CN109626350B - Method for preparing battery-grade iron phosphate from waste lithium iron phosphate battery positive plates - Google Patents
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Abstract
The invention belongs to the technical field of waste power lithium battery recovery, and particularly relates to a method for preparing battery-grade iron phosphate from positive plates of waste lithium iron phosphate batteries, which comprises the following steps: removing organic matters from the waste lithium iron phosphate-based positive electrode material obtained by disassembling the battery by using an organic solvent, and drying; adding the obtained anode material into a phosphoric acid solution, adding an oxidant, and heating for dissolving; adding a ferric iron source solution into a solution obtained by oxidizing and dissolving lithium iron phosphate, and reacting to obtain iron phosphate slurry; filtering, washing, drying and dehydrating to obtain battery-grade iron phosphate; according to the method, the lithium iron phosphate is dissolved by the phosphoric acid, and the ferric iron source is subsequently added, so that the utilization rate of the phosphoric acid is improved, more battery-grade iron phosphate is obtained, the content of various impurity ions in the waste liquid is reduced, the cost of further precipitating lithium from the filtrate is greatly reduced, and the addition of alkali in the process of generating the iron phosphate by reaction is avoided, so that the requirements of low cost and high environmental protection are met.
Description
Technical Field
The invention belongs to the technical field of recycling and comprehensive utilization of waste lithium ion power batteries, and relates to a method for preparing battery-grade iron phosphate from a positive plate of a waste lithium iron phosphate battery.
Background
At present, pure electric vehicles and hybrid electric vehicles are already industrialized and scaled. In 2018, the annual sales volume of the new energy electric automobile exceeds 200 thousands, and the year-by-year increase is 722%. The new energy automobile creates green travel and brings corresponding problems, the accumulated scrappage of the power battery of the electric automobile in China can reach the scale of 12-17 ten thousand tons by 2020 years according to the average service life of 5 years of the battery of the new energy automobile. Further troublesome is the complex battery construction, lack of uniform standards, and complex recycling processes.
The acid dissolution method is one of the main methods for recovering valuable metal materials in lithium iron phosphate at present, and for example, patent application 201610991868.1 discloses a comprehensive method for preparing a lithium iron phosphate anode material, which comprises the following specific steps: (1) preparing a lithium iron phosphate positive electrode material into slurry, mixing the slurry with acid for leaching reaction, and then carrying out liquid-solid separation to obtain a leachate and residues; (2) adjusting the pH value of the leachate to 1.5-3, and performing solid-liquid separation to obtain iron phosphate and iron-removing acid liquid; (3) adjusting the pH value of the iron-removing acidic solution to 5-8, and performing solid-liquid separation to obtain aluminum and iron precipitates and a lithium-containing purified solution; (4) and (4) carrying out post-treatment on the purified solution to obtain a lithium product and a precipitation mother solution. Although the method has a simple recovery process and low requirements on equipment, the utilization rate of iron and phosphorus is low in the recovery process, and the iron and phosphorus content in the filtrate is high, so that the method is very unfavorable for subsequent lithium precipitation.
In addition, patent 201710657055.3 discloses another method for recovering waste lithium iron phosphate positive electrode material, which comprises the following steps: pretreating the lithium iron phosphate anode material to volatilize organic matters in the anode; adding a decomposition accelerator into the obtained lithium iron phosphate raw material, and directly leaching with water after sulfating roasting; and regulating the pH value with alkali liquor to precipitate the iron phosphate, refining to obtain a battery-grade iron phosphate product, and precipitating the filtrate with sodium carbonate to obtain a lithium carbonate product. Although the process does not need to add an oxidant, a large amount of concentrated sulfuric acid solution is added, the utilization rate of sulfuric acid is low, a large amount of energy is consumed when sulfate radicals are concentrated and evaporated through waste water to generate sodium sulfate, a large amount of alkaline solution is required to be added in the process of depositing iron phosphate to adjust the pH value of the solution, and the recovery cost is very high.
Therefore, research and development of a novel recovery technology can improve the material utilization rate, reduce the contents of phosphorus, iron and acid radical ions in waste liquid, and reduce the consumption of alkali in the process is an important challenge for recovering lithium iron phosphate battery materials.
