CN114709504A - Clean recovery method of waste lithium iron phosphate anode material - Google Patents
Clean recovery method of waste lithium iron phosphate anode material Download PDFInfo
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- CN114709504A CN114709504A CN202210330561.2A CN202210330561A CN114709504A CN 114709504 A CN114709504 A CN 114709504A CN 202210330561 A CN202210330561 A CN 202210330561A CN 114709504 A CN114709504 A CN 114709504A
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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
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- 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
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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
- H01M10/05—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
Abstract
The invention provides a clean recovery method of waste lithium iron phosphate anode materials, which comprises the following steps: (1) pretreating and separating aluminum foil, binder and carbon from the waste lithium iron phosphate positive electrode material to obtain a mixed material containing phosphorus, iron and lithium; (2) carrying out oxidation leaching on the mixed material in a sodium hydroxide solution to obtain mixed slurry, and carrying out solid-liquid separation to obtain ferric hydroxide precipitate and a leaching solution; (3) mixing sodium carbonate and the leachate, precipitating lithium and carrying out solid-liquid separation to obtain lithium carbonate and a separation solution; crystallizing and carrying out solid-liquid separation on the separation liquid to obtain sodium phosphate crystals; (4) and (3) mixing the lithium carbonate obtained in the step (2), the ferric hydroxide precipitate obtained in the step (3), phosphoric acid and carbon powder, and calcining to obtain the lithium iron phosphate. The clean recovery method can realize high-purity and high-efficiency recovery of the waste lithium iron phosphate anode material, and the process flow is clean and environment-friendly.
Description
Technical Field
The invention relates to the technical field of lithium ion waste battery recovery, in particular to a clean recovery method of a waste lithium iron phosphate positive electrode material.
Background
The gradual maturity of a series of novel power lithium ion batteries represented by lithium ion batteries becomes a solid foundation for the rapid development of the electric automobile industry. LiFePO over time4The number of used batteries will increase continuously. The huge number of waste power lithium ion batteries contain harmful substances such as waste organic electrolyte, binder conductive agent and the like and abundant lithium resources, and if reasonable and efficient harmless treatment and available resource recovery are not carried out, not only can the ecological environment be polluted, the human health is threatened, but also the resources are seriously wasted. Researchers have conducted a great deal of research on recycling and reusing waste lithium iron phosphate, but the effect is not good enough.
CN113582153A discloses a repairing and regenerating waste lithium iron phosphate positive electrode material and a repairing and regenerating method thereof, the method comprises the following steps: (1) uniformly mixing the waste lithium iron phosphate anode material with the material A, the carbon source and the metal additive ions to obtain a mixed material B; the material A comprises lithium carbonate and lithium hydroxide which are uniformly mixed; (2) and roasting the mixed material B in an inert or reducing atmosphere at a low temperature, and cooling to obtain the repaired and regenerated waste lithium iron phosphate material. The repaired and regenerated waste lithium iron phosphate anode material is of a core-shell coating structure, a coating layer is a carbon layer, and metal additive ion-doped lithium iron phosphate is coated by the carbon layer. However, impurities still remain in the lithium iron phosphate obtained by the method, and the electrochemical performance is not good.
CN113991204A discloses a short-process recovery method of waste lithium iron phosphate anode material, which comprises the following steps: placing the anode sheet material of the waste lithium iron phosphate battery in deionized water at 25 ℃ and 90 ℃ for repeatedly and alternately soaking for three times to obtain a waste lithium iron phosphate sheet material; drying the flaky waste lithium iron phosphate material, and then placing the dried flaky waste lithium iron phosphate material in a ball mill to grind for 1-3 hours to obtain waste lithium iron phosphate material powder; placing the waste lithium iron phosphate material powder in N-methyl-2-pyrrolidone, magnetically stirring for 10-14 h, filtering after stirring to obtain a black precipitate, centrifuging by using an organic solvent, cleaning, and drying to obtain the waste lithium iron phosphate anode material. Vanadium the lithium iron phosphate anode material recovered by the method has the problems of low product purity and difficulty in being directly used as battery-grade lithium iron phosphate.
At present, a clean and efficient recovery method of waste lithium iron phosphate cathode materials needs to be developed to improve the electrochemical performance of the recovered lithium iron phosphate.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a clean recovery method of waste lithium iron phosphate anode materials, the method is simple to operate, the raw materials for synthesizing lithium iron phosphate can be obtained after being treated by a hydrometallurgical method, battery-grade lithium iron phosphate can be synthesized again, sodium phosphate by-products are obtained at the same time, the leachate can be recycled for leaching out the lithium iron phosphate anode materials, no pollutants are discharged in the whole process, and the method is a clean waste battery recovery method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a clean recovery method of waste lithium iron phosphate anode materials, which comprises the following steps:
(1) pretreating and separating the waste lithium iron phosphate anode material to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out oxidation leaching on the mixed material in a sodium hydroxide solution to obtain mixed slurry, and carrying out solid-liquid separation to obtain ferric hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate and the leachate, precipitating lithium and carrying out solid-liquid separation to obtain lithium carbonate and a separation solution; crystallizing and carrying out solid-liquid separation on the separation liquid to obtain sodium phosphate crystals;
(4) and (3) mixing the lithium carbonate obtained in the step (2), the ferric hydroxide precipitate obtained in the step (3), phosphoric acid and carbon powder, and calcining to obtain the lithium iron phosphate.
