CN116759686A - Method for recycling valuable metal from lithium iron phosphate battery anode material - Google Patents
Method for recycling valuable metal from lithium iron phosphate battery anode material Download PDFInfo
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- CN116759686A CN116759686A CN202310977678.4A CN202310977678A CN116759686A CN 116759686 A CN116759686 A CN 116759686A CN 202310977678 A CN202310977678 A CN 202310977678A CN 116759686 A CN116759686 A CN 116759686A
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- iron phosphate
- lithium iron
- reactor
- calciner
- regenerated
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 37
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002739 metals Chemical class 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000002699 waste material Substances 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 13
- 239000002121 nanofiber Substances 0.000 claims abstract description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 45
- 239000000460 chlorine Substances 0.000 claims description 45
- 239000000706 filtrate Substances 0.000 claims description 43
- 230000005484 gravity Effects 0.000 claims description 40
- 239000002244 precipitate Substances 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 23
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 21
- 239000005750 Copper hydroxide Substances 0.000 claims description 21
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 21
- 229960004887 ferric hydroxide Drugs 0.000 claims description 21
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000011812 mixed powder Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 36
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery comprises the following steps: pretreating a waste lithium iron phosphate battery; vacuum treatment and chlorine gas introduction calcination; adding phosphoric acid solution to regulate pH to precipitate iron; adding ammonia water to adjust pH for copper removal; adding phosphoric acid solution again to remove aluminum; regenerating lithium iron phosphate and ball-milling and mixing into carbonized fiber. According to the invention, regenerated lithium iron phosphate is synthesized through hydrothermal synthesis, polyacrylonitrile nano fiber and polyvinylpyrrolidone are used as raw materials, and the carbonized composite fiber is prepared through spinning, hydrothermal treatment, solidification and carbonization, so that the regenerated composite lithium iron phosphate prepared by ball milling and mixing the carbonized composite fiber and the regenerated lithium iron phosphate has better electrochemical performance than that of directly regenerated lithium iron phosphate, and the purpose of better recycling the anode material of the lithium iron phosphate battery is realized.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for recycling valuable metals from a lithium iron phosphate battery anode material.
Background
The lithium iron phosphate battery is one of lithium ion batteries, and mainly comprises a lithium iron phosphate positive electrode, a diaphragm, a graphite negative electrode, an electrolyte and a battery shell, wherein compared with a waste ternary lithium battery, the waste lithium iron phosphate battery has higher recovery value of only lithium element, but if the waste lithium iron phosphate battery is not recovered, not only is the waste of resources caused, but also serious environmental pollution is caused.
At present, two methods of leaching and recovering valuable metal elements and recovering regenerated lithium iron phosphate are mainly used for recovering the waste lithium iron phosphate battery, and as other metal elements in the waste lithium iron phosphate battery are hardly provided with recovery values except lithium elements, the waste lithium iron phosphate battery is recovered by adopting a regenerated lithium iron phosphate method, but impurities in the waste lithium iron phosphate battery cannot be completely removed, so that the electrochemical performance of the regenerated lithium iron phosphate is poor, and the use effect is poor.
Therefore, the method for recycling valuable metals from the lithium iron phosphate battery anode material, which can remove impurities to improve the electrochemical performance of the regenerated lithium iron phosphate, is provided to recycle the lithium iron phosphate battery anode material and reduce the resource waste.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery.
A method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery comprises the following steps:
s1: pretreatment of waste lithium iron phosphate battery
Discharging and disassembling the waste lithium iron phosphate battery, then putting the disassembled electrode slice into a freezing box, freezing for 0.5-1h, putting into boiling water, and stripping aluminum foil to obtain a positive electrode slice;
s2: vacuum treatment and chlorine gas charging calcination
Treating the inside of a calciner into a vacuum environment, then introducing chlorine, crushing and grinding the positive plate, and then placing the crushed and ground positive plate into the calciner for calcination to obtain mixed powder;
s3: adding phosphoric acid solution to regulate pH value to deposit iron
Adding ammonia water into the mixed powder until the pH value is regulated to 3.3-3.5, carrying out suction filtration to obtain ferric hydroxide precipitate and deironing filtrate, and washing the ferric hydroxide precipitate;
s4: adding ammonia water to regulate pH value for removing copper
Adding ammonia water into the deironing filtrate until the pH value is adjusted to 5-7, performing filter pressing to obtain copper hydroxide precipitate and copper removal filtrate, washing and drying the copper hydroxide precipitate, and recovering a copper hydroxide product;
s5: adding phosphoric acid solution again to remove aluminum
Adding phosphoric acid solution into the copper removal filtrate until the pH value is 4-4.5, performing centrifugal separation to obtain aluminum hydroxide precipitate and aluminum removal filtrate, and washing and drying the aluminum hydroxide precipitate to obtain a dry aluminum hydroxide product;
s6: regenerating lithium iron phosphate and ball milling and mixing with carbonized fiber
Adding the ferric hydroxide precipitate into the aluminum removal filtrate, adding a lithium supplementing agent, reacting to obtain regenerated lithium iron phosphate, preparing carbonized composite fibers by taking polyacrylonitrile nanofibers and polyvinylpyrrolidone as raw materials, and ball-milling and mixing the carbonized composite fibers with the regenerated lithium iron phosphate to obtain the regenerated composite lithium iron phosphate.
