CN111547697B - Method for repairing waste lithium iron phosphate material - Google Patents
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Abstract
The invention relates to a method for repairing a waste lithium iron phosphate material, which comprises the following steps: 1) measuring the content of Li, Fe and P elements in the waste lithium iron phosphate material; 2) preparing a mixed solution containing lithium salt, ferric salt and phosphoric acid, adding the waste lithium iron phosphate material into the mixed solution according to the final stoichiometric ratio of Li to Fe to P of 0.75-1.25 to 1, stirring and mixing, and controlling the pH value of the mixed solution to be 5.5-8.5 by using ammonia water in the stirring process to obtain a mixture; 3) carrying out hydrothermal reaction on the mixture at 100-200 ℃ to obtain a lithium iron phosphate precursor; 4) and carrying out carbon coating reaction on the lithium iron phosphate precursor at the temperature of 650-800 ℃ to obtain the repaired lithium iron phosphate battery material. The method realizes the direct repair of the anode material of the waste lithium iron phosphate battery.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, hydrometallurgy and resource circulation, in particular to a method for repairing a waste lithium iron phosphate material.
Background
At present, the service life of the lithium iron phosphate battery is about 5 years, and with the use of a large amount of lithium iron phosphate power electric automobiles, the amount of waste lithium iron phosphate batteries is gradually increased, and the amount of waste lithium iron phosphate reaches 12-17 ten thousand tons by estimation in this year. The lithium-ion power battery contains a large amount of lithium elements, and the lithium elements are used as main raw materials for producing the lithium-ion power battery, so that the lithium elements are recycled and are very important for the development of lithium-ion power automobiles. Meanwhile, the waste lithium iron phosphate batteries contain a large amount of electrolyte, organic wastes and other pollutants, and are not treated and are discarded at will, so that serious environmental problems are caused, and therefore, the recycling of the waste lithium iron phosphate batteries has important economic and environmental protection significance.
The recovery industry of waste power lithium ion batteries mainly adopts a wet method to recover valuable metals in positive electrode materials, inorganic acid is adopted to dissolve the valuable metals, and metal compounds are obtained by extraction and separation and are sold as products, for example, Chinese patents CN201810592130.7 and CN201910711370.9 disclose a method for recovering valuable metal elements such as lithium in lithium iron phosphate by a leaching process, but the subsequent treatment of a large amount of acid and alkali consumption and environmental pollutants in the process is very complicated.
The method is characterized in that the waste lithium iron phosphate anode material reacts with supplementary raw materials to repair damaged lattices and form regular olivine lithium iron phosphate crystals again, for example, Chinese patents CN201010253859.5 and CN201610623808.4 enable related elements to exist in an ion form through acid leaching, and then the lithium iron phosphate materials are prepared again through processes of ball milling, calcining and the like.
Disclosure of Invention
Based on the technical background, the invention uses a hydrothermal method as a regeneration process method, solves the technical problem of directly repairing the anode material of the waste lithium iron phosphate battery, and obtains a new lithium iron phosphate material through high-temperature calcination, thereby realizing the cyclic utilization of valuable metals and carbon, avoiding leaching, being green and environment-friendly, improving the recovery efficiency and saving the production cost.
In order to solve the technical problems, the invention provides a method for repairing a waste lithium iron phosphate material.
The invention provides a method for repairing a waste lithium iron phosphate material, which comprises the following steps:
1) measuring the content of Li, Fe and P elements in the waste lithium iron phosphate material;
2) preparing a mixed solution containing lithium salt, ferric salt and phosphoric acid, adding the waste lithium iron phosphate material into the mixed solution according to the final stoichiometric ratio of Li to Fe to P of 0.75-1.25 to 1, stirring and mixing, and controlling the pH value of the mixed solution to be 5.5-8.5 by using ammonia water in the stirring process to obtain a mixture;
3) carrying out hydrothermal reaction on the mixture at 100-200 ℃ to obtain a lithium iron phosphate precursor;
4) and carrying out carbon coating reaction on the lithium iron phosphate precursor at the temperature of 650-800 ℃ to obtain the repaired lithium iron phosphate battery material.
Preferably, in the step 2), the waste lithium iron phosphate material is added into the mixed solution according to a solid-to-liquid ratio of 50-150 g/L.
Preferably, in step 3), the mixture is subjected to a hydrothermal reaction at 100 to 200 ℃ for 2 to 10 hours.
Preferably, in step 3), the mixture is placed in an autoclave and N is passed through2Controlling the air pressure to be 0.05-0.2MPa, and carrying out hydrothermal reaction for 2-10 hours at the temperature of 100-200 ℃.