In the invention, after the aluminum foil, the binder and the carbon are separated, the lithium iron phosphate battery anode material is subjected to oxidation leaching in NaOH solution, and LiFePO is obtained4Fe (II) in (b) is oxidized to Fe (III) to form Fe (OH)3Precipitation, the equation is as follows:
LiFePO4+NaOH+O2→Fe(OH)3+Na3PO4+LiOH
and continuously adding sodium carbonate into the leachate after the reaction to obtain a lithium carbonate precipitate, wherein the reaction equation is as follows:
2LiOH+Na2CO3＝Li2CO3+2NaOH
thus, Li and Fe in the leaching solution are separated, and Na also exists in the solution3PO4And excess NaOH, while Na3PO4The solubility of the sodium hydroxide is very sensitive to temperature, and Na can be obtained by a cooling crystallization method3PO4And (4) purifying the crystal to obtain a sodium phosphate product.
Precipitating the obtained Li2CO3、Fe(OH)3Mixing with phosphoric acid and carbon powder according to a certain proportion, calcining, and reducing Fe (III) into Fe (II) by the carbon powder to obtain the battery-grade lithium iron phosphate.
The invention realizes the preparation of battery-grade lithium iron phosphate from waste lithium iron phosphate cathode materials, the process is easy to industrialize, the operation is simple, and the obtained battery-grade lithium iron phosphate has high purity and excellent electrochemical performance.
Preferably, the pretreatment in step (1) comprises sequentially: the waste lithium iron phosphate positive electrode material is subjected to alkaline leaching separation aluminum foil and ball milling treatment to obtain a granular material, and the granular material is sequentially subjected to organic solvent soaking separation binder and roasting separation carbon.
Preferably, the alkaline solution of the alkaline leaching in step (1) comprises a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the concentration of the alkali solution is 0.05 to 1mol/L, and may be, for example, 0.05mol/L, 0.16mol/L, 0.27mol/L, 0.37mol/L, 0.48mol/L, 0.58mol/L, 0.69mol/L, 0.79mol/L, 0.9mol/L or 1mol/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, drying is included between the alkaline leaching and the ball milling treatment in step (1).
Preferably, the drying temperature is 80 to 120 ℃, for example, 80 ℃, 85 ℃, 89 ℃, 94 ℃, 98 ℃, 103 ℃, 107 ℃, 112 ℃, 116 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the drying time is 2 to 5 hours, for example, 2 hours, 2.4 hours, 2.7 hours, 3 hours, 3.4 hours, 3.7 hours, 4 hours, 4.4 hours, 4.7 hours, or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the ball milling treatment is followed by sieving.
Preferably, the sieving controls the particle size of the particulate material to be below 15 μm.
Preferably, the organic solvent soaking is performed under ultrasonic conditions.
Preferably, the organic solvent for soaking in the organic solvent comprises any one of acetone, N-methyl pyrrolidone or dimethylformamide or a combination of at least two of them, wherein typical but non-limiting combinations are a combination of acetone and N-methyl pyrrolidone, a combination of dimethylformamide and N-methyl pyrrolidone, and a combination of acetone and dimethylformamide.
Preferably, the organic solvent is soaked for 1 to 4 hours, for example, 1 hour, 1.4 hours, 1.7 hours, 2 hours, 2.4 hours, 2.7 hours, 3 hours, 3.4 hours, 3.7 hours or 4 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the calcination in the step (1) is 200 to 400 ℃, and may be, for example, 200 ℃, 223 ℃, 245 ℃, 267 ℃, 289 ℃, 312 ℃, 334 ℃, 356 ℃, 378 ℃ or 400 ℃, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the baking time is 2 to 5 hours, for example, 2 hours, 2.4 hours, 2.7 hours, 3 hours, 3.4 hours, 3.7 hours, 4 hours, 4.4 hours, 4.7 hours, or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the concentration of the sodium hydroxide solution in step (2) is 10 to 20 wt%, for example, 10 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
In the invention, the concentration of the sodium hydroxide solution is preferably controlled within the range, which is more favorable for improving the leaching rate, thereby improving the purity of ferric hydroxide precipitation and the purity and recovery rate of subsequent lithium carbonate.