Further, the step S2 of vacuum treatment and calcination by introducing chlorine gas specifically comprises the following steps:
s2.1: putting the positive plate obtained in the step S1 into a crushing grinder, and fully crushing and grinding to obtain positive powder;
s2.2: opening a discharge valve of the crusher, pouring the anode powder into the calciner until a first gravity sensor in the calciner detects that the gravity in the calciner is not increased any more, and sending a signal to a controller by the first gravity sensor;
s2.3: after the controller receives the signal sent by the first gravity sensor, the calciner is controlled to calcine for 3-5 hours at 400-500 ℃;
s2.4: the controller controls a vacuum valve on the calciner to be opened for vacuum treatment, and the inside of the calciner is treated into a vacuum environment;
s2.5: the controller controls the inlet valve of the calciner to open, and chlorine is introduced into the calciner through the inlet valve until a chlorine detector in the calciner detects that the chlorine content in the calciner reaches 50-65%, and the chlorine detector sends a signal to the controller;
s2.6: and after receiving the signal sent by the chlorine detector, the controller controls the air inlet valve to be closed, and controls the calciner to calcine at 200-300 ℃ for 2-3 hours, so as to obtain the mixed powder.
Further, the step S3 of adding a phosphoric acid solution to adjust the pH value to precipitate iron comprises the following steps:
s3.1: adding the mixed powder prepared in the step S2.6 into a first reactor until a second gravity sensor in the first reactor detects that the gravity in the first reactor is not increased any more, and sending a signal to a controller by the second gravity sensor;
s3.2: after receiving the signal sent by the second gravity sensor, the controller controls the first hydraulic pump to start, and the phosphoric acid solution is added into the first reactor through the first hydraulic pump;
s3.3: until the first pH detector in the first reactor detects the pH=3.3-3.5 in the first reactor, a first mixture is obtained, and the first pH detector sends a signal to a controller;
s3.4: after receiving the signal sent by the first pH detector, the controller controls the first hydraulic pump to stop adding the phosphoric acid solution, controls the suction filtration device in the first reactor to start, performs suction filtration on the first mixture to obtain ferric hydroxide sediment and deironing filtrate, and then deionizes and washes the ferric hydroxide sediment for 2-3 times.
Further, the step S4 of adding ammonia water to adjust pH for removing copper specifically comprises the following steps:
s4.1: pumping the deironing filtrate obtained in the step S3.4 into a second reactor through a suction filtration device until a liquid level sensor in the second reactor detects that the liquid level of the deironing filtrate is not increased any more, and sending a signal to a controller by the liquid level sensor;
s4.2: after receiving the signal sent by the liquid level sensor, the controller controls the second hydraulic pump to introduce ammonia water into the second reactor until the second pH detector in the second reactor detects pH=5-7 in the second reactor to obtain a second mixture, and the second pH detector sends a signal to the controller;
s4.3: after the controller receives the signal sent by the second pH detector, the second hydraulic pump is controlled to stop adding ammonia water, the filter pressing device in the second reactor is controlled to start, the second mixture is filter pressed to obtain copper hydroxide sediment and copper removal filtrate, and then the copper hydroxide sediment is washed and dried to recover a dry copper hydroxide product.
Further, the regenerated lithium iron phosphate of the step S6 is mixed into the carbonized fiber by ball milling, and the method specifically comprises the following steps:
s6.1: adding the aluminum removal filtrate obtained in the step S5 into a hydrothermal reaction kettle, adding the ferric hydroxide precipitate obtained in the step S3.4 into the hydrothermal reaction kettle, adding a lithium supplementing agent, adjusting the temperature of the hydrothermal reaction kettle to be 200-220 ℃, and carrying out hydrothermal reaction for 2-3 hours to obtain regenerated lithium iron phosphate;
s6.2: adding polyacrylonitrile nanofiber and polyvinylpyrrolidone into N, N dimethylformamide according to a mass ratio of 1:1-3, stirring for 10-12h by using a stirrer, and then adding into a spinning machine for spinning to obtain composite fibers;
s6.3: carrying out hydrothermal treatment on the composite fiber for 5-6h at 80-90 ℃, then placing the composite fiber into a muffle furnace, and curing the composite fiber for 1-2h at 250-270 ℃ to obtain a cured composite fiber;
s6.4: placing the solidified fiber into a tube furnace, heating to 950-1050 ℃ at a speed of 5-10 ℃/min, and reacting for 1-3h to obtain carbonized composite fiber;
s6.5: adding the regenerated lithium iron phosphate and the carbonized composite fiber into a ball mill according to the mass ratio of 10-12:1, ball milling for 1-2 hours, and uniformly mixing to obtain the regenerated composite lithium iron phosphate.