At present, no reports related to the efficient recovery of waste lithium iron phosphate positive plates and the continuous preparation of iron phosphate by a phosphoric acid dissolution method in a published document are found.
Disclosure of Invention
In order to meet the requirements of environmental protection and cost in the process of recycling lithium iron phosphate battery materials, the invention improves the utilization rate of phosphoric acid by a method of dissolving lithium iron phosphate by phosphoric acid and subsequently adding a ferric iron source, obtains more battery-grade iron phosphate, reduces the content of impurity ions in waste liquid, and avoids the addition of alkali in the process of generating iron phosphate by reaction, thereby realizing the requirements of low cost and high environmental protection.
The invention provides a method for preparing battery-grade iron phosphate on the basis of a waste lithium iron phosphate battery positive plate, which is characterized by comprising the following steps of:
(1) roasting the waste lithium iron phosphate positive plate disassembled from the battery at low temperature, crushing and screening to obtain an aluminum sheet and a positive material mainly containing lithium iron phosphate, and treating the positive material with an organic solvent after continuously ball-milling to remove organic matters;
(2) adding the anode material treated in the step (1) into a phosphoric acid solution, adding an oxidant while stirring, and heating to dissolve lithium iron phosphate;
(3) adding a ferrous iron source solution into an oxidant, adding an oxidized ferric iron source solution into the solution obtained in the step (2), and heating to generate iron phosphate slurry;
(4) and (4) filtering, washing, drying and dehydrating the iron phosphate slurry prepared in the step (3) to obtain the battery-grade iron phosphate.
Preferably, in step (1):
the low-temperature roasting temperature is 200-500 ℃, and the roasting time is 1-6 h.
The particle size of the anode material after ball milling is less than or equal to 50 meshes, and the particle size is less than or equal to, for example, 100 meshes is smaller than 50 meshes.
The organic solvent can be any organic solvent capable of removing organic matters; more preferably one or more of NMP, acetone, methanol, toluene.
Preferably, in step (2):
the mass fraction of phosphoric acid in the added phosphoric acid solution is 10-85%, and the liquid-solid mass ratio of the phosphoric acid solution to the anode material is 3:1-7: 1.
In the step (2) and the step (3), the oxidizing agents are the same or different and can be one or more of hydrogen peroxide, sodium hypochlorite and ozone.
In the step (2), the heating temperature is 30-100 ℃, and the heating time is 0.5-4 h.
Preferably, in step (3):
the ferrous source is one or more selected from ferrous sulfate heptahydrate, ferrous nitrate and ferrous chloride, the oxidation temperature is 20-70 ℃, and the oxidation time is 0.2-3 h.
The molar ratio of the ferric iron source oxidized in the step (3) to the phosphoric acid added in the step (2) is 0.7:1-1.1:1, and after the ferric iron source is added, the heating temperature is 40-100 ℃ and the time is 0.5-5 h.
Preferably, in step (4):
the drying temperature is 60-120 ℃, and the drying time is 1-4 h; the dehydration temperature is 450 ℃ and 700 ℃, and the time is 1-4 h.
By adopting the technical scheme, the invention has the advantages that:
(1) according to the method for preparing the battery-grade iron phosphate by taking the waste lithium iron phosphate battery positive plate as the raw material, low-temperature roasting is adopted, energy is saved, the raw material utilization rate is high in the whole reaction process, the recovery rates of phosphate radicals and iron ions respectively reach 99.3% and 99.7%, the contents of iron and phosphorus in filtrate reach the ppm level, a purer raw material source is provided for subsequent lithium recovery, and the subsequent lithium precipitation cost is greatly reduced;
(2) the phosphoric acid solution is used as a solvent for dissolving the lithium iron phosphate and also used as a phosphorus source for generating the iron phosphate by reacting with ferric ions, so that the problems that a large amount of sulfuric acid is required to be consumed to dissolve the lithium iron phosphate in the conventional recovery process of the positive plate of the lithium iron phosphate battery and the later-stage sulfate radicals are difficult to treat are solved, alkaline substances are not required to be added in the whole process of generating the iron phosphate, and the recovery cost is greatly reduced;
(3) the iron phosphate particles obtained by the method are uniformly distributed, the phosphorus-iron ratio is close to 1:1, the impurity content is low, the tap density is high, D50 is less than 13 mu m, and the requirement of battery-grade lithium iron phosphate is met.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a flow chart of an embodiment of phosphoric acid dissolution of lithium iron phosphate cathode material to prepare iron phosphate.
