CN112047320A - Treatment method for low-pollution recycling of lithium iron phosphate material - Google Patents
Treatment method for low-pollution recycling of lithium iron phosphate material Download PDFInfo
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Abstract
The invention discloses a treatment method for recycling a lithium iron phosphate material with low pollution, which comprises the steps of firstly, discharging, disassembling and separating waste lithium iron phosphate batteries to obtain positive and negative pole pieces, using a combination method of hot acid solution soaking, ultrasonic wave loosening and high-pressure water gun stripping to obtain a lithium iron phosphate mixed material, then calcining the lithium iron phosphate mixed material, detecting the contents of elements Fe, Li and P in the lithium iron phosphate mixed material, supplementing an Fe source, an Li source, a P source and a sugar source according to the detection result, simultaneously adding an Mg source, a Ti source and an Mn source for doping, loosening a grain structure of the calcined material by using an acid solution with the weight percentage concentration of 1-5%, adding a proportioned supplementing material to obtain a slurry, finally grinding the slurry, spraying, pelletizing and drying, and calcining again to obtain the lithium iron phosphate material. The method is simple to operate, the waste lithium iron phosphate battery is recycled and utilized as a qualified lithium iron phosphate finished product, the pollution is low, the conversion rate is high, and the performance is good and stable.
Description
Technical Field
The invention relates to the technical field of lithium iron phosphate battery recovery, in particular to a treatment method for low-pollution recovery and reuse of a lithium iron phosphate material.
Background
The electric vehicle industry has developed vigorously, and batteries, one of the core accessories, have been widely researched and paid attention to. The olivine-type lithium iron phosphate has the advantages of low raw material price, high specific energy, good thermal stability, no pollution to the environment and the like, and is widely applied to the aspect of power batteries. According to the requirement of 'notice on carrying out new energy automobile power storage battery recycling and pilot plant work by organizations' (Ministry of industry and communications 'Union letter No. [ 2018 ] 68'), government related departments strengthen experience exchange and cooperation with pilot plant areas and enterprises, promote to form a cross-region and cross-industry cooperation mechanism, and ensure efficient recycling and harmless disposal of the power storage battery. Comprehensively considers the recycling of the lithium iron phosphate anode material for reproduction, and is beneficial to saving resources and protecting environment.
Abnormal materials are inevitably produced in the production of the lithium iron phosphate due to equipment failure or other reasons. Including oxidation during production, unbalanced raw material ratio, overburning and the like. In order to reduce the production loss to the maximum extent, the treatment method for recycling, doping and modifying the lithium iron phosphate material has simple process, and effectively recycles and resynthesizes the lithium iron phosphate material.
At present, lithium batteries are mostly recycled on anode materials with higher values, and the recycling routes are as follows:
direct calcination: for example, CN 200710129898.2, a recycling method of waste lithium iron phosphate power batteries, calcining a positive electrode material at 450-600 ℃ for 2-5 hours, adding an ethanol solution of ferric salt, mixing, calcining at 300-500 ℃ for 2-5 hours, and using nitrogen as a protective gas. The obtained lithium iron phosphate anode material has high cost and unstable material performance.
Dissolving: for example, CN 201010148325.6, a comprehensive recycling method for waste lithium iron phosphate batteries, which is to dissolve lithium iron phosphate with acid, remove copper ions with sodium sulfide, precipitate iron and lithium in the solution with NaOH or ammonia water, add an iron source, a lithium source or a phosphorus source compound to the precipitate to adjust the components of iron, lithium and phosphorus, add a carbon source, ball mill, and calcine in an inert atmosphere to obtain a new lithium iron phosphate positive electrode material. The cost is high, the pollution is large, meanwhile, the product consistency is difficult to ensure, and the industrialized recovery of the lithium iron phosphate can not be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a treatment method for recycling a lithium iron phosphate material with low pollution, so that the waste of resources is avoided, and the cost for preparing the lithium iron phosphate material is reduced.