Further, in the step S6.1, ammonia generated by the reaction is collected through an exhaust gas collecting device at the top of the hydrothermal reaction kettle while the hydrothermal reaction is performed, ammonia is reacted with water in the exhaust gas collecting device to generate ammonia after entering the exhaust gas collecting device, then the ammonia generated in the exhaust gas collecting device is sucked through a hydraulic pump in the step S4.2, and then the ammonia is introduced into a second reactor to perform the reaction.
Further, the phosphoric acid solution is prepared by mixing phosphoric acid and water according to the volume ratio of 1:2-3.
Further, the lithium supplementing agent is LiOH, li 2 SO 4 ·H 2 O and Li 2 CO 3 One of them.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, regenerated lithium iron phosphate is synthesized through hydrothermal synthesis, polyacrylonitrile nano fiber and polyvinylpyrrolidone are used as raw materials, and the carbonized composite fiber is prepared through spinning, hydrothermal treatment, solidification and carbonization, so that the regenerated composite lithium iron phosphate prepared by ball milling and mixing the carbonized composite fiber and the regenerated lithium iron phosphate has better electrochemical performance than that of directly regenerated lithium iron phosphate, and the purpose of better recycling the anode material of the lithium iron phosphate battery is realized.
2. According to the invention, the anode plate is crushed and then calcined to remove the organic binder, and then chlorine is introduced to perform high-temperature calcination, so that valuable metals are converted into metal chlorides, subsequent leaching and impurity removal are facilitated, the purity of the prepared regenerated lithium iron phosphate is higher, and in addition, the decomposition of the generated metal chlorides caused by excessive chlorine can be prevented by controlling the introduction amount of the chlorine.
3. According to the invention, valuable metals are oxidized to be the highest price through chlorine, so that a reducing agent is not needed to be used in the hydrothermal synthesis of lithium iron phosphate, and ammonia gas generated in the hydrothermal reaction is converted into ammonia water again by utilizing an exhaust gas collecting device so as to be recycled, thereby achieving the effect of saving resources.
Drawings
Fig. 1 is a flow chart of a method for recovering valuable metals from a positive electrode material of a lithium iron phosphate battery according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery, as shown in fig. 1, comprises the following steps:
s1: pretreatment of waste lithium iron phosphate battery
Discharging and disassembling the waste lithium iron phosphate battery, then putting the disassembled electrode slice into a freezing box, freezing for 0.5h, putting into boiling water, and stripping aluminum foil to obtain a positive electrode slice;
s2: vacuum treatment and chlorine gas charging calcination
The method comprises the steps of putting the positive plate into a crushing grinder, fully crushing and grinding to obtain positive powder, then opening a discharge valve of the crusher, pouring the positive powder into a calciner until a first gravity sensor in the calciner detects that the gravity in the calciner is not increased, sending a signal to a controller by the first gravity sensor, controlling the calciner to calcine for 3 hours at 400 ℃ after receiving the signal sent by the first gravity sensor, controlling a vacuum valve on the calciner by the controller to open, performing vacuum treatment, treating the interior of the calciner into a vacuum environment, controlling an air inlet valve of the calciner to open by the controller, introducing chlorine into the calciner through the air inlet valve until the chlorine content in the calciner reaches 50%, sending a signal to the controller by the chlorine detector, controlling the air inlet valve to close after receiving the signal sent by the chlorine detector, controlling the calciner to calcine at 200 ℃, obtaining mixed powder after calcining for 2 hours, removing an organic binder through calcination after crushing the positive plate, introducing chlorine into high-temperature calcination, converting valuable metal into metal chloride, facilitating subsequent leaching, and controlling the chlorine into high-purity chlorine to be more convenient, and preventing the generation of excessive chlorine, and further reducing the generation of high-purity chlorine, and reducing the excessive chlorine;
s3: adding phosphoric acid solution to regulate pH value to deposit iron