Preferably, the temperature of the oxidative leaching is 100 to 150 ℃, for example, 100 ℃, 106 ℃, 112 ℃, 117 ℃, 123 ℃, 128 ℃, 134 ℃, 139 ℃, 145 ℃ or 150 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the oxygen partial pressure of the oxidative leaching is 0.1 to 0.5MPa, and may be, for example, 0.1MPa, 0.13MPa, 0.15MPa, 0.17MPa, 0.19MPa, 0.22MPa, 0.24MPa, 0.26MPa, 0.28MPa, 0.3MPa, 0.4MPa or 0.5MPa, but not limited to the values listed, and other values not listed in this range are also applicable.
The invention further controls the oxygen partial pressure and temperature of the oxidation leaching within the range, and is beneficial to improving the leaching rate and the purity of the final lithium iron phosphate product.
Preferably, the time of the oxidative leaching is 60-120 min, such as 60min, 67min, 74min, 80min, 87min, 94min, 100min, 107min, 114min or 120min, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, after the oxidation leaching, solid-liquid separation is carried out after temperature reduction.
Preferably, the temperature after temperature reduction is 80 to 90 ℃, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the sodium carbonate is added in step (3) in a molar ratio of carbonate to lithium ions in the leachate of 1-2: 1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the temperature of the mixing in step (3) is 80 to 95 ℃, for example, 80 ℃, 82 ℃, 84 ℃, 85 ℃, 86 ℃, 88 ℃, 90 ℃, 91 ℃, 92 ℃, 94 ℃ or 95 ℃, but not limited to the cited values, and other values not listed in the range are also applicable.
Preferably, the crystallization comprises cooling crystallization.
Preferably, the temperature of the final point of the cooling crystallization is 30 to 40 ℃, and may be, for example, 30 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the crystallization mother liquor obtained by solid-liquid separation after crystallization is supplemented with sodium hydroxide and then recycled for oxidation leaching in step (2).
Preferably, the molar ratio of the lithium carbonate, the ferric hydroxide precipitate, the phosphoric acid and the carbon powder in the step (4) is (0.98-1.02) - (0.28-0.32), and other values such as 0.98:0.98:1.00:0.28, 0.99:0.98:1.00:0.28, 1.00:0.98:1.00:0.28, 1.01:0.98:1.00:0.28, 1.02:0.98:1.00:0.28, 0.99:0.99:1.00:0.28, 0.99:1.02:1.02: 1.00:0.28, 0.99:1.02: 0.32, 0.99:1.02:1.02: 0.29: 0.02: 0.29.0.02: 1.0.02: 0.28, 0.02: 1.02: 0.31: 0.0.0.0.0.0.02: 1.0.0.0.0.0.0.0.0.02: 1.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.0.02, and the like are not specifically recited, but not limited to the above.
Preferably, the carbon powder comprises any one of graphite, acetylene black, carbon black or graphene or a combination of at least two of the graphite, the acetylene black, the carbon black and the graphene, and the graphite and the graphene are typically, but not limited to, a combination of graphite and acetylene black.
Preferably, the calcination comprises three stages of calcination, respectively a first calcination, a second calcination and a third calcination.
Preferably, the temperature of the first calcination is 280 to 320 ℃, for example, 280 ℃, 285 ℃, 289 ℃, 294 ℃, 298 ℃, 303 ℃, 307 ℃, 312 ℃, 316 ℃ or 320 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the first calcination is 1.5 to 3 hours, for example, 1.5 hours, 1.7 hours, 1.9 hours, 2 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.7 hours, 2.9 hours, or 3 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the first calcination is performed under vacuum conditions.
Preferably, the temperature of the second calcination is 420 to 480 ℃, for example, 420 ℃, 427 ℃, 434 ℃, 440 ℃, 447 ℃, 454 ℃, 460 ℃, 467 ℃, 474 ℃, or 480 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the second calcination is 2 to 4 hours, for example, 2 hours, 2.3 hours, 2.5 hours, 2.7 hours, 2.9 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, or 4 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the second calcination is carried out in a protective atmosphere.
Preferably, the temperature of the third calcination is 600 to 800 ℃, for example, 600 ℃, 623 ℃, 645 ℃, 667 ℃, 689 ℃, 712 ℃, 734 ℃, 756 ℃, 778 ℃ or 800 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the third calcination is 12 to 36 hours, for example, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 26 hours, 28 hours, 31 hours, 34 hours or 36 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the third calcination is carried out in a protective atmosphere.
Preferably, the protective atmosphere in the second calcination and the third calcination is a nitrogen atmosphere.
The invention further prefers to calcine in three sections, and can prepare the lithium iron phosphate anode material with proper and uniform granularity.