The technical scheme of the invention is as follows:
a treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive pole piece, a negative pole piece and a shell;
(2) respectively soaking the positive and negative electrode plates in a hot acid solution or an organic solution at the temperature of 80-100 ℃ and simultaneously ultrasonically loosening the material structure for 40-60min, then spraying and stripping the electrode plate material by using a high-pressure water gun, filtering to obtain leaching filtrate and filter residue, and melting, metallurgically recycling and reusing the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at the temperature of 450-600 ℃ for 60-90min, thereby removing carbon and other organic components;
(4) after the content of elements Fe, Li and P in the calcined material in the step (3) is detected, a Fe source, a Li source, a P source and a sugar source are supplemented according to the detection result, and an Mg source, a Ti source and a Mn source are added for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the mol ratio of Fe, Li and P in the materials after supplementing Fe source, Li source and P source is Li: fe: p is 1-1.1:1:1.02-1.04, and the molar ratio of Fe element in the calcined material and the supplementary Fe source is 0.8-8;
(5) loosening the grain structure of the calcined material in the step (3) for 2-10h by using an acid solution with the weight percentage concentration of 1-5%, and adding the prepared supplementary material in the step (4) to obtain slurry;
(6) grinding the slurry proportioned in the step (5) by using a sand mill until the granularity D50 of the slurry is 0.35-0.5 mu m, then spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700-790 ℃ for 8-12h to obtain the lithium iron phosphate material.
The hot acid solution in the step (2) is one or more than two acid solutions of oxalic acid, acetic acid, malic acid and citric acid, and the weight percentage concentration of the hot acid solution is 1-10%.
The organic solution in the step (2) is one or more than two of ethanol, glycol and alkylphenol polyoxyethylene, and the weight percentage concentration of the organic solution is 1-10%.
The ultrasonic power of the ultrasonic material loosening structure in the step (2) is 400-1000W, and the flow of the high-pressure water gun is 4-10L/min.
In the step (4), the Fe source is one or a mixture of two or more of iron phosphate, iron oxalate and iron oxide, the Li source is one or a mixture of two or more of lithium carbonate, lithium hydroxide and lithium phosphate, and the P source is one or a mixture of two or more of phosphoric acid, ammonium hydrogen phosphate and lithium phosphate.
In the step (4), the carbon source is one or a mixture of more than two of glucose, sucrose and starch, and the supplementary mass of the sugar source is 7-15% of the total mass of reactants after Li, Fe and P are supplemented.
In the step (4), the Mg source is one or a mixture of more than two of magnesium carbonate, magnesium acetate and magnesium phosphate, the Ti source is one or a mixture of more than two of titanium dioxide, titanic acid and butyl titanate, and the Mn source is one or a mixture of more than two of trimanganese tetroxide, manganese acetate and manganese carbonate; the Mg source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, the Ti source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, and the Mn source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented.
The acid solution with the weight percentage concentration of 1-5% in the step (5) is one or a mixed solution of more than two of oxalic acid, acetic acid, malic acid and citric acid.
The solid content of the slurry obtained in the step (5) is 30-35%.
The invention has the advantages that:
(1) the lithium iron phosphate mixed material is obtained by a combined method of soaking in a hot acid solution, ultrasonic wave loosening and high-pressure water gun stripping, and has a good combination effect and high efficiency; impurities introduced into the separated material are less, copper impurities and the like are less introduced compared with a mechanical separation mode, and the copper impurities are key control items of the impurities of the positive electrode material; meanwhile, the pollution is reduced, organic matters can be burnt into carbon, the recovery and the reutilization are convenient, and the stripped copper and aluminum pole pieces are also convenient to be melted again, metallurgically recovered and reused;
(2) the method comprises the following steps of calcining the anode filter residue in the air to remove C and other organic impurities in the material, loosening a grain structure of the calcined material by using an acid solution, wherein the grain structure of the material is compacted due to calcination, so that the directly-reproduced lithium iron phosphate material has high internal resistance, such as citric acid and the like, has a certain chelation effect, the grains can be loosened by using a proper amount of the acid solution (but a large amount of the acid solution can damage the structural performance of the material), supplementing raw materials to participate in reaction to play a role in guiding reaction and grain growth, doping Mg to improve ion transmission, doping Mn and Ti to prevent the material from being over-burnt and improve the cycle performance of the material;
(3) the treatment method is simple to operate, the waste lithium iron phosphate battery is recycled and utilized as a qualified lithium iron phosphate finished product, the pollution is low, the conversion rate is high, and the performance is good and stable.