Adding the mixed powder into a first reactor until a second gravity sensor in the first reactor detects that the gravity in the first reactor is not increased any more, sending a signal to a controller by the second gravity sensor, controlling a first hydraulic pump to start after receiving the signal sent by the second gravity sensor, adding a phosphoric acid solution prepared by mixing phosphoric acid and water according to the volume ratio of 1:2 into the first reactor by the first hydraulic pump until a first pH detector in the first reactor detects that the pH value in the first reactor is=3.3, obtaining a first mixture, sending a signal to the controller by the first pH detector, controlling the first hydraulic pump to stop adding the phosphoric acid solution after receiving the signal sent by the first pH detector, controlling a suction filtration device in the first reactor to start, performing suction filtration on the first mixture to obtain ferric hydroxide precipitate and deironing filtrate, and washing the ferric hydroxide precipitate for 2 times by deironing;
s4: adding ammonia water to regulate pH value for removing copper
Pumping the deironing filtrate into a second reactor through a suction filtration device until a liquid level sensor in the second reactor detects that the liquid level of the deironing filtrate is not increased any more, sending a signal to a controller by the liquid level sensor, controlling a second hydraulic pump to absorb ammonia water generated in an exhaust gas collecting device in the step S6 after receiving the signal sent by the liquid level sensor, introducing the ammonia water into the second reactor until a second pH detector in the second reactor detects pH=5 in the second reactor, obtaining a second mixture, sending a signal to the controller by the second pH detector, controlling the second hydraulic pump to stop adding the ammonia water after receiving the signal sent by the second pH detector, controlling a filter pressing device in the second reactor to start, performing filter pressing on the second mixture to obtain copper hydroxide precipitate and a copper removal filtrate, washing and drying the copper hydroxide precipitate, and recovering a dry copper hydroxide product;
s5: adding phosphoric acid solution again to remove aluminum
Adding phosphoric acid solution into the copper removal filtrate until the pH value is=4, and then carrying out centrifugal separation to obtain aluminum hydroxide precipitate and aluminum removal filtrate, and washing and drying the aluminum hydroxide precipitate to obtain a dry aluminum hydroxide product;
s6: regenerating lithium iron phosphate and ball milling and mixing with carbonized fiber
Adding the aluminum removal filtrate into a hydrothermal reaction kettle, adding the ferric hydroxide precipitate into the hydrothermal reaction kettle, adding LiOH, regulating the temperature of the hydrothermal reaction kettle to 200 ℃, carrying out hydrothermal reaction for 2 hours, collecting ammonia gas generated by the reaction through an exhaust gas collecting device at the top of the hydrothermal reaction kettle, allowing the ammonia gas to enter the exhaust gas collecting device, reacting with water in the exhaust gas collecting device to generate ammonia water to obtain regenerated lithium iron phosphate, wherein in the step S2, valuable metals are oxidized into the highest price through chlorine gas, so that a reducing agent is not needed to be used in the hydrothermal synthesis of the lithium iron phosphate, ammonia gas generated in the hydrothermal reaction is converted into ammonia water again by the exhaust gas collecting device for recycling, the effect of saving resources is achieved, then adding the polyacrylonitrile nanofiber and the polyvinylpyrrolidone into N according to the mass ratio of 1:1, stirring N dimethylformamide for 10 hours by using a stirrer, adding into a spinning machine for spinning to obtain composite fibers, carrying out hydrothermal treatment on the composite fibers at 80 ℃ for 5 hours, putting into a muffle furnace, curing at 250 ℃ for 1 hour to obtain cured composite fibers, putting the cured fibers into a tube furnace, heating to 950 ℃ at the speed of 5 ℃/min, reacting for 1 hour to obtain carbonized composite fibers, adding the regenerated lithium iron phosphate and the carbonized composite fibers into a ball mill according to the mass ratio of 10:1, ball milling for 1 hour, uniformly mixing to obtain regenerated lithium iron phosphate, carrying out hydrothermal synthesis on the regenerated lithium iron phosphate, taking polyacrylonitrile nano fibers and polyvinylpyrrolidone as raw materials, carrying out spinning, hydrothermal treatment, curing and carbonization to obtain carbonized composite fibers, compared with directly regenerated lithium iron phosphate, the regenerated composite lithium iron phosphate prepared by ball milling and mixing the carbonized composite fiber and the regenerated lithium iron phosphate has more excellent electrochemical performance, thereby realizing the purpose of better recycling the lithium iron phosphate battery anode material.