Preferably, in the step 4), the carbon-coated reaction of the lithium iron phosphate precursor is performed at a temperature of 650 to 800 ℃ for 4 to 8 hours.
Preferably, in the step 4), the lithium iron phosphate precursor is calcined in a tube furnace by using N2The carbon coating reaction is carried out at the temperature of 650-800 ℃ in protective atmosphere.
Preferably, in step 2), the lithium salt is selected from one or more of lithium hydroxide, lithium chloride and lithium sulfate.
Preferably, in step 2), the iron salt is selected from one or both of ferrous sulfate and ferrous chloride.
Preferably, in step 1), the waste lithium iron phosphate material is obtained through the following steps: the method comprises the steps of discharging waste lithium iron phosphate batteries, disassembling and separating out positive plates, crushing and separating the positive plates to obtain positive materials and aluminum foils, and further performing gravity screening and impurity removal to obtain the waste lithium iron phosphate materials.
Compared with the prior art, the invention has the advantages that: measuring the content of Li, Fe and P elements in the waste lithium iron phosphate material to obtain the content of three elements in the waste lithium iron phosphate material, then preparing a mixed solution containing lithium salt, iron salt and phosphoric acid according to the stoichiometric ratio of Li to Fe to P of 0.75-1.25: 1:1, adding the waste lithium iron phosphate material into the mixed solution to supplement corresponding reaction raw materials for repairing the lithium iron phosphate battery material, stirring and mixing, fully contacting the reaction raw materials with the lithium iron phosphate battery material to be repaired, controlling the pH value to be 5.5-8.5 by using ammonia water in the stirring process to obtain a mixture, adjusting the pH value to 5.5-8.5 by using the ammonia water to meet the requirement of precipitation, simultaneously decomposing the ammonia water at high temperature to reduce the introduction of impurities, and then carrying out hydrothermal reaction on the mixture at 100-200 ℃, wherein the hydrothermal condition and appropriate pH control ensure that crystal grains are completely developed, small in particle size, uniformly distributed and lighter in agglomerated particles, the method has the advantages that the defects of grain growth, defect formation, impurity introduction and the like caused in the calcining process of the traditional repairing process are avoided, carbon is facilitated to fall off from damaged lithium iron phosphate crystals into a lithium iron phosphate precursor, the hydrothermal reaction in the prior art is generally used for realizing the synthesis of the lithium iron phosphate material, the hydrothermal reaction has the effects of repairing the waste lithium iron phosphate material, the carbon in the waste lithium iron phosphate material falls off into the precursor, the carbon is conveniently coated on the repaired lithium iron phosphate material, then the carbon coating reaction is carried out on the lithium iron phosphate precursor at the temperature of 650-800 ℃, the fallen carbon is coated on the surface of the lithium iron phosphate material, and the repaired lithium iron phosphate material is obtained, so that the waste lithium iron phosphate material is directly repaired. The method has the advantages of mild process conditions, simple preparation process, low cost, no need of leaching, no generation of a large amount of waste and environmental protection, and can effectively realize the recycling of valuable metals and carbon in the anode material.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 is a process flow diagram of the method of the present invention.
Fig. 2 is an XRD pattern of the waste lithium iron phosphate as it is, the lithium iron phosphate precursor prepared by the present invention at 150 ℃, and the lithium iron phosphate material prepared by the final calcination of the present invention in example 1 of the present invention.
Fig. 3 is an SEM image of the waste lithium iron phosphate material, which is subjected to separation and impurity removal in example 2 of the present invention, magnified 2000 times.
Fig. 4 is an SEM image of the waste lithium iron phosphate material subjected to separation and impurity removal according to example 2 of the present invention, which is enlarged by 5000 times.
Fig. 5 is an SEM image of the waste lithium iron phosphate material subjected to separation and impurity removal according to embodiment 2 of the present invention, which is magnified 10000 times.
Fig. 6 is an SEM image of an enlarged 2000 of the lithium iron phosphate precursor prepared by a hydrothermal method in example 2 of the present invention.
Fig. 7 is an SEM image of a lithium iron phosphate precursor prepared by a hydrothermal method according to example 2 of the present invention at an enlargement of 5000 a.
Fig. 8 is an SEM image of a lithium iron phosphate precursor prepared by a hydrothermal method in example 2 of the present invention at an enlargement of 10000.
