CN114583306A - Method for recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs (metal-organic frameworks) material by organic acid integrated two-in-one double-effect - Google Patents
Method for recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs (metal-organic frameworks) material by organic acid integrated two-in-one double-effect Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 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 26
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 24
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 title description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000006228 supernatant Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000010926 waste battery Substances 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 50
- 238000003828 vacuum filtration Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 229910010710 LiFePO Inorganic materials 0.000 claims description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000012064 sodium phosphate buffer Substances 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000002386 leaching Methods 0.000 abstract description 5
- 239000010802 sludge Substances 0.000 abstract description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 9
- 239000013291 MIL-100 Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000013144 Fe-MIL-100 Substances 0.000 description 2
- 239000013302 MIL-88A Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000013255 MILs Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Iron (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling all elements of waste lithium iron phosphate batteries and preparing an iron-based MOFs material by integrating organic acid into a whole, which comprises the following steps: in waste battery LiFePO4Adding deionized water into the positive electrode powder; adding organic acid into the solution formed in the first step, stirring for reaction, and filtering acid sludge; adding hydrogen peroxide into the filtered solution, and stirring for reaction; adding the reacted solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a hydrothermal box, crystallizing the high-pressure reaction kettle for 6 to 15 hours at the temperature of 100 to 180 ℃, and naturally cooling the high-pressure reaction kettle to room temperature; centrifuging, washing and drying the solution for later use; sequentially adding the dried powder into deionized water and ethanol, stirring and filtering, collecting and drying to obtain the iron-based MOFs material; adjusting the pH of the supernatant obtained by centrifugation in step five to make Li+And PO4 3‑Concentrated crystallization conversion into Li3PO4Precipitating; the invention utilizes an organic acid integrated dual-purpose method to complete element leaching and Fe impurity removal.
Description
Technical Field
The invention belongs to the technical field of waste battery recovery and functional material preparation, and particularly relates to a method for recovering all elements of waste lithium iron phosphate batteries and preparing an iron-based MOFs material by using organic acid.
Background
Metal organic framework compounds (MOFs) are multifunctional materials, and the mesh porous structure thereof has a variety of excellent properties such as adsorption, separation and gas storage, and is widely applied in various fields. The iron-based MOFs (MILs series) with iron as a central atom has the characteristics of low cost, no toxicity, good environmental protection and the like, and the Fe-MOFs has great application potential in the field of catalysis due to the characteristics of high porosity, chemical resistance and the like.
Currently, the synthesis of MOFs mainly includes hydrothermal synthesis, microwave synthesis, ultrasonic synthesis, etc., and the hydrothermal synthesis is the most widely used synthesis method. FeCl is needed in the hydrothermal synthesis of Fe-MOFs3Or Fe (NO)3)3Adding specific organic ligand and solvent into the raw material of the isolyotropic salt, mixing according to a certain proportion, and putting the mixture into a high-pressure reaction kettle to generate the required product.
With the large-scale application of lithium iron phosphate batteries, research on the recycling problem of the lithium iron phosphate batteries is deepened continuously, and lithium iron phosphate (LiFePO) is treated by strong acid in the traditional acid leaching process4) Conversion to Li+、Fe3+、PO4 3-The impurity Fe is firstly mixed by adjusting the pH through adding a large amount of alkali3+Conversion to Fe (OH)3And FePO4Filtering the mixed precipitate, and adding NaCO into the supernatant3，Li+With CO3 2-Concentrated crystalline conversion to Li2CO3Realization of valuable metal Li+And (4) recovering.
In the iron removal step, a large amount of alkali is added to adjust the pH value, the recovery process complexity is increased, and meanwhile, Fe and P elements cannot be effectively recycled, and special treatment is needed in the form of acid sludge, so that resource waste is caused.