Example 2
A method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery, as shown in fig. 1, comprises the following steps:
s1: pretreatment of waste lithium iron phosphate battery
Discharging and disassembling the waste lithium iron phosphate battery, then putting the disassembled electrode slice into a freezing box, freezing for 0.75h, putting into boiling water, and stripping aluminum foil to obtain a positive electrode slice;
s2: vacuum treatment and chlorine gas charging calcination
The method comprises the steps of putting the positive plate into a crushing grinder, fully crushing and grinding to obtain positive powder, then opening a discharge valve of the crusher, pouring the positive powder into a calciner until a first gravity sensor in the calciner detects that the gravity in the calciner is not increased, sending a signal to a controller by the first gravity sensor, controlling the calciner to calcine for 4 hours at 450 ℃ after receiving the signal sent by the first gravity sensor, controlling a vacuum valve on the calciner by the controller to open, performing vacuum treatment, treating the interior of the calciner into a vacuum environment, controlling an air inlet valve of the calciner to open by the controller, introducing chlorine into the calciner through the air inlet valve until the chlorine content in the calciner reaches 55%, sending a signal to the controller by the chlorine detector, controlling the air inlet valve to close after receiving the signal sent by the chlorine detector, controlling the calciner to calcine at 250 ℃, obtaining mixed powder after calcining for 2.5 hours, removing an organic binder by calcining, and introducing chlorine into high-temperature to calcine, so as to convert valuable metals into metal chloride, facilitating the subsequent leaching of chlorine, and preventing the chlorine from being decomposed into high-purity phosphoric acid, and further reducing the excessive chlorine to produce the high-purity metal chloride;
s3: adding phosphoric acid solution to regulate pH value to deposit iron
Adding the mixed powder into a first reactor until a second gravity sensor in the first reactor detects that the gravity in the first reactor is not increased any more, sending a signal to a controller by the second gravity sensor, controlling a first hydraulic pump to start after receiving the signal sent by the second gravity sensor, adding a phosphoric acid solution prepared by mixing phosphoric acid and water according to the volume ratio of 1:2.5 into the first reactor by the first hydraulic pump, obtaining a first mixture until a first pH detector in the first reactor detects that the pH value in the first reactor is=3.4, sending a signal to the controller by the first pH detector, controlling the first hydraulic pump to stop adding the phosphoric acid solution after receiving the signal sent by the first pH detector, controlling a suction filtration device in the first reactor to start, performing suction filtration on the first mixture to obtain ferric hydroxide precipitate and iron removal filtrate, and washing the ferric hydroxide precipitate for 2 times by deionized water;
s4: adding ammonia water to regulate pH value for removing copper
Pumping the deironing filtrate into a second reactor through a suction filtration device until a liquid level sensor in the second reactor detects that the liquid level of the deironing filtrate is not increased any more, sending a signal to a controller by the liquid level sensor, controlling a second hydraulic pump to absorb ammonia water generated in an exhaust gas collecting device in the step S6 after receiving the signal sent by the liquid level sensor, introducing the ammonia water into the second reactor until a second pH detector in the second reactor detects pH=6 in the second reactor, obtaining a second mixture, sending a signal to the controller by the second pH detector, controlling the second hydraulic pump to stop adding the ammonia water after receiving the signal sent by the second pH detector, controlling a filter pressing device in the second reactor to start, performing filter pressing on the second mixture to obtain copper hydroxide precipitate and a copper removal filtrate, washing and drying the copper hydroxide precipitate, and recovering a dry copper hydroxide product;
s5: adding phosphoric acid solution again to remove aluminum
Adding phosphoric acid solution into the copper removal filtrate until the pH value is=4.3, performing centrifugal separation to obtain aluminum hydroxide precipitate and aluminum removal filtrate, and washing and drying the aluminum hydroxide precipitate to obtain a dry aluminum hydroxide product;
s6: regenerating lithium iron phosphate and ball milling and mixing with carbonized fiber
Adding the aluminum removal filtrate into a hydrothermal reaction kettle, adding the ferric hydroxide precipitate into the hydrothermal reaction kettle, and adding Li 2 SO 4 ·H 2 O, adjusting the temperature of the hydrothermal reaction kettle to 210 ℃, carrying out hydrothermal reaction for 2.5h, and introducingThe ammonia gas generated by the reaction is collected by an exhaust gas collecting device at the top of the hydrothermal reaction kettle, the ammonia gas enters the exhaust gas collecting device and reacts with water in the exhaust gas collecting device to generate ammonia water, so that regenerated lithium iron phosphate is obtained, because valuable metal is oxidized into the highest price through chlorine gas in the step S2, a reducing agent is not needed to be used again in hydrothermal synthesis of the lithium iron phosphate, ammonia gas generated in the hydrothermal reaction is converted into ammonia water again by the exhaust gas collecting device so as to be recycled, the effect of saving resources is achieved, then polyacrylonitrile nano fibers and polyvinylpyrrolidone are added into N, N dimethylformamide according to the mass ratio of 1:2, the mixture is stirred for 11 hours by a stirrer and then added into a spinning machine to be spun, the composite fibers are subjected to hydrothermal treatment at the temperature of 85 ℃ for 5-6 hours, the composite fibers are cured for 1.5 hours at the temperature of 260 ℃, the cured composite fibers are placed in a tubular furnace, the temperature is raised to 1000 ℃ at the speed of 7.5 ℃/min, the composite fibers are obtained, the regenerated lithium iron phosphate and the composite fibers are mixed with the lithium iron phosphate according to the mass ratio of the polyacrylonitrile nano fibers and the lithium iron phosphate to the lithium iron phosphate material which is better than the lithium iron phosphate, and the composite material is obtained through ball milling and the electrochemical treatment of the lithium iron phosphate.