Preferably, the cleaning and recycling method comprises the following steps:
(1) carrying out alkaline leaching separation on the waste lithium iron phosphate positive electrode material by using 0.05-1 mol/L of alkali, carrying out solid-liquid separation, drying at 80-120 ℃ for 2-5 h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular material in an organic solvent under an ultrasonic condition for 1-4 h to separate a binder and roasting at 200-400 ℃ for 2-5 h to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out oxidation leaching on the mixed material for 60-120 min at 100-150 ℃ under the conditions that the concentration of a sodium hydroxide solution is 10-20 wt% and the oxygen partial pressure is 0.1-0.5 MPa, cooling the obtained mixed slurry to 80-90 ℃, and then carrying out solid-liquid separation to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate and the leachate according to the molar ratio of carbonate to lithium ions in the leachate being 1-2: 1, precipitating lithium and carrying out solid-liquid separation to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 30-40 ℃, and then carrying out solid-liquid separation to obtain sodium phosphate crystals;
(4) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder according to a molar ratio of (0.98-1.02) to (0.28-0.32), and sequentially performing first calcination at 280-320 ℃ for 1.5-3 h under a vacuum condition, second calcination at 420-480 ℃ for 2-4 h under a nitrogen atmosphere and second calcination at 600-800 ℃ for 12-36 h under a nitrogen atmosphere to obtain the lithium iron phosphate.
The solid-liquid separation in the above process is not particularly limited in the present invention, and any device and method for solid-liquid separation known to those skilled in the art can be used, and may be adjusted according to the actual process, such as filtration, centrifugation, or sedimentation, or may be a combination of different methods.
The drying in the above process is not limited in any way, and any device and method for drying known to those skilled in the art can be used, and can be adjusted according to the actual process, such as air drying, vacuum drying, oven drying or freeze drying, or a combination of different methods.
The ball milling in the above process is not limited in any way, and any device and method for ball milling known to those skilled in the art can be used, and can be adjusted according to the actual process, such as planetary ball milling, etc., or a combination of different methods.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the clean recovery method of the waste lithium iron phosphate anode material provided by the invention can be used for re-synthesizing battery-grade lithium iron phosphate, the recovery rates of lithium, phosphorus and iron are respectively more than 91%, more than 85% and more than 91%, the purity of the intermediate product ferric hydroxide precipitate is more than 99.3%, the purity of lithium carbonate is more than 99.9%, the purity of the final lithium iron phosphate is more than 99.92%, a sodium phosphate byproduct is obtained at the same time, the purity of the byproduct sodium phosphate is more than 99.1%, and no pollutant is discharged in the whole process;
(2) the lithium iron phosphate product obtained by the clean recovery method of the waste lithium iron phosphate anode material provided by the invention has high purity, the granularity of the lithium iron phosphate is within the range of 5-8 mu m, the 0.5 specific discharge capacity is more than 144mAh/g, the specific discharge capacity is more than 138mAh/g after 300 times of circulation, and the electrochemical performance is good;
(3) the method for cleanly recovering the waste lithium iron phosphate anode material has the advantages of high purity of the sodium phosphate byproduct and high recovery rate.
Drawings
Fig. 1 is a schematic flow chart of a method for cleaning and recovering a waste lithium iron phosphate positive electrode material provided in embodiment 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the appended claims.
Example 1
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, as shown in fig. 1, the clean recovery method includes the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a sodium hydroxide solution with the concentration of 1mol/L for 200r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 microns; the granular materials are sequentially soaked in an organic solvent in N-methyl pyrrolidone for 4 hours under the ultrasonic condition (power of 90W) to separate the binder, then filtered and dried, and then roasted at 300 ℃ for 4 hours to separate carbon, so as to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 100 ℃ oxidation leaching on the mixed material for 60min under the conditions that the concentration of a sodium hydroxide solution is 10 wt% and the oxygen partial pressure is 0.1MPa, cooling the obtained mixed slurry to 80 ℃, and then filtering to carry out solid-liquid separation and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 40 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder at the temperature of 80 ℃ according to the molar ratio of 0.98:1:0.98:0.3, and sequentially performing first calcination at 300 ℃ for 2h under a vacuum condition, second calcination at 450 ℃ in a nitrogen atmosphere for 2.5h and third calcination at 800 ℃ in the nitrogen atmosphere for 36h to obtain the lithium iron phosphate.