Detailed Description
With reference to fig. 1, the present embodiment provides a method for repairing a waste lithium iron phosphate material, including the following steps:
1) after the waste lithium iron phosphate battery is subjected to discharge treatment, the metal shell is disassembled and removed, and the positive plate, the negative plate, the diaphragm and the electrolyte are separated. Crushing and separating the obtained positive plate to obtain a positive material and an aluminum foil, further performing gravity screening to obtain the waste lithium iron phosphate material, physically removing impurities to ensure that the total impurity element content is lower than 0.5%, and determining the content of elements such as Li, Fe, P and the like in the waste lithium iron phosphate material; aluminum and copper existing in a metal form can be removed through a reselection mode, the total impurity element content in the obtained waste lithium iron phosphate material is lower than 0.5%, and the impurity content in the material is lower than the specified impurity content of industrial-grade lithium iron phosphate. The total content of impurity elements in the waste lithium iron phosphate material is lower than 0.5%, the amount of impurities can be almost ignored, and the low-content impurities cannot influence the follow-up repair of the waste lithium iron phosphate material.
2) Preparing a mixed solution containing lithium salt, ferric salt and phosphoric acid, adding the waste lithium iron phosphate material into the mixed solution according to a final stoichiometric ratio of Li to Fe to P of 0.75-1.25 to 1 and a solid-to-liquid ratio of 50-150 g/L, stirring and mixing, and controlling the pH value of the mixed solution to be 5.5-8.5 by using ammonia water in the stirring process to obtain a mixture; the lithium salt is selected from one or more of lithium hydroxide, lithium chloride and lithium sulfate; the iron salt is selected from one or two of ferrous sulfate and ferrous chloride;
3) the mixture was placed in an autoclave and N was passed through2Controlling the air pressure to be 0.05-0.2MPa, carrying out hydrothermal reaction at 100-200 ℃ for 2-10 hours while stirring at the stirring speed of 600 rpm, filtering, and drying at 100-120 ℃ for 3-5 hours to obtain a lithium iron phosphate precursor;
4) putting the lithium iron phosphate precursor into a tube furnace for calcination, and adding N2The carbon coating reaction is carried out for 4 to 8 hours at the temperature of 650 to 800 ℃ in the protective atmosphere to obtain the repaired lithium iron phosphate battery material.
To further illustrate the methods set forth in the practice of the present invention, the methods of the present invention are illustrated by the following detailed examples.
Example 1
A method for repairing a waste lithium iron phosphate material comprises the following steps:
1) after the waste lithium iron phosphate battery is subjected to discharge treatment, the metal shell is disassembled and removed, and the positive plate, the negative plate, the diaphragm and the electrolyte are separated. And crushing and separating the obtained positive plate to obtain a positive material and an aluminum foil, further performing gravity screening to obtain a waste lithium iron phosphate material, physically removing impurities to ensure that the total content of impurity elements is less than 0.5%, and determining the content of elements such as Li, Fe, P and the like.
2) Preparing a small amount of LiOH and FeSO with corresponding concentrations from 20g of waste lithium iron phosphate material4，H3PO4And (3) uniformly mixing 20mL of the solution, adding a raw material sample, adding 180mL of deionized water, controlling the solid-liquid ratio to be 100g/L, fully stirring and mixing, and controlling the pH value to be 7.5 by using ammonia water in the stirring process to obtain a mixture, wherein the stoichiometric ratio of Li to Fe to P is 1:1: 1.
3) The mixture was placed in an autoclave and N was introduced2Hydrothermal synthesis at 150 deg.c for 4 hr under 0.1MPa while stirring at 600 rpm, filtering and drying at 10 deg.c for 3 hr to obtain precursor of lithium iron phosphate.
4) Putting the precursor into a tube furnace for calcination, and adding N2And performing carbon coating reaction for 5 hours at the temperature of 700 ℃ in a protective atmosphere to obtain the lithium iron phosphate material.
The XRD analysis results of fig. 2 show that: the waste lithium iron phosphate material has a wider XRD diffraction peak and a weaker peak strength, and the crystal structure of the material is not ideal. Diffraction peaks of the precursor obtained by a hydrothermal method and the lithium iron phosphate material obtained by calcination gradually become sharp, the crystallization effect of the material is improved, the orderliness of atoms in the crystal structure of the material is gradually enhanced, the crystal lattice is more and more complete, and other byproducts are not contained, so that the waste lithium iron phosphate material is well repaired;
in addition, carbon in the original waste lithium iron phosphate material exists in an amorphous carbon form, so that a carbon peak value does not exist in an XRD (X-ray diffraction) diagram, and the carbon peak value can be obviously seen in the XRD diagram of the precursor after hydrothermal treatment, which indicates that carbon coated on the waste lithium iron phosphate material falls off into the precursor and becomes crystalline carbon in the hydrothermal treatment process, and a calcined sample obtained by calcining does not have the carbon peak value, indicates that carbon coating is realized, and further indicates that the waste lithium iron phosphate material is repaired;
in addition, supplementary raw materials in the hydrothermal reaction are in good contact with the original lithium iron phosphate, so that the reaction is sufficient, and the crystal repair is facilitated.