The recovery process needs strong acid and strong base leaching and impurity removal, and has the problems of strict requirements on operating equipment, waste of element resources and poor economic benefit.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an organic acid integrated two-effect recovery method for all elements of waste lithium iron phosphate batteries and a method for preparing the sameThe method for preparing the iron-based MOFs material utilizes an organic acid integrated dual-purpose method to fulfill the aims of element leaching and Fe impurity removal and reduce the acid sludge yield, and converts iron impurities into the MOFs functional material in the process, and meanwhile Li+And P element with Li3PO4The way of (2) is effectively recovered.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recycling all elements of waste lithium iron phosphate batteries and preparing an iron-based MOFs material in an organic acid integrated two-effect mode comprises the following steps:
step one, according to the solid-to-liquid ratio of 5-40 mL/g, waste battery LiFePO is added4Adding deionized water into the positive electrode powder;
step two, in the solution formed in the step one, according to the ratio of the Fe element to the organic ligand substance of 1: (0.2-2.0) adding an organic acid;
step three, adding LiFePO into the solution formed in the step two4Amount ratio to hydrogen peroxide substance 1: (2.9-5.0) adding hydrogen peroxide, and stirring and reacting for 2-24 hours at the temperature of 20-100 ℃;
adding the reacted solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a hydrothermal box, performing hydrothermal crystallization for 6-15 hours at the temperature of 100-180 ℃, and naturally cooling to room temperature;
step five, centrifuging the solution after the hydrothermal reaction, and washing, centrifuging and drying the separated powder for later use;
step six, sequentially adding the dried powder in the step five into deionized water and ethanol, stirring and filtering, and collecting and drying the filtered powder to obtain the iron-based MOFs material;
seventhly, regulating the pH of the supernatant obtained in the step five by centrifugation to 11-13 to ensure that Li+And PO4 3-Concentrated crystal is converted into Li3PO4Precipitating and separating from the solution.
The invention also has the following technical characteristics:
preferably, the organic acid is trimesic acid or fumaric acid.
Preferably, in the fifth step, the centrifugal rotating speed is 6000 to 11000r/min, and the centrifugal time is 5 to 10 min.
Preferably, the washing in the fifth step is centrifugal washing with deionized water for 2-3 times.
Preferably, the drying in the fifth step is drying in an oven at 60 ℃ for 12 h.
Preferably, in the sixth step, the powder dried in the fifth step is mixed with excessive deionized water, stirred for 3 hours at a constant temperature of 80 ℃, and then subjected to primary vacuum filtration.
Preferably, in the sixth step, the crystal obtained by the first suction filtration is dissolved in excess ethanol, stirred for 3 hours at the constant temperature of 60 ℃, and then vacuum filtered again.
Preferably, the collection and drying in the sixth step are collected in a culture dish and dried in an oven at 100 ℃ for 12 hours.
Preferably, in the seventh step, ammonia water, sodium phosphate buffer solution or sodium hydroxide is used for adjusting the pH value of the solution.
Compared with the prior art, the invention has the following technical effects:
the invention provides an integrated dual-purpose method by utilizing organic acid, which simultaneously achieves the dual purposes of element leaching, iron element impurity removal and high-value utilization; in the process, the organic acid can be used as a ligand to form Fe-MOF with Fe, so that iron impurities are converted into high-value MOFs functional materials, and Li in the solution+And PO4 3-With Li3PO4Is recovered in the form of Li+P element is effectively recovered, and the high value of all elements is realized;
according to the method, the mild organic acid replaces a strong corrosive inorganic acid to successfully etch the lithium iron phosphate material and participate in MOFs construction, so that the problems that a large amount of acidic solution is used and a solution system is too complex are avoided, the acid residue amount and the salt concentration in waste liquid are reduced, the alkali consumption is reduced, the equipment requirement is low, and the operation environment is friendly;
the method has short synthesis period, and the used reagent is cheap and easy to obtain, and is suitable for large-scale production.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of example 1 showing characteristic diffraction peaks for MIL-100 (Fe);
FIG. 2 is an X-ray diffraction pattern (XRD) of example 1, showing Li as a recovered product3PO4Characteristic diffraction peaks of (a);
FIG. 3 is a SEM photograph of example 1 showing the bulk morphology at 35000 times MIL-100 (Fe);
FIG. 4 is a SEM photograph of example 1 showing the bulk morphology at a magnification of MIL-100(Fe) of 60000.
