide in the leaching experiment in the step (2) is 1:1, and the reaction temperature is 60 ℃. The leaching rate of lithium under the chlorine dioxide system is measured to be 95.07%, and the leaching rate of iron is measured to be 5.36%, so that the efficient and selective leaching of lithium in the waste lithium iron phosphate battery black powder is realized.
Example 4
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder in the embodiment is the same as that in embodiment 1, except that: the leaching experiment reaction time in the step (2) is 10min. The leaching rate of lithium under the chlorine dioxide system is 88.19 percent, and the leaching rate of iron is 3.65 percent, thus realizing the efficient and selective leaching of lithium in the waste lithium iron phosphate battery black powder.
Comparative example 1
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder of the comparative example is the same as in example 1 except that:
in the step (2), the aqueous hydrogen peroxide solution is used for replacing the aqueous chlorine dioxide solution, and the pH value in the leaching process is 7. The leaching rate of lithium was 44.09% and the leaching rate of iron was 0.06%. At this time, efficient leaching of lithium cannot be realized, so that the leaching process adopts chlorine dioxide as a leaching agent, which is a key point of the invention.
Comparative example 2
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder of the comparative example is the same as in example 1 except that: the mass ratio of the battery black powder to the chlorine dioxide in the leaching experiment in the step (2) is 1:0.25. The leaching rate of lithium was measured to be 62.64% and the leaching rate of iron was 0.04%. At this time, efficient leaching of lithium cannot be achieved, so that a proper mass ratio between the battery black powder and chlorine dioxide in the leaching process is an important factor affecting selective leaching of lithium.
Comparative example 3
The method for selectively leaching and recovering lithium in the waste lithium iron phosphate battery black powder of the comparative example is the same as in example 1 except that: the pH of the leaching experiment in step (2) was 8. The leaching rate of lithium was measured to be 43.37% and the leaching rate of iron was measured to be 7.89%. At this time, efficient leaching of lithium cannot be achieved, and thus a proper pH value in the leaching process is an important factor affecting selective leaching of lithium.
The leaching rate data of lithium and iron elements in examples 1 to 4 are summarized in table 2.
TABLE 2 Leaching Rate of lithium and iron in different examples
| Metal leaching rate (%) | Example 1 | Example 2 | Example 3 | Example 4 |
| Lithium ion battery | 99.76 | 96.13 | 95.07 | 88.19 |
| Iron (Fe) | 4.56 | 3.57 | 5.36 | 3.65 |
From the above table, the chlorine dioxide aqueous solution is used as the leaching agent of the waste lithium iron phosphate battery black powder, so that the selective leaching of lithium can be effectively realized, and other impurity ions can not be introduced into the leaching solution. The method effectively solves the problem that the leaching solution is required to be additionally subjected to lithium-iron separation after leaching under the prior technical conditions, and realizes the efficient selective leaching of lithium in the waste lithium iron phosphate battery black powder.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing embodiments and description merely illustrates the principles of the invention, and that various changes and modifications may be effected therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.
Claims (6)
1. A selective leaching and recycling method of lithium in waste lithium iron phosphate batteries is characterized by comprising the following steps:
(1) Disassembling the waste lithium iron phosphate battery into battery monomers, and discharging, crushing and sorting to obtain black powder rich in anode active materials;
(2) Adding the black powder obtained in the step (1) into 0.1-0.5 wt.% of chlorine dioxide aqueous solution for reaction, and after the reaction is finished, carrying out solid-liquid separation on a reaction system to obtain lithium-containing leaching solution and filter residues;
(3) Adding saturated sodium carbonate solution into the lithium-containing leaching solution obtained in the step (2), precipitating lithium carbonate, and washing and drying for multiple times to obtain battery-grade lithium carbonate with purity of more than 99.5%;
(4) Washing the filter residue obtained in the step (2) with pure water, drying, wherein the main component of the obtained powder is ferric phosphate, and preparing a positive electrode material precursor by utilizing the characteristic that graphite is easy to float upwards and purifying through a floatation method;
(5) And (3) mixing the battery grade lithium carbonate obtained in the step (3) with the positive electrode material precursor obtained in the step (4), and roasting at high temperature to prepare the lithium iron phosphate positive electrode material, so that closed loop recycling is realized.