Example 2
A method for repairing a waste lithium iron phosphate material comprises the following steps:
1) after the waste lithium iron phosphate battery is subjected to discharge treatment, the metal shell is disassembled and removed, and the positive plate, the negative plate, the diaphragm and the electrolyte are separated. And crushing and separating the obtained positive plate to obtain a positive material and an aluminum foil, further performing gravity screening to obtain a waste lithium iron phosphate material, physically removing impurities to ensure that the total content of impurity elements is less than 0.5%, and determining the content of elements such as Li, Fe, P and the like.
2) Preparing a small amount of LiOH and FeSO with corresponding concentrations from 20g of waste lithium iron phosphate material4，H3PO4And (3) uniformly mixing 20mL of the solution, adding a raw material sample, adding 180mL of deionized water, controlling the solid-liquid ratio to be 100g/L, fully stirring and mixing, and controlling the pH value to be 7.5 by using ammonia water in the stirring process to obtain a mixture, wherein the stoichiometric ratio of Li to Fe to P is 1:1: 1.
3) The mixture was placed in an autoclave and N was introduced2Hydrothermal synthesis at 170 ℃ for 4 hours under the air pressure of 0.1MPa, stirring at the stirring speed of 600 rpm, filtering, and drying at 10 ℃ for 3 hours to obtain the lithium iron phosphate precursor.
4) Putting the precursor into a tube furnace for calcination, and adding N2And performing carbon coating reaction for 5 hours at the temperature of 700 ℃ in a protective atmosphere to obtain the lithium iron phosphate material.
Fig. 3 to 5 are SEM images of the waste lithium iron phosphate material, and it can be seen from the SEM images that the particles have irregular shapes and are seriously agglomerated.
The SEM analysis results of fig. 6-8 show that: the waste lithium iron phosphate material is repaired by a hydrothermal method, and the repaired lithium iron phosphate crystal has a good crystal structure and does not contain other byproducts.
Example 3
A method for repairing a waste lithium iron phosphate material comprises the following steps:
1) after the waste lithium iron phosphate battery is subjected to discharge treatment, the metal shell is disassembled and removed, and the positive plate, the negative plate, the diaphragm and the electrolyte are separated. And crushing and separating the obtained positive plate to obtain a positive material and an aluminum foil, further performing gravity screening to obtain a waste lithium iron phosphate material, physically removing impurities to ensure that the total content of impurity elements is less than 0.5%, and determining the content of elements such as Li, Fe, P and the like.
2) Preparing a small amount of LiOH and FeSO with corresponding concentrations from 20g of waste lithium iron phosphate material4，H3PO420mL of the solution is evenly mixed, then a raw material sample is added to ensure that the stoichiometric ratio of Li to Fe to P is 1:1:1, 180mL of deionized water is added, the solid-liquid ratio is controlled to be 100g/L, the mixture is fully stirred and mixed, and the pH value is controlled to be 7.5 by ammonia water in the stirring processA mixture was obtained.
3) The mixture was placed in an autoclave and N was introduced2Hydrothermal synthesis is carried out for 8 hours at the temperature of 150 ℃ under the air pressure of 0.1MPa, stirring is carried out simultaneously, the stirring speed is 600 r/min, and the precursor of the lithium iron phosphate is obtained after filtering and drying for 3 hours at the temperature of 10 ℃.
4) Putting the precursor into a tube furnace for calcination, and adding N2And performing carbon coating reaction for 5 hours at the temperature of 700 ℃ in a protective atmosphere to obtain the lithium iron phosphate material.
The detection result shows that: the lithium iron phosphate material has a good crystal structure and does not contain other byproducts.
Other beneficial effects of the invention are as follows:
1. not only the process flow is short and short, the working procedures are compact and continuous, but also the required treatment temperature is greatly reduced; the prepared lithium iron phosphate material does not need complex subsequent treatment and can be directly applied to the production of lithium iron phosphate batteries.
2. The waste lithium iron phosphate material is treated by a hydrothermal method, and the prepared powder has the advantages of complete crystal grain development, small granularity, uniform distribution, light particle aggregation and the like, the hydrothermal method avoids the defects of crystal grain growth, defect formation, impurity introduction and the like caused in the calcining process of the traditional repair process, and is beneficial to carbon and the like to fall off from damaged lithium iron phosphate crystals, so that the repair is directly carried out under the appropriate condition to obtain the lithium iron phosphate crystals.