Drawings
FIG. 1 is a processing device for processing positive and negative plates to obtain a lithium iron phosphate mixed material, and the device comprises an ultrasonic emitter 1, an upper high-pressure water gun 2, a lower high-pressure water gun 3, a hot acid solution or an organic solution 4, a positive plate or a negative plate 5, a filtrate discharge port 6 and a transmission roller 7.
Figure 2 is an electrical property diagram of examples 1-3 of the present invention.
FIG. 3 is an XRD pattern of the calcined materials of examples 1-3 of the present invention.
Figure 4 is a finished XRD pattern of examples 1-3 of the present invention.
FIG. 5 is a SEM photograph of a finished product of example 1 of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively soaking positive and negative electrode plates 5 in 10 wt% citric acid solution 4 at 80 ℃ and simultaneously releasing the material structure by using an ultrasonic emitter 1 to emit 1000W ultrasonic power for 40min, stripping the materials on the positive and negative electrode plates 5 by using upper and lower high-pressure water guns 2 and 3 (with the flow rate of 3L/min), filtering to obtain leaching filtrate and filter residues, allowing the filtrate to flow out from an aluminum liquid discharge port 6 for recycling, and melting, metallurgically recycling the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 450 ℃ for 90min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li: Fe: 1.0744 and Fe: supplementing iron phosphate, lithium carbonate and glucose according to the detection result, and adding magnesium acetate, titanium dioxide and manganous-manganic oxide for doping, so as to improve the ion transmission performance and rate capability of the material; wherein the molar ratio of Fe, Li and P in the material supplemented with the iron phosphate and the lithium carbonate is Li: fe: p is 1:1:1.02, the molar ratio of Fe in the calcined material to the supplemented iron phosphate is 5, the supplemented mass of glucose is 7% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, magnesium acetate is 0.1% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, titanium dioxide is 5% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, and manganous oxide is 0.2% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate;
(5) loosening the grain structure of the calcined material in the step (3) for 10 hours by using a citric acid solution with the weight percentage concentration of 1%, and then adding the prepared supplementary material in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 30%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2h, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.35 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700 ℃ for 12h to obtain the lithium iron phosphate material.
5) And (3) after the calcined material in the step 4) is subjected to grain structure loosening for 10 hours by using 1 wt% of citric acid solution, adding the prepared raw material, taking pure water as a medium, grinding the slurry to obtain a particle size D500.35 micrometers by using a sand mill, then performing spray drying, and calcining the dried material in nitrogen at 700 ℃ for 12 hours to obtain the lithium iron phosphate anode material.
Example 2
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 100 ℃ glycol solution with the weight percentage concentration of 1% for soaking, simultaneously using 400W ultrasonic power to release the material structure for 60min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 10L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 600 ℃ for 60min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li: Fe: 1.0744 and Fe: supplementing iron phosphate, lithium carbonate and glucose according to the detection result, and adding magnesium acetate, titanium dioxide and manganous-manganic oxide for doping, so as to improve the ion transmission performance and rate capability of the material; wherein the molar ratio of Fe, Li and P in the material supplemented with the iron phosphate and the lithium carbonate is Li: fe: p is 1.02:1:1.03, the molar ratio of Fe in the calcined material to the supplemented iron phosphate is 3, the supplemented mass of glucose is 15% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, magnesium acetate is 5% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, titanium dioxide is 0.1% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, and mangano-manganic oxide is 0.2% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate;
(5) loosening the grain structure of the material calcined in the step (3) for 2 hours by using oxalic acid solution with the weight percentage concentration of 5%, and then adding the supplement material proportioned in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 35%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2 hours, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.5 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 790 ℃ for 8 hours to obtain the lithium iron phosphate anode material.