Detailed Description
The present invention will be explained in further detail with reference to examples.
In the following examples, the methods and the experimental equipment used are conventional methods and instruments unless otherwise specified. The method used in the examples is a hydrothermal synthesis of Fe-MOFs, using experimental equipment including a bench top high speed centrifuge, (H1650) field emission scanning electron microscope (Gemini SEM 500) and X-ray diffraction spectrometer (Bruker D8 Advance).
The first embodiment is as follows:
a method for synthesizing MIL-100 (Fe).
At room temperature, 1.32g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 2.48g of trimesic acid (H) weighed out3BTC), adding 3mL of 30% hydrogen peroxide into the solution, reacting at 60 ℃ for 2h, pouring the solution into two 50mL high-pressure reaction kettles in equal amount, placing the reaction kettles into a hydrothermal box, setting the reaction temperature at 180 ℃, and reacting for 12 h;
after the high-pressure reaction is finished, centrifuging the product for 10min at the rotating speed of 8000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding ammonia water to adjust the pH of the supernatant to 11, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 3 times, centrifuging at 10000r/min for 5min, and drying the washed product in a 60 ℃ oven for 12 h; mixing the dried powder with 50mL of deionized water, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
Concentrating and crystallizing the obtained solid from the supernatant, wherein an X-ray diffraction spectrum (figure 1) of the solid shows a characteristic diffraction peak of MIL-100 (Fe); drying gave a bright orange powder whose X-ray diffraction pattern (FIG. 2) showed Li3PO4Characteristic diffraction peaks of (a); the field emission scanning electron microscope photos (FIG. 3, FIG. 4) show the morphological structure of the MIL-100(Fe) material; the scanning electron micrograph (FIG. 3) at 35000 times magnification shows that the synthetic material has a relatively blocky structure, and the scanning electron micrograph (FIG. 4) at 60000 times magnification shows that the synthetic material has a structure of blocky small particles of 50-150 nm.
Example two:
a method for synthesizing MIL-100 (Fe).
At room temperature, 1.32g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 2.48g of trimesic acid (H) weighed out3BTC) immersion solution;
adding 3mL of 30% hydrogen peroxide into the solution, adding 0.3g of 1M NaOH reagent, and reacting at 60 ℃ for 2 h; after the reaction is finished, the solution is orange viscous, the solution is poured into two 50mL high-pressure reaction kettles in equal amount, then the reaction kettles are placed into a hydrothermal box, the reaction temperature is set to be 180 ℃, and the reaction time is 12 hours;
after the high-pressure reaction is finished, centrifuging the product for 10min at the rotating speed of 8000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding sodium phosphate buffer solution to adjust the pH of the supernatant to 12, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 3 times, centrifuging at 10000r/min for 5min, and drying the washed product in a 60 ℃ oven for 12 h; mixing the dried powder with 50mL of deionized water, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
Example three:
a method for synthesizing MIL-100 (Fe).
At room temperature, 1.32g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 2.48g of trimesic acid (H) weighed out3BTC) immersion solution;
adding 3mL of 30% peroxide into the solution, uniformly mixing the medicines by ultrasonic treatment, and then adding H3NO4(65-65%) 1.14mL, HF (40%) 0.6mL, reacting at 60 ℃ for 2h, pouring the solution into two 50mL high-pressure reaction kettles in equal amount, placing the reaction kettles into a hydrothermal box, setting the reaction temperature at 180 ℃ and the reaction time at 12h, wherein the solution is orange and sticky after the reaction;
after the high-pressure reaction is finished, centrifuging the product for 10min at the rotating speed of 8000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding sodium hydroxide to adjust the pH of the supernatant to 13, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 2-3 times, centrifuging at 10000r/min for 5min, and drying the washed product in an oven at 60 ℃ for 12 h; mixing the dried powder with 50mL of deionized water, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
In the reaction processes of the embodiment 2 and the embodiment 3, a strong acid or strong base assistant is added for regulating and controlling the appearance of the iron-based MOFs material, so that the iron-based MOFs material with irregular shape tends to grow into uniform spindle-shaped nanorods, and the crystallinity is obviously improved.