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; after cleaning, putting the mixture into a heating furnace for roasting for 3 hours at 200 ℃; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 50 meshes, treating the anode material powder with an NMP solvent and drying the anode material powder;
(2) adding 100 g of the positive electrode material obtained in the step (1) into 300ml of 10% phosphoric acid solution, adding 60ml of 30% hydrogen peroxide while stirring, and mixing and heating in a 70 ℃ water bath kettle for 30min to dissolve lithium iron phosphate;
(3) adding 0.23mol of ferrous sulfate solution into hydrogen peroxide for oxidation, oxidizing for 12min at 20 ℃, adding the completely oxidized solution into the solution dissolved by the lithium iron phosphate, and heating in a 70 ℃ water bath for 30min to generate an iron phosphate solution;
(4) and (3) filtering and washing the iron phosphate solution generated in the step (3), drying at 100 ℃ for 3h, and continuously carrying out air firing at 450 ℃ for 4h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Example 2
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; after cleaning, putting the mixture into a heating furnace for 500 ℃, and roasting for 1 h; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the positive electrode material to obtain positive electrode material powder with the particle size of less than 100 meshes, treating the positive electrode material powder with an acetone solvent and drying the positive electrode material powder;
(2) adding 200 g of the positive electrode material obtained in the step (1) into 1L of phosphoric acid solution with the mass fraction of 40%, adding industrial-grade sodium peroxide while stirring, and mixing and heating in a 100 ℃ water bath kettle for 4 hours to dissolve lithium iron phosphate;
(3) adding 4.45mol of ferrous nitrate solution into hydrogen peroxide for oxidation, oxidizing for 2h at 40 ℃, adding the completely oxidized solution into the solution dissolved by the lithium iron phosphate, and heating for 3h in a water bath at 100 ℃ to generate an iron phosphate solution;
(4) and (3) filtering and washing the iron phosphate solution generated in the step (3), drying at 120 ℃ for 4h, and continuously carrying out air firing at 600 ℃ for 3h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Example 3
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; cleaning, placing into a heating furnace at 300 ℃, and roasting for 6 h; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 200 meshes, treating the anode material powder with a methanol solvent and drying the anode material powder;
(2) adding 100 g of the positive electrode material obtained in the step (1) into 700ml of 85 mass percent phosphoric acid solution, adding industrial grade sodium hypochlorite while stirring, and mixing and heating in a 30 ℃ water bath kettle for 2 hours to dissolve lithium iron phosphate;
(3) adding 11.3mol of ferrous chloride solution into sodium peroxide for oxidation, oxidizing the solution at 70 ℃ for 3h, adding the completely oxidized solution into the solution in which the lithium iron phosphate is dissolved, and heating the solution in a water bath at 40 ℃ for 5h to generate an iron phosphate solution;
(4) and (4) filtering and washing the iron phosphate solution generated in the step (3), drying at 60 ℃ for 1h, and continuously carrying out air firing at 700 ℃ for 1h to obtain the battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Example 4
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; cleaning, placing into a heating furnace at 400 ℃, and roasting for 4 h; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 150 meshes, treating the anode material powder with a toluene solvent and drying the anode material powder;
(2) adding 200 g of the positive electrode material obtained in the step (1) into 1.2L of 30% phosphoric acid solution, introducing ozone while stirring, and mixing and heating in a 50 ℃ water bath kettle for 3 hours to dissolve lithium iron phosphate;
(3) adding 4.2mol of ferrous chloride solution into sodium hypochlorite for oxidation, oxidizing for 2.5h at 60 ℃, adding the completely oxidized solution into the solution in which the lithium iron phosphate is dissolved, and heating in a water bath at 80 ℃ for 2h to generate an iron phosphate solution;
(4) and (4) filtering and washing the iron phosphate solution generated in the step (3), drying at 90 ℃ for 3h, and continuously carrying out air firing at 700 ℃ for 3h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Example 5