Example 2
The embodiment provides a clean recovery method of a waste lithium iron phosphate anode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a potassium hydroxide solution with the concentration of 0.1mol/L for 240r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular material in an organic solvent in dimethylformamide under an ultrasonic condition (power of 110W) for 2h to separate the binder, filtering and drying, and roasting at 200 ℃ for 4.5h to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 150 ℃ oxidation leaching on the mixed material for 120min under the conditions that the concentration of a sodium hydroxide solution is 20 wt% and the oxygen partial pressure is 0.5MPa, cooling the obtained mixed slurry to 90 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 2:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 30 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder at the temperature of 95 ℃ according to the molar ratio of 1.02:1:1.02:0.3, and sequentially performing first calcination at 300 ℃ for 2h under a vacuum condition, second calcination at 450 ℃ in a nitrogen atmosphere for 3h and third calcination at 700 ℃ in the nitrogen atmosphere for 24h to obtain the lithium iron phosphate.
Example 3
The embodiment provides a clean recovery method of a waste lithium iron phosphate anode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a sodium hydroxide solution with the concentration of 0.2mol/L for 300r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular material in an organic solvent in dimethylformamide under an ultrasonic condition (power of 120W) for 3 hours to separate the binder, then filtering and drying, and roasting at 400 ℃ for 2.5 hours to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 120 ℃ oxidation leaching on the mixed material for 90min under the conditions that the concentration of a sodium hydroxide solution is 15 wt% and the oxygen partial pressure is 0.3MPa, cooling the obtained mixed slurry to 85 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1.5:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 35 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder at the temperature of 85 ℃ according to the molar ratio of 1:0.98:1:0.28, and sequentially performing primary calcination at 320 ℃ for 1.5 hours under a vacuum condition, secondary calcination at 480 ℃ in a nitrogen atmosphere for 2 hours and tertiary calcination at 650 ℃ in a nitrogen atmosphere for 20 hours to obtain the lithium iron phosphate.
Example 4
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a sodium hydroxide solution with the concentration of 0.8mol/L for 400r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular materials in an organic solvent in acetone under an ultrasonic condition (power of 80W) for 5 hours to separate the binder, then filtering and drying, and roasting at 280 ℃ for 4 hours to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 130 ℃ oxidation leaching on the mixed material for 110min under the conditions that the concentration of a sodium hydroxide solution is 10 wt% and the oxygen partial pressure is 0.2MPa, cooling the obtained mixed slurry to 84 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1.2:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 37 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate obtained in the step (2), the ferric hydroxide precipitate obtained in the step (3), phosphoric acid and carbon powder according to a molar ratio of 1.02:1:1:0.3 at 88 ℃, and sequentially performing first calcination at 320 ℃ for 1.5h under a vacuum condition, second calcination at 420 ℃ in a nitrogen atmosphere for 4h and third calcination at 750 ℃ in the nitrogen atmosphere for 30h to obtain the lithium iron phosphate.
Example 5
The embodiment provides a clean recovery method of a waste lithium iron phosphate anode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in 0.9mol/L potassium hydroxide solution at the speed of 350r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at the temperature of 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular material in an organic solvent in acetone under an ultrasonic condition (power of 100W) for 2 hours to separate the binder, then filtering and drying, and roasting at 330 ℃ for 5 hours to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out oxidation leaching on the mixed material at 140 ℃ for 80min under the conditions that the concentration of a sodium hydroxide solution is 10 wt% and the oxygen partial pressure is 0.4MPa, cooling the obtained mixed slurry to 88 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 40 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder at a molar ratio of 1:1.02:1:0.32 at 90 ℃, and sequentially performing first calcination at 280 ℃ for 3h under a vacuum condition, second calcination at 420 ℃ in a nitrogen atmosphere for 4h and third calcination at 780 ℃ in the nitrogen atmosphere for 35h to obtain the lithium iron phosphate.
Example 6
The embodiment provides a clean recovery method of a waste lithium iron phosphate anode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a sodium hydroxide solution with the concentration of 0.1mol/L for 380r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular materials in an organic solvent in acetone under an ultrasonic condition (power of 50W) for 1.5h to separate the binder, filtering and drying, and roasting at 290 ℃ for 2h to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 150 ℃ oxidation leaching on the mixed material for 110min under the conditions that the concentration of a sodium hydroxide solution is 17 wt% and the oxygen partial pressure is 0.35MPa, cooling the obtained mixed slurry to 83 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1.3:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 40 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate obtained in the step (2), the ferric hydroxide precipitate obtained in the step (3), phosphoric acid and carbon powder according to a molar ratio of 1:1:1:0.31 at 85 ℃, and sequentially performing first calcination at 300 ℃ for 2h under a vacuum condition, second calcination at 450 ℃ in a nitrogen atmosphere for 3h and third calcination at 700 ℃ in the nitrogen atmosphere for 33h to obtain the lithium iron phosphate.