Example four:
a method for synthesizing MIL-88A (Fe).
At room temperature, 1.57g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 2.60g of fumaric acid (C) weighed4H4O4) Immersing in the solution;
adding 3mL of 30% peroxide into the solution, reacting at 60 ℃ for 2h, pouring the solution into two 50mL high-pressure reaction kettles in equal amount, placing the reaction kettles into a hydrothermal box, setting the reaction temperature at 100 ℃, and reacting for 12 h;
after the high-pressure reaction is finished, centrifuging the product for 10min at the rotating speed of 8000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding ammonia water to adjust the pH of the supernatant to 11, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 2 times, and centrifuging at 10000r/min for 10 min; drying the washed product in an oven at 60 ℃ for 12 h; adding the dried powder into 50mL of deionized water, mixing, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
Example five:
a method for synthesizing MIL-88A (Fe).
Weighing 16mmol of lithium iron phosphate cathode powder (LiFePO) at room temperature4) 50mL of deionized water was added to the solution, and 24mmol of fumaric acid (C) weighed out was added4H4O4) Immersing in the solution;
3mL of 30% peroxide is added into the solution, the solution reacts violently for 24 hours at 60 ℃, the solution is orange viscous after the reaction is finished, the solution is poured into two 50mL high-pressure reaction kettles in equal quantity, then the reaction kettles are placed into a hydrothermal box, the reaction temperature is set to be 120 ℃, and the reaction time is 12 hours;
after the high-pressure reaction is finished, the reaction kettle is naturally cooled, the product is centrifuged for 10min at the rotating speed of 8000r/min, supernatant and orange precipitate are generated, sodium hydroxide is added to adjust the pH of the supernatant to 12, and Li is separated out under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 3 times, centrifuging at 10000r/min for 5min, drying the washed product in a 60 ℃ drying oven for 12h, mixing the dried powder with 50mL of deionized water, stirring at the constant temperature of 80 ℃ for 3h, separating the mixed solution by adopting a vacuum filtration method, dissolving the MOFs on the filtered filter paper in 50mL of ethanol, stirring at the constant temperature of 60 ℃ for 3h, separating the mixed solution by adopting a vacuum filtration method again, collecting the MOFs on the filtered filter paper in a culture dish, and drying the sample in the 100 ℃ drying oven for 12 h.
Example six:
a method for synthesizing MIL-100 (Fe).
At room temperature, 10.0g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 2.66g of trimesic acid (H) weighed out3BTC) immersion solution;
adding 18.5mL of 30% hydrogen peroxide into the filtered solution, reacting at 20 ℃ for 12h, pouring the solution into two 50mL high-pressure reaction kettles in equal amount, placing the reaction kettles into a hydrothermal box, setting the reaction temperature at 180 ℃ and the reaction time at 6h, wherein the solution is orange viscous after the reaction is finished;
after the high-pressure reaction is finished, centrifuging the product for 8min at the rotating speed of 6000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding ammonia water to adjust the pH of the supernatant to 12, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 2 times, centrifuging at 6000r/min for 8min, and drying the washed product in a 60 ℃ oven for 12 h; mixing the dried powder with 50mL of deionized water, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
Example seven:
a method for synthesizing MIL-100 (Fe).