2. The method for selectively leaching and recovering lithium in a spent lithium iron phosphate battery according to claim 1, characterized by: in the step (2), the mass ratio of the battery black powder to the chlorine dioxide is 1:0.5-1:10, the reaction temperature is 20-60 ℃, the leaching time is 5-180 min, and the pH value of the solution in the leaching process is 1-7.
3. The method for selectively leaching and recovering lithium in a spent lithium iron phosphate battery according to claim 1, characterized by: in the step (2), the mass ratio of the battery black powder to the chlorine dioxide is 1:1-1:5, the reaction temperature is 20-60 ℃, the leaching time is 5-30 min, and the pH value of the solution in the leaching process is 1-3.
4. The method for selectively leaching and recovering lithium in a spent lithium iron phosphate battery according to claim 1, characterized by: in the step (3), sodium carbonate is added for 60-180 min, and water with the temperature of 60-80 ℃ is adopted for washing lithium carbonate.
5. The method for selectively leaching and recovering lithium in a spent lithium iron phosphate battery according to claim 1, characterized by: in the step (4), the drying temperature is 80-105 ℃.
6. The method for selectively leaching and recovering lithium in a spent lithium iron phosphate battery according to claim 1, characterized by: in the step (5), the roasting temperature is 500-750 ℃ and the roasting time is 1-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338526.XA CN116387668A (en) | 2023-03-31 | 2023-03-31 | Selective leaching and recycling method for lithium in waste lithium iron phosphate battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338526.XA CN116387668A (en) | 2023-03-31 | 2023-03-31 | Selective leaching and recycling method for lithium in waste lithium iron phosphate battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116387668A true CN116387668A (en) | 2023-07-04 |
Family
ID=86976325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310338526.XA Pending CN116387668A (en) | 2023-03-31 | 2023-03-31 | Selective leaching and recycling method for lithium in waste lithium iron phosphate battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116387668A (en) |
-
2023
- 2023-03-31 CN CN202310338526.XA patent/CN116387668A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111206148B (en) | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery | |
| CN108550939B (en) | A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell | |
| WO2022127117A1 (en) | Method for treating positive electrode material of waste lithium battery | |
| CN111825110A (en) | Recycling method of waste lithium ion battery anode material | |
| CN109626350B (en) | Method for preparing battery-grade iron phosphate from waste lithium iron phosphate battery positive plates | |
| CN111790728B (en) | Disposal method for efficiently reducing and recycling waste lithium batteries by using water vapor | |
| CN111082043A (en) | Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material | |
| CN106848473B (en) | Method for selectively recovering lithium in waste lithium iron phosphate batteries | |
| CN101871048A (en) | Method for recovering cobalt, nickel and manganese from waste lithium cells | |
| CN111484044A (en) | Method for extracting lithium in lithium battery waste at front end | |
| CN111254294A (en) | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation | |
| CN111926191B (en) | Method for recycling lithium iron phosphate battery | |
| CN111987381A (en) | Method for synchronously defluorinating valuable metals leached from waste lithium ion batteries | |
| CN111455177A (en) | Method for recovering valuable metals of lithium battery positive electrode material by using saccharides and hydrogen peroxide | |
| CN114249313A (en) | Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder | |
| CN113528824A (en) | Method for recovering elemental copper from waste lithium ion battery powder and application | |
| CN114477240A (en) | Preparation method of battery-grade lithium hydroxide | |
| CN116190843A (en) | Recycling method of waste lithium iron phosphate battery anode powder | |
| CN114317977A (en) | Method for recovering metal from waste lithium cobalt oxide battery | |
| CN115448335B (en) | Recycling method of waste lithium iron manganese phosphate battery | |
| CN111129488A (en) | Preparation method of lithium ion battery nickel-cobalt binary oxide positive electrode material precursor | |
| CN114314617B (en) | Method for recycling metal from waste ternary lithium ion battery anode material | |
| CN115947323A (en) | Method for extracting lithium from waste lithium iron phosphate and preparing iron phosphate | |
| CN115275415A (en) | Method for recovering lithium from retired lithium battery and regenerating positive electrode material | |
| CN115161483A (en) | Method for fully recycling waste lithium ion batteries and realizing metal separation |
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 |