Example 3
A method for recycling valuable metals from a positive electrode material of a lithium iron phosphate battery, as shown in fig. 1, comprises the following steps:
s1: pretreatment of waste lithium iron phosphate battery
Discharging and disassembling the waste lithium iron phosphate battery, then putting the disassembled electrode slice into a freezing box, freezing for 1h, putting into boiling water, and stripping aluminum foil to obtain a positive electrode slice;
s2: vacuum treatment and chlorine gas charging calcination
Placing the positive plate into a crushing grinder to fully crush and grind to obtain positive powder, then opening a discharge valve of the crusher, pouring the positive powder into a calciner until a first gravity sensor in the calciner detects that the gravity in the calciner is not increased, sending a signal to a controller by the first gravity sensor, controlling the calciner to calcine for 5 hours at 500 ℃ after receiving the signal sent by the first gravity sensor by the controller, controlling a vacuum valve on the calciner to open by the controller, performing vacuum treatment, processing the interior of the calciner into a vacuum environment, controlling an air inlet valve of the calciner to open by the controller, introducing chlorine into the calciner through the air inlet valve until the chlorine content in the calciner reaches 65%, sending a signal to the controller by the chlorine detector, controlling the air inlet valve to close after receiving the signal sent by the chlorine detector, controlling the calciner to calcine at 300 ℃, obtaining mixed powder after calcining for 3 hours, removing an organic binder after crushing the positive plate, introducing chlorine into high-temperature to calcine, converting valuable metal into metal chloride, facilitating subsequent leaching, and controlling the chlorine into high-purity chlorine to be more convenient, and preventing the generation of excessive chlorine, and further reducing the generation of high-purity chlorine, and reducing the excessive chlorine;
s3: adding phosphoric acid solution to regulate pH value to deposit iron
Adding the mixed powder into a first reactor until a second gravity sensor in the first reactor detects that the gravity in the first reactor is not increased any more, sending a signal to a controller by the second gravity sensor, controlling a first hydraulic pump to start after receiving the signal sent by the second gravity sensor, adding a phosphoric acid solution prepared by mixing phosphoric acid and water according to the volume ratio of 1:3 into the first reactor by the first hydraulic pump until a first pH detector in the first reactor detects that the pH value in the first reactor is=3.5, obtaining a first mixture, sending a signal to the controller by the first pH detector, controlling the first hydraulic pump to stop adding the phosphoric acid solution after receiving the signal sent by the first pH detector, controlling a suction filtration device in the first reactor to start, performing suction filtration on the first mixture to obtain ferric hydroxide precipitate and deironing filtrate, and washing the ferric hydroxide precipitate for 3 times by deironing;
s4: adding ammonia water to regulate pH value for removing copper
Pumping the deironing filtrate into a second reactor through a suction filtration device until a liquid level sensor in the second reactor detects that the liquid level of the deironing filtrate is not increased any more, sending a signal to a controller by the liquid level sensor, controlling a second hydraulic pump to absorb ammonia water generated in an exhaust gas collecting device in the step S6 after receiving the signal sent by the liquid level sensor, introducing the ammonia water into the second reactor until a second pH detector in the second reactor detects pH=7 in the second reactor, obtaining a second mixture, sending a signal to the controller by the second pH detector, controlling the second hydraulic pump to stop adding the ammonia water after receiving the signal sent by the second pH detector, controlling a filter pressing device in the second reactor to start, performing filter pressing on the second mixture to obtain copper hydroxide precipitate and a copper removal filtrate, washing and drying the copper hydroxide precipitate, and recovering a dry copper hydroxide product;
s5: adding phosphoric acid solution again to remove aluminum
Adding phosphoric acid solution into the copper removal filtrate until the pH value is=4.5, performing centrifugal separation to obtain aluminum hydroxide precipitate and aluminum removal filtrate, and washing and drying the aluminum hydroxide precipitate to obtain a dry aluminum hydroxide product;
s6: regenerating lithium iron phosphate and ball milling and mixing with carbonized fiber