Example 3
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 90 ℃ alkylphenol polyoxyethylene ether solution with the weight percentage concentration of 5% for soaking, simultaneously using 900W ultrasonic power to release the material structure for 50min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 6L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 500 ℃ for 70min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the content of the elements Fe, Li and P in the calcined material, wherein the molar ratio of the three elements Li to Fe is 0.954, and the molar ratio of Fe to P is Fe: supplementing ferric oxalate, lithium phosphate and starch according to a detection result, and adding magnesium acetate, butyl titanate and manganese acetate for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the molar ratio of Fe, Li and P in the material supplemented with ferric oxalate and lithium phosphate is Li: fe: p is 1.1:1:1.04, the molar ratio of Fe in the calcined material to the supplemented ferric oxalate is 8, the supplemented mass of starch is 10% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, magnesium acetate is 1% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, butyl titanate is 0.1% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, and manganese acetate is 5% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented;
(5) loosening the grain structure of the calcined material in the step (3) for 2 hours by using an acetic acid solution with the weight percentage concentration of 2%, and then adding the prepared supplementary material in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 32%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2 hours, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.45 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 750 ℃ for 10 hours to obtain the lithium iron phosphate anode material.
Example 4
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 90 ℃ alkylphenol polyoxyethylene ether solution with the weight percentage concentration of 2% for soaking, simultaneously using 700W ultrasonic power to release the material structure for 50min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 5L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 480 ℃ for 80min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li, Fe is 1.024, Fe: supplementing ferric oxalate, lithium phosphate and cane sugar according to a detection result, and adding magnesium acetate, butyl titanate and manganese acetate for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the molar ratio of Fe, Li and P in the material supplemented with ferric oxalate and lithium phosphate is Li: fe: p is 1.04:1:1.03, the molar ratio of Fe in the calcined material to the supplemented ferric oxalate is 0.8, the supplemented mass of sucrose is 8% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, magnesium acetate is 2% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, butyl titanate is 3% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, and manganese acetate is 5% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate;
(5) loosening the grain structure of the material calcined in the step (3) for 2 hours by using a malic acid solution with the weight percentage concentration of 2%, and then adding the supplement material proportioned in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 32%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2h, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.4 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 770 ℃ for 9h to obtain the lithium iron phosphate anode material.
Preparing the lithium iron phosphate positive electrode material obtained in the embodiment 1-3 into a semi-finished battery according to a mass ratio, wherein the lithium iron phosphate positive electrode material in the semi-finished battery is as follows: SP: PVDF 8:1:1, and the semi-finished cell was subjected to 0.2C, 1C charge/discharge tests, and the test results are shown in fig. 2. And the first charge and discharge efficiency (first charge and discharge efficiency ═ first discharge capacity/first charge capacity) was obtained from the data in fig. 2. The results of the power-off test are shown in Table 1.
TABLE 1
See FIG. 3, calcined material and Li3Fe2(PO4)3The standard spectrum of the material is close to that of the calcined material (450/600/500 ℃) and Li3Fe2(PO4)3If there is a peak not consistent with Li3Fe2(PO4)3、Fe2O3Partial peak coincidence, i.e. a portion of Li3Fe2(PO4)3Not converted, some of the Fe is oxidized to Fe2O3。
Referring to fig. 4, the lithium iron phosphate cathode material prepared in examples 1 to 3 has a standard lithium iron phosphate spectrum, and the lower vertical line in fig. 4 is a standard spectrum peak line.
As shown in fig. 5, it can be seen that the grains on the prepared lithium iron phosphate cathode material in the spheroidal structure are similar to spherical grains, the sizes of the grains are uniformly distributed as a whole, and individual large grains can be seen.
In summary, when the raw materials such as iron phosphate are not added at all, the improvement is not good, but a large amount of raw materials are added, like when the normal raw materials are used for synthesizing the lithium iron phosphate, impurities (calcined materials) are also added, so that the mutual influence is caused, and the electrical property of the material is not as good as that of the pure raw materials by direct synthesis.