Example 7
The embodiment provides a clean recovery method of a waste lithium iron phosphate anode material, which comprises the following steps:
(1) stirring the waste lithium iron phosphate positive electrode material in a potassium hydroxide solution with the concentration of 0.7mol/L for 280.r/min, carrying out alkaline leaching to separate aluminum foil, filtering and washing the material, drying the material at 100 ℃ for 3h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular materials in an organic solvent in acetone under an ultrasonic condition (power of 150W) for 1h to separate the binder, filtering and drying, and roasting at 380 ℃ for 4h to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out 120 ℃ oxidation leaching on the mixed material for 100min under the conditions that the concentration of a sodium hydroxide solution is 17 wt% and the oxygen partial pressure is 0.4MPa, cooling the obtained mixed slurry to 80 ℃, and then filtering and washing to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate with the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1:1, precipitating lithium, filtering and washing to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 33 ℃, then filtering to obtain sodium phosphate crystals, and supplementing a sodium hydroxide solution into the crystallization mother liquid for circularly using the crystallization mother liquid for the oxidation leaching in the step (2);
(4) and (3) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder at the temperature of 95 ℃ according to the molar ratio of 1.02:0.98:1:0.3, and sequentially performing first calcination at 300 ℃ for 2h under a vacuum condition, second calcination at 450 ℃ in a nitrogen atmosphere for 2h and third calcination at 750 ℃ in the nitrogen atmosphere for 36h to obtain the lithium iron phosphate.
Example 8
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as the embodiment 1 except that the concentration of a sodium hydroxide solution in the step (2) is 25 wt%.
Example 9
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as the embodiment 1 except that the concentration of a sodium hydroxide solution in the step (2) is 5 wt%.
Example 10
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as that in embodiment 1 except that the partial pressure of oxygen subjected to oxidation leaching in step (2) is 0.05 MPa.
Example 11
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as that in embodiment 1 except that the partial pressure of oxygen subjected to oxidation leaching in step (2) is 0.7 MPa.
Example 12
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as the embodiment 1 except that the step (4) is not subjected to primary calcination.
Example 13
The embodiment provides a clean recovery method of a waste lithium iron phosphate positive electrode material, which is the same as the embodiment 1 except that the step (4) is not subjected to secondary calcination.
Comparative example 1
The comparative example provides a clean recovery method of a waste lithium iron phosphate positive electrode material, and the clean recovery method is the same as the embodiment 1 except that no organic solvent is soaked in the step (1).
Comparative example 2
The comparative example provides a clean recovery method of a waste lithium iron phosphate positive electrode material, and the clean recovery method is the same as the embodiment 1 except that roasting is not performed in the step (1) to separate carbon.
The test method comprises the following steps: testing the purity of lithium carbonate and ferric oxalate dihydrate by adopting an ICP (inductively coupled plasma) method, and calculating the recovery rate of lithium and iron by adopting a ratio method of the content of Li and Fe in lithium carbonate and ferric hydroxide products to the content of Li and Fe in the waste lithium iron phosphate positive electrode material; testing the purity of the lithium iron phosphate and the sodium phosphate by adopting an ICP method; calculating the recovery rate of phosphorus by adopting a ratio method of P in a sodium phosphate product to P in a waste lithium iron phosphate anode material; testing the granularity of the lithium iron phosphate by adopting a laser granularity distribution instrument; and testing the electrochemical performance of the lithium iron phosphate by adopting an electrochemical workstation method.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive embodiments 1 to 7 that the clean recovery method of the waste lithium iron phosphate cathode material provided by the invention can realize high-purity and high-efficiency recovery of the waste lithium iron phosphate cathode material, wherein the recovery rates of lithium, phosphorus and iron are respectively more than 91%, more than 85% and more than 91%; the purity of the obtained ferric hydroxide precipitate is more than 99.3 percent, the purity of lithium carbonate is more than 99.9 percent, the purity of the finally obtained lithium iron phosphate is more than 99.92 percent, the purity of a by-product sodium phosphate is more than 99.1 percent, the granularity of the obtained lithium iron phosphate is within the range of 5-8 mu m, the charge and discharge performance of the product is excellent, wherein the 0.5 specific discharge capacity is more than 144mAh/g, and the specific discharge capacity is more than 138mAh/g after 300 times of circulation;
(2) it can be seen from the comprehensive results of the examples 1 and 8-9 that the concentration of sodium hydroxide in the example 8 is up to 25 wt%, and the concentration of sodium hydroxide in the example 9 is only 5 wt%, wherein the recovery rates of Li, Fe and P in the example 8 are slightly higher than those in the example 1, but the discharge performance of the product is lower than that in the example 1, and the recovery rates of Li, Fe and P in the example 9 are significantly reduced, thereby indicating that the recovery rate and the product performance can be better ensured by controlling the concentration of sodium hydroxide within a specific range;