Adding the aluminum removal filtrate into a hydrothermal reaction kettle, adding the ferric hydroxide precipitate into the hydrothermal reaction kettle, and adding Li 2 CO 3 The temperature of the hydrothermal reaction kettle is regulated to 220 ℃ for hydrothermal reaction for 3 hours, meanwhile, ammonia gas generated by the reaction is collected through an exhaust gas collecting device at the top of the hydrothermal reaction kettle, after the ammonia gas enters the exhaust gas collecting device, ammonia water is generated by reaction with water in the exhaust gas collecting device, and regenerated lithium iron phosphate is obtained, and as valuable metals are oxidized to be the highest price through chlorine gas in the step S2, a reducing agent is not needed to be used in the hydrothermal synthesis of lithium iron phosphate, and the exhaust gas collecting device is utilized to carry out water synthesisThe ammonia gas generated during the thermal reaction is converted into ammonia water again for recycling, the effect of saving resources is achieved, then polyacrylonitrile nanofiber and polyvinylpyrrolidone are added into N, N-dimethylformamide according to the mass ratio of 1:3, the mixture is stirred for 12 hours by a stirrer, the mixture is added into a spinning machine for spinning, the composite fiber is obtained, the composite fiber is subjected to hydrothermal treatment at 90 ℃ for 6 hours, then is put into a muffle furnace for curing at 270 ℃ for 2 hours, the cured fiber is put into a tube furnace, the temperature of the cured fiber is increased to 1050 ℃ at the speed of 10 ℃/min for 3 hours, the carbonized composite fiber is obtained, the regenerated lithium iron phosphate and the carbonized composite fiber are added into a ball mill according to the mass ratio of 12:1, the regenerated lithium iron phosphate is obtained after uniform mixing, the regenerated lithium iron phosphate is synthesized through hydrothermal synthesis, the carbonized composite fiber is obtained by taking the polyacrylonitrile nanofiber and the polyvinylpyrrolidone as raw materials, and is subjected to hydrothermal treatment, curing and carbonization, the regenerated composite fiber and the regenerated lithium iron phosphate obtained after the regenerated composite fiber and the regenerated lithium iron phosphate are subjected to ball milling and mixing are better in electrochemical recycling performance to the battery compared with the regenerated lithium iron phosphate.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery is characterized by comprising the following steps of:
s1: pretreatment of waste lithium iron phosphate battery
Discharging and disassembling the waste lithium iron phosphate battery, then putting the disassembled electrode slice into a freezing box, freezing for 0.5-1h, putting into boiling water, and stripping aluminum foil to obtain a positive electrode slice;
s2: vacuum treatment and chlorine gas charging calcination
Treating the inside of a calciner into a vacuum environment, then introducing chlorine, crushing and grinding the positive plate, and then placing the crushed and ground positive plate into the calciner for calcination to obtain mixed powder;
s3: adding phosphoric acid solution to regulate pH value to deposit iron
Adding ammonia water into the mixed powder until the pH value is regulated to 3.3-3.5, carrying out suction filtration to obtain ferric hydroxide precipitate and deironing filtrate, and washing the ferric hydroxide precipitate;
s4: adding ammonia water to regulate pH value for removing copper
Adding ammonia water into the deironing filtrate until the pH value is adjusted to 5-7, performing filter pressing to obtain copper hydroxide precipitate and copper removal filtrate, washing and drying the copper hydroxide precipitate, and recovering a copper hydroxide product;
s5: adding phosphoric acid solution again to remove aluminum
Adding phosphoric acid solution into the copper removal filtrate until the pH value is 4-4.5, performing centrifugal separation to obtain aluminum hydroxide precipitate and aluminum removal filtrate, and washing and drying the aluminum hydroxide precipitate to obtain a dry aluminum hydroxide product;
s6: regenerating lithium iron phosphate and ball milling and mixing with carbonized fiber
Adding the ferric hydroxide precipitate into the aluminum removal filtrate, adding a lithium supplementing agent, reacting to obtain regenerated lithium iron phosphate, preparing carbonized composite fibers by taking polyacrylonitrile nanofibers and polyvinylpyrrolidone as raw materials, and ball-milling and mixing the carbonized composite fibers with the regenerated lithium iron phosphate to obtain the regenerated composite lithium iron phosphate.
2. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery according to claim 1, wherein the vacuum treatment and the calcination by introducing chlorine in the step S2 specifically comprises the following steps:
s2.1: putting the positive plate obtained in the step S1 into a crushing grinder, and fully crushing and grinding to obtain positive powder;
s2.2: opening a discharge valve of the crusher, pouring the anode powder into the calciner until a first gravity sensor in the calciner detects that the gravity in the calciner is not increased any more, and sending a signal to a controller by the first gravity sensor;
s2.3: after the controller receives the signal sent by the first gravity sensor, the calciner is controlled to calcine for 3-5 hours at 400-500 ℃;
s2.4: the controller controls a vacuum valve on the calciner to be opened for vacuum treatment, and the inside of the calciner is treated into a vacuum environment;
s2.5: the controller controls the inlet valve of the calciner to open, and chlorine is introduced into the calciner through the inlet valve until a chlorine detector in the calciner detects that the chlorine content in the calciner reaches 50-65%, and the chlorine detector sends a signal to the controller;
s2.6: and after receiving the signal sent by the chlorine detector, the controller controls the air inlet valve to be closed, and controls the calciner to calcine at 200-300 ℃ for 2-3 hours, so as to obtain the mixed powder.
3. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery according to claim 2, wherein the step S3 of adding the phosphoric acid solution to adjust the pH value for iron precipitation comprises the following steps:
s3.1: adding the mixed powder prepared in the step S2.6 into a first reactor until a second gravity sensor in the first reactor detects that the gravity in the first reactor is not increased any more, and sending a signal to a controller by the second gravity sensor;
s3.2: after receiving the signal sent by the second gravity sensor, the controller controls the first hydraulic pump to start, and the phosphoric acid solution is added into the first reactor through the first hydraulic pump;
s3.3: until the first pH detector in the first reactor detects the pH=3.3-3.5 in the first reactor, a first mixture is obtained, and the first pH detector sends a signal to a controller;
s3.4: after receiving the signal sent by the first pH detector, the controller controls the first hydraulic pump to stop adding the phosphoric acid solution, controls the suction filtration device in the first reactor to start, performs suction filtration on the first mixture to obtain ferric hydroxide sediment and deironing filtrate, and then deionizes and washes the ferric hydroxide sediment for 2-3 times.
4. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery according to claim 3, wherein the step S4 of adding ammonia water to adjust pH for copper removal comprises the following steps:
s4.1: pumping the deironing filtrate obtained in the step S3.4 into a second reactor through a suction filtration device until a liquid level sensor in the second reactor detects that the liquid level of the deironing filtrate is not increased any more, and sending a signal to a controller by the liquid level sensor;
s4.2: after receiving the signal sent by the liquid level sensor, the controller controls the second hydraulic pump to introduce ammonia water into the second reactor until the second pH detector in the second reactor detects pH=5-7 in the second reactor to obtain a second mixture, and the second pH detector sends a signal to the controller;
s4.3: after the controller receives the signal sent by the second pH detector, the second hydraulic pump is controlled to stop adding ammonia water, the filter pressing device in the second reactor is controlled to start, the second mixture is filter pressed to obtain copper hydroxide sediment and copper removal filtrate, and then the copper hydroxide sediment is washed and dried to recover a dry copper hydroxide product.
5. The method for recovering valuable metals from the positive electrode material of the lithium iron phosphate battery according to claim 4, wherein the regenerated lithium iron phosphate of the step S6 is mixed into the carbonized fiber by ball milling, and the method specifically comprises the following steps:
s6.1: adding the aluminum removal filtrate obtained in the step S5 into a hydrothermal reaction kettle, adding the ferric hydroxide precipitate obtained in the step S3.4 into the hydrothermal reaction kettle, adding a lithium supplementing agent, adjusting the temperature of the hydrothermal reaction kettle to be 200-220 ℃, and carrying out hydrothermal reaction for 2-3 hours to obtain regenerated lithium iron phosphate;
s6.2: adding polyacrylonitrile nanofiber and polyvinylpyrrolidone into N, N dimethylformamide according to a mass ratio of 1:1-3, stirring for 10-12h by using a stirrer, and then adding into a spinning machine for spinning to obtain composite fibers;
s6.3: carrying out hydrothermal treatment on the composite fiber for 5-6h at 80-90 ℃, then placing the composite fiber into a muffle furnace, and curing the composite fiber for 1-2h at 250-270 ℃ to obtain a cured composite fiber;
s6.4: placing the solidified fiber into a tube furnace, heating to 950-1050 ℃ at a speed of 5-10 ℃/min, and reacting for 1-3h to obtain carbonized composite fiber;
s6.5: adding the regenerated lithium iron phosphate and the carbonized composite fiber into a ball mill according to the mass ratio of 10-12:1, ball milling for 1-2 hours, and uniformly mixing to obtain the regenerated composite lithium iron phosphate.
6. The method for recycling valuable metals from the positive electrode material of the lithium iron phosphate battery according to claim 5, wherein in the step S6.1, ammonia generated by the reaction is collected through an exhaust gas collecting device at the top of a hydrothermal reaction kettle while the hydrothermal reaction is performed, ammonia is reacted with water in the exhaust gas collecting device to generate ammonia after entering the exhaust gas collecting device, then the ammonia generated in the exhaust gas collecting device is sucked by a hydraulic pump in the step S4.2, and then the ammonia is introduced into a second reactor to adjust the pH value for the reaction.
7. The method for recycling valuable metals from the lithium iron phosphate battery anode material according to claim 3, wherein the phosphoric acid solution is prepared by mixing phosphoric acid and water according to a volume ratio of 1:2-3.
8. The method for recovering valuable metals from lithium iron phosphate battery positive electrode material according to claim 5, wherein the lithium supplementing agent is LiOH, li 2 SO 4 ·H 2 O and Li 2 CO 3 One of them.
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