The carbon removing material contains more hard particles, which is not beneficial to production and processing, the structure of the carbon removing material is considered to be firstly loosened by using the acid solution, the material processing is facilitated, meanwhile, the crystal grain appearance of the carbon removing material can be changed by the acid solution, the desired structural performance of the lithium iron phosphate is facilitated to be obtained, and the carbon removing material can also be used as a partial carbon source and is additionally supplemented with the carbon source. Considering that the carbon material is removed by the pretreatment of citric acid, the carbon material is used as a partial carbon source while the structure is loosened, the more the acid solution is, the poorer the electrical property of the lithium iron phosphate material is, and the lithium iron phosphate material obtained by the experiment after the treatment of the acid solution with the weight percentage concentration of 1-5% has better electrical property and smaller internal resistance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A treatment method for low-pollution recycling of lithium iron phosphate materials is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive pole piece, a negative pole piece and a shell;
(2) respectively soaking the positive and negative electrode plates in a hot acid solution or an organic solution at the temperature of 80-100 ℃ and simultaneously ultrasonically loosening the material structure for 40-60min, then spraying and stripping the electrode plate material by using a high-pressure water gun, filtering to obtain leaching filtrate and filter residue, and melting, metallurgically recycling and reusing the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at the temperature of 450-600 ℃ for 60-90min, thereby removing carbon and other organic components;
(4) after the content of elements Fe, Li and P in the calcined material in the step (3) is detected, a Fe source, a Li source, a P source and a sugar source are supplemented according to the detection result, and an Mg source, a Ti source and a Mn source are added for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the mol ratio of Fe, Li and P in the materials after supplementing Fe source, Li source and P source is Li: fe: p is 1-1.1:1:1.02-1.04, and the molar ratio of Fe element in the calcined material and the supplementary Fe source is 0.8-8;
(5) loosening the grain structure of the calcined material in the step (3) for 2-10h by using an acid solution with the weight percentage concentration of 1-5%, and adding the prepared supplementary material in the step (4) to obtain slurry;
(6) grinding the slurry proportioned in the step (5) by using a sand mill until the granularity D50 of the slurry is 0.35-0.5 mu m, then spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700-790 ℃ for 8-12h to obtain the lithium iron phosphate material.
2. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the hot acid solution in the step (2) is one or more than two acid solutions of oxalic acid, acetic acid, malic acid and citric acid, and the weight percentage concentration of the hot acid solution is 1-10%.
3. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the organic solution in the step (2) is one or more than two of ethanol, glycol and alkylphenol polyoxyethylene, and the weight percentage concentration of the organic solution is 1-10%.
4. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the ultrasonic power of the ultrasonic material loosening structure in the step (2) is 400-1000W, and the flow of the high-pressure water gun is 4-10L/min.
5. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the Fe source is one or a mixture of two or more of iron phosphate, iron oxalate and iron oxide, the Li source is one or a mixture of two or more of lithium carbonate, lithium hydroxide and lithium phosphate, and the P source is one or a mixture of two or more of phosphoric acid, ammonium hydrogen phosphate and lithium phosphate.
6. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the carbon source is one or a mixture of more than two of glucose, sucrose and starch, and the supplementary mass of the sugar source is 7-15% of the total mass of reactants after Li, Fe and P are supplemented.
7. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the Mg source is one or a mixture of more than two of magnesium carbonate, magnesium acetate and magnesium phosphate, the Ti source is one or a mixture of more than two of titanium dioxide, titanic acid and butyl titanate, and the Mn source is one or a mixture of more than two of trimanganese tetroxide, manganese acetate and manganese carbonate; the Mg source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, the Ti source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, and the Mn source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented.
8. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the acid solution with the weight percentage concentration of 1-5% in the step (5) is one or a mixed solution of more than two of oxalic acid, acetic acid, malic acid and citric acid.
9. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the solid content of the slurry obtained in the step (5) is 30-35%.
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