(3) it can be seen from the comprehensive results of example 1 and examples 10 to 11 that the acid-leaching oxygen partial pressure is low in example 10, the recovery rates of Li, Fe and P are reduced, the acid-leaching oxygen partial pressure is relatively high in example 11, the recovery rates of Li, Fe and P are not affected, but the product performance is not improved, and the oxygen content is increased, so that the oxygen partial pressure is controlled to ensure the recovery rate and the product performance and reduce the oxygen consumption;
(4) it can be seen from the comprehensive examples 1 and 12 to 13 that, in examples 12 to 13, the first calcination and the second calcination are not performed, the average particle size of the lithium iron phosphate in example 1 is only 5.6 μm, while in examples 12 to 13, the average particle sizes are as high as 34.6 μm and 44.5 μm, respectively, and the corresponding discharge performance and cycle performance are significantly reduced, thereby indicating that the performance of the lithium iron phosphate product is significantly improved by strictly controlling the calcination step of the lithium iron phosphate;
(5) it can be seen from the comprehensive examples 1 and 1-2 that, in the comparative example 2, the roasting separation of carbon is not performed, the lithium carbonate, ferric hydroxide and lithium iron phosphate have low purity, and the lithium iron phosphate product has poor discharge performance and cycle performance, and in the comparative example 1, the organic solvent soaking is not performed, so that the lithium carbonate, ferric hydroxide and lithium iron phosphate have low purity, and the lithium iron phosphate product has poor discharge performance and cycle performance.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A clean recovery method of waste lithium iron phosphate anode materials is characterized by comprising the following steps:
(1) pretreating and separating the waste lithium iron phosphate anode material to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out oxidation leaching on the mixed material in a sodium hydroxide solution to obtain mixed slurry, and carrying out solid-liquid separation to obtain ferric hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate and the leachate, precipitating lithium and carrying out solid-liquid separation to obtain lithium carbonate and a separation solution; crystallizing and carrying out solid-liquid separation on the separation liquid to obtain sodium phosphate crystals;
(4) and (3) mixing the lithium carbonate obtained in the step (2), the ferric hydroxide precipitate obtained in the step (3), phosphoric acid and carbon powder, and calcining to obtain the lithium iron phosphate.
2. The clean recycling method according to claim 1, wherein the pretreatment in step (1) comprises sequentially: carrying out alkaline leaching separation on aluminum foil and ball milling treatment on the waste lithium iron phosphate positive electrode material to obtain a granular material; and the granular material is sequentially soaked in an organic solvent to separate the binder and roasted to separate carbon.
3. The cleaning recovery method according to claim 2, wherein the alkaline solution of the alkaline leaching in step (1) comprises a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the concentration of the alkali solution is 0.05-1 mol/L.
4. The clean recovery method according to claim 2 or 3, characterized in that the step (1) comprises drying between the alkali leaching and the ball milling treatment;
preferably, the drying temperature is 80-120 ℃;
preferably, the drying time is 2-5 h;
preferably, the ball milling treatment is followed by sieving;
preferably, the sieving controls the particle size of the particulate material to be below 15 μm;
preferably, the organic solvent soaking is performed under ultrasonic conditions;
preferably, the organic solvent soaked by the organic solvent comprises any one or a combination of at least two of acetone, N-methyl pyrrolidone or dimethylformamide;
preferably, the soaking time of the organic solvent is 1-4 h.
5. The clean recycling method according to any one of claims 2 to 4, wherein the roasting temperature in step (1) is 200 to 400 ℃;
preferably, the roasting time is 2-5 h.
6. The clean recovery method according to any one of claims 1 to 5, wherein the concentration of the sodium hydroxide solution in the step (2) is 10 to 20 wt%;
preferably, the temperature of the oxidation leaching is 100-150 ℃;
preferably, the oxygen partial pressure of the oxidation leaching is 0.1-0.5 MPa;
preferably, the time of the oxidation leaching is 60-120 min;
preferably, after the oxidation leaching, the solid-liquid separation is carried out after the temperature reduction;
preferably, the temperature after cooling is 80-90 ℃.
7. The clean recovery method according to any one of claims 1 to 6, characterized in that the sodium carbonate is added in the step (3) according to the molar ratio of carbonate to lithium ions in the leachate of 1-2: 1;
preferably, the mixing temperature in the step (3) is 80-95 ℃;
preferably, the crystallization comprises cooling crystallization;
preferably, the final temperature of the cooling crystallization is 30-40 ℃;
preferably, the crystallization mother liquor obtained by solid-liquid separation after crystallization is supplemented with sodium hydroxide and then recycled for oxidation leaching in step (2).
8. The clean recovery method according to any one of claims 1 to 7, wherein the molar ratio of the lithium carbonate, the ferric hydroxide precipitate, the phosphoric acid and the carbon powder in step (4) is (0.98-1.02): (0.28-0.32);
preferably, the carbon powder comprises any one or a combination of at least two of graphite, acetylene black, carbon black or graphene.