At room temperature, 1.25g of lithium iron phosphate positive electrode powder (LiFePO) is weighed4) 50mL of deionized water was added to the solution, and 3.33g of trimesic acid (H) weighed out3BTC) is immersed in the solution, stirred and reacted for 4 hours, and then acid sludge is filtered;
adding 4mL of 30% hydrogen peroxide into the filtered solution, reacting for 2 hours at 100 ℃ violently, pouring the solution into two 50mL high-pressure reaction kettles in equal amount, placing the reaction kettles into a hydrothermal box, setting the reaction temperature at 100 ℃, and reacting for 15 hours, wherein the solution is orange viscous after the reaction is finished;
after the high-pressure reaction is finished, centrifuging the product for 5min at the rotating speed of 11000r/min after the reaction kettle is naturally cooled to generate supernatant and orange precipitate, adding ammonia water to adjust the pH of the supernatant to 13, and separating Li under the action of concentration and crystallization3PO4Filtering and collecting a solid product;
washing the orange precipitate with deionized water for 3 times, centrifuging at 10000r/min for 5min, and drying the washed product in an oven at 60 ℃ for 12 h; mixing the dried powder with 50mL of deionized water, stirring for 3h at the constant temperature of 80 ℃, separating the mixed solution by adopting a vacuum filtration mode, dissolving the MOFs on the filtered paper into 50mL of ethanol, stirring for 3h at the constant temperature of 60 ℃, separating the mixed solution by adopting the vacuum filtration mode again, collecting the MOFs on the filtered paper in a culture dish, and drying the sample in an oven at the temperature of 100 ℃ for 12 h.
Claims (9)
1. A method for recycling all elements of waste lithium iron phosphate batteries and preparing an iron-based MOFs material in an organic acid integrated two-effect mode is characterized by comprising the following steps:
step one, LiFePO is added into waste batteries according to the solid-liquid ratio of 5-40 mL/g4Adding deionized water into the positive electrode powder;
step two, in the solution formed in the step one, according to the ratio of the Fe element to the organic ligand substance of 1: (0.2-2.0) adding an organic acid;
step three, adding LiFePO into the solution formed in the step two4Amount ratio to hydrogen peroxide substance 1: (2.9-5.0) adding hydrogen peroxide, and stirring and reacting for 2-24 hours at the temperature of 20-100 ℃;
adding the reacted solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a hydrothermal box, performing hydrothermal crystallization for 6-15 hours at the temperature of 100-180 ℃, and naturally cooling to room temperature;
step five, centrifuging the solution after the hydrothermal reaction, and washing, centrifuging and drying the separated powder for later use;
step six, sequentially adding the dried powder in the step five into deionized water and ethanol, stirring and filtering, and collecting and drying the filtered powder to obtain the iron-based MOFs material;
seventhly, regulating the pH of the supernatant obtained in the step five by centrifugation to 11-13 to ensure that Li+And PO4 3-Concentrated crystallization conversion into Li3PO4Precipitating and separating from the solution.
2. The method for integrally and efficiently recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs materials according to claim 1, wherein the organic acid is trimesic acid or fumaric acid.
3. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an integrated manner by using the organic acid as claimed in claim 1, wherein in the fifth step, the centrifugal rotation speed is 6000-11000 r/min, and the centrifugal time is 5-10 min.
4. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an organic acid integrated and dual-effect manner according to claim 3, wherein the washing in the fifth step is centrifugal washing with deionized water for 2-3 times.
5. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an integrated and two-way manner by using the organic acid as claimed in claim 4, wherein the drying in the fifth step is drying in an oven at 60 ℃ for 12 hours.
6. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an integrated and two-effect manner according to claim 1, wherein in the sixth step, the powder dried in the fifth step is mixed with excessive deionized water, stirred for 3 hours at a constant temperature of 80 ℃, and then subjected to vacuum filtration once.
7. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an integrated and two-effect manner according to claim 1 or 6, wherein in the sixth step, the crystals obtained by one-time suction filtration are dissolved in excessive ethanol, stirred for 3 hours at a constant temperature of 60 ℃, and subjected to vacuum filtration again.
8. The method for recycling all elements of the waste lithium iron phosphate batteries and preparing the iron-based MOFs material in an integrated and dual-effect manner according to claim 1, wherein the collection and drying in the sixth step are carried out by collecting in a culture dish and drying in an oven at 100 ℃ for 12 hours.
9. The method for recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs materials according to claim 1, wherein ammonia water, sodium phosphate buffer solution or sodium hydroxide are used to adjust the pH value of the solution in step seven.
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