3. The method effectively recovers valuable metals in the anode material of the waste lithium iron phosphate battery, recovers carbon in the anode material, and carbon carried by the raw material is used for carbon coating of the lithium iron phosphate crystal again in the subsequent calcining process, so that the resource circulation maximization is realized.
4. The raw material treatment process has mild conditions, the raw material is treated by a physical method, high-concentration acid is not needed, the problem of environmental pollution caused by recovering lithium iron phosphate by acid leaching after roasting in the traditional process is solved, a large amount of solid waste and waste water are not generated, the resource is saved, and the method is green and environment-friendly.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Claims (8)
1. The method for repairing the waste lithium iron phosphate material is characterized by comprising the following steps of:
1) measuring the content of Li, Fe and P elements in the waste lithium iron phosphate material;
2) preparing a mixed solution containing lithium salt, ferric salt and phosphoric acid, adding the waste lithium iron phosphate material into the mixed solution according to the final stoichiometric ratio of Li to Fe to P = 0.75-1.25 to 1, stirring and mixing, and controlling the pH value of the mixed solution to be 5.5-8.5 by using ammonia water in the stirring process to obtain a mixture;
3) carrying out hydrothermal reaction on the mixture at 100-200 ℃ for 2-10 h to obtain a lithium iron phosphate precursor;
4) and carrying out carbon coating reaction on the lithium iron phosphate precursor at the temperature of 650-800 ℃ to obtain the repaired lithium iron phosphate battery material.
2. Repair method according to claim 1, characterized in that, in step 2),
and adding the waste lithium iron phosphate material into the mixed solution according to a solid-to-liquid ratio of 50-150 g/L.
3. Repair method according to claim 1, characterized in that in step 3) the mixture is placed in an autoclave and N is passed through2Controlling the air pressure to be 0.05-0.2MPa, and carrying out hydrothermal reaction for 2-10 hours at the temperature of 100-200 ℃.
4. The repairing method according to claim 1, wherein in the step 4), the carbon-coated reaction of the lithium iron phosphate precursor is performed at a temperature of 650 ℃ to 800 ℃ for 4 hours to 8 hours.
5. The repair method according to claim 1, wherein in step 4), the lithium iron phosphate precursor is calcined in a tube furnace to produce N2The carbon coating reaction is carried out at a temperature of 650-800 ℃ in a protective atmosphere.
6. The repair method according to claim 1, wherein in step 2), the lithium salt is selected from one or more of lithium hydroxide, lithium chloride and lithium sulfate.
7. The repair method according to claim 1, wherein, in the step 2), the iron salt is selected from one or two of ferrous sulfate and ferrous chloride.
8. The repair method according to claim 1, wherein in step 1), the waste lithium iron phosphate material is obtained by: the method comprises the steps of discharging waste lithium iron phosphate batteries, disassembling and separating out positive plates, crushing and separating the positive plates to obtain positive materials and aluminum foils, and further performing gravity screening and impurity removal to obtain the waste lithium iron phosphate materials.
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| CN112047319A (en) * | 2020-09-11 | 2020-12-08 | 南昌航空大学 | Method for recovering battery-grade iron phosphate from waste iron phosphate slag |
| CN112897492B (en) * | 2021-01-25 | 2022-06-24 | 中南大学 | Method for regenerating and recycling high-impurity lithium iron phosphate waste powder |
| CN114725555A (en) * | 2022-03-29 | 2022-07-08 | 西安交通大学 | Method for in-situ repairing of waste lithium iron phosphate lithium battery anode material by supercritical water |
| CN115744857B (en) * | 2022-10-21 | 2024-04-09 | 广东邦普循环科技有限公司 | Method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate battery |
| CN115924879B (en) * | 2023-01-18 | 2024-07-05 | 河南佰利新能源材料有限公司 | Method for recycling lithium iron phosphate from scrapped lithium iron phosphate material |
| CN117712544B (en) * | 2024-02-06 | 2024-04-12 | 邢东(河北)锂电科技有限公司 | Resource utilization method of waste lithium iron phosphate battery |
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| CN102208707A (en) * | 2011-05-12 | 2011-10-05 | 合肥工业大学 | Method for repair and regeneration of waste lithium iron phosphate battery cathode material |
| CN110112481A (en) * | 2019-04-23 | 2019-08-09 | 北京科技大学 | Waste lithium iron phosphate battery recycles the method for preparing lithium iron phosphate positive material |
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