9. The clean recovery method of any one of claims 1 to 8, wherein the calcination comprises three stages of calcination, namely a first calcination, a second calcination and a third calcination;
preferably, the temperature of the first calcination is 280-320 ℃;
preferably, the time of the first calcination is 1.5-3 h;
preferably, the first calcination is carried out under vacuum conditions;
preferably, the temperature of the second calcination is 420-480 ℃;
preferably, the time of the second calcination is 2-4 h;
preferably, the second calcination is carried out in a protective atmosphere;
preferably, the temperature of the third calcination is 600-800 ℃;
preferably, the time of the third calcination is 12-36 h;
preferably, the third calcination is carried out in a protective atmosphere;
preferably, the protective atmosphere in the second calcination and the third calcination is a nitrogen atmosphere.
10. The clean recycling method according to any one of claims 1 to 9, characterized in that the clean recycling method comprises the steps of:
(1) carrying out alkaline leaching separation on the waste lithium iron phosphate positive electrode material by using 0.05-1 mol/L of alkali, carrying out solid-liquid separation, drying at 80-120 ℃ for 2-5 h, carrying out ball milling treatment and vibrating screening to obtain a granular material with the particle size of below 15 mu m; sequentially soaking the granular material in an organic solvent under an ultrasonic condition for 1-4 h to separate a binder and roasting at 200-400 ℃ for 2-5 h to separate carbon to obtain a mixed material containing phosphorus, iron and lithium;
(2) carrying out oxidation leaching on the mixed material at 100-150 ℃ for 60-120 min under the conditions that the concentration of a sodium hydroxide solution is 10-20 wt% and the oxygen partial pressure is 0.1-0.5 MPa, cooling the obtained mixed slurry to 80-90 ℃, and then carrying out solid-liquid separation to obtain an iron hydroxide precipitate and a leaching solution;
(3) mixing sodium carbonate and the leachate according to the molar ratio of carbonate to lithium ions in the leachate of 1-2: 1, precipitating lithium and carrying out solid-liquid separation to obtain lithium carbonate and a separation solution; cooling and crystallizing the separation liquid, wherein the final temperature of the cooling and crystallizing is 30-40 ℃, and then carrying out solid-liquid separation to obtain sodium phosphate crystals;
(4) mixing the lithium carbonate in the step (2), the ferric hydroxide precipitate in the step (3), phosphoric acid and carbon powder according to a molar ratio of (0.98-1.02) to (0.28-0.32), and sequentially performing first calcination at 280-320 ℃ for 1.5-3 h under a vacuum condition, second calcination at 420-480 ℃ for 2-4 h in a nitrogen atmosphere and second calcination at 600-800 ℃ for 12-36 h in a nitrogen atmosphere to obtain the lithium iron phosphate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115149140A (en) * | 2022-08-23 | 2022-10-04 | 宜春天赐高新材料有限公司 | Method for recovering iron and lithium from waste lithium iron phosphate batteries |
| CN116462172A (en) * | 2023-05-22 | 2023-07-21 | 甘肃睿思科新材料有限公司 | Method for preparing battery-grade ferric phosphate by using carbon-containing crude ferric phosphate generated by selectively extracting lithium from waste ferric phosphate |
| CN116692952A (en) * | 2023-06-30 | 2023-09-05 | 江西三吨锂业有限公司 | Method for treating waste lithium iron phosphate anode material and co-producing FeOOH and lithium phosphate |
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2022
- 2022-03-30 CN CN202210330561.2A patent/CN114709504A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115149140A (en) * | 2022-08-23 | 2022-10-04 | 宜春天赐高新材料有限公司 | Method for recovering iron and lithium from waste lithium iron phosphate batteries |
| CN116462172A (en) * | 2023-05-22 | 2023-07-21 | 甘肃睿思科新材料有限公司 | Method for preparing battery-grade ferric phosphate by using carbon-containing crude ferric phosphate generated by selectively extracting lithium from waste ferric phosphate |
| CN116462172B (en) * | 2023-05-22 | 2023-09-19 | 甘肃睿思科新材料有限公司 | Method for preparing battery-grade ferric phosphate by using carbon-containing crude ferric phosphate generated by selectively extracting lithium from waste ferric phosphate |
| CN116692952A (en) * | 2023-06-30 | 2023-09-05 | 江西三吨锂业有限公司 | Method for treating waste lithium iron phosphate anode material and co-producing FeOOH and lithium phosphate |
| CN116692952B (en) * | 2023-06-30 | 2024-04-05 | 江西三吨锂业有限公司 | Method for treating waste lithium iron phosphate anode material and co-producing FeOOH and lithium phosphate |
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