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; cleaning, placing into a heating furnace at 350 ℃, and roasting for 5 h; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 75 meshes, treating with NMP and a toluene solvent and drying;
(2) adding 200 g of the positive electrode material obtained in the step (1) into 800ml of 20 mass percent phosphoric acid solution, adding hydrogen peroxide and sodium peroxide solid under stirring, and mixing and heating in a 60 ℃ water bath kettle for 3.5 hours to dissolve lithium iron phosphate;
(3) adding 1mol of ferrous chloride solution and 0.82mol of ferrous sulfate heptahydrate solution into hydrogen peroxide for oxidation, oxidizing for 2h at 50 ℃, adding the completely oxidized solution into the solution in which the lithium iron phosphate is dissolved, and heating for 3h in a water bath at 90 ℃ to generate an iron phosphate solution;
(4) and (3) filtering and washing the iron phosphate solution generated in the step (3), drying at 85 ℃ for 3h, and continuously carrying out air firing at 650 ℃ for 2h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Example 6
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; cleaning, placing into a heating furnace at 400 ℃, and roasting for 4 h; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 100 meshes, treating with NMP, acetone and a toluene solvent and drying;
(2) adding 100 g of the positive electrode material obtained in the step (1) into 800ml of phosphoric acid solution with the mass fraction of 18%, adding hydrogen peroxide and sodium peroxide solid under stirring, and mixing and heating in a 50 ℃ water bath kettle for 3.5 hours to dissolve lithium iron phosphate;
(3) adding 0.5mol of ferrous nitrate solution and 0.4mol of ferrous sulfate heptahydrate solution into hydrogen peroxide and sodium hypochlorite for oxidation at 650 ℃ for 2h, adding the completely oxidized solution into the solution in which the lithium iron phosphate is dissolved, and heating in a water bath at 85 ℃ for 2h to generate iron phosphate solution;
(4) and (4) filtering and washing the iron phosphate solution generated in the step (3), drying at 95 ℃ for 3h, and continuously carrying out air firing at 700 ℃ for 1h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Comparative example 1
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; after cleaning, putting the mixture into a heating furnace at 600 ℃, and roasting for 3 hours; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the anode material to obtain anode material powder with the particle size of less than 50 meshes, treating the anode material powder with an NMP solvent and drying the anode material powder;
(2) adding 100 g of the positive electrode material obtained in the step (1) into 300ml of 10% phosphoric acid solution, adding 60ml of 30% hydrogen peroxide while stirring, and mixing and heating in a 70 ℃ water bath kettle for 30min to dissolve lithium iron phosphate;
(3) adding 0.23mol of ferrous sulfate solution into hydrogen peroxide for oxidation, oxidizing for 12min at 20 ℃, adding the completely oxidized solution into the solution dissolved by the lithium iron phosphate, and heating in a 70 ℃ water bath for 30min to generate an iron phosphate solution;
(4) and (3) filtering and washing the iron phosphate solution generated in the step (3), drying at 100 ℃ for 3h, and continuously carrying out air firing at 450 ℃ for 4h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Comparative example 2
(1) Disassembling the lithium iron phosphate battery, and taking out the positive pole piece; after cleaning, putting the mixture into a heating furnace for roasting for 3 hours at 200 ℃; taking out the pole piece, mechanically crushing, and screening to obtain an aluminum sheet and a positive electrode material mainly comprising lithium iron phosphate; continuously ball-milling the positive electrode material to obtain positive electrode material powder with the particle size smaller than 10 meshes, treating the positive electrode material powder with an NMP solvent and drying the positive electrode material powder;
(2) adding 100 g of the positive electrode material obtained in the step (1) into 300ml of 10% phosphoric acid solution, adding 60ml of 30% hydrogen peroxide while stirring, and mixing and heating in a 70 ℃ water bath kettle for 30min to dissolve lithium iron phosphate;
(3) adding 0.23mol of ferrous sulfate solution into hydrogen peroxide for oxidation, oxidizing for 12min at 20 ℃, adding the completely oxidized solution into the solution dissolved by the lithium iron phosphate, and heating in a 70 ℃ water bath for 30min to generate an iron phosphate solution;
(4) and (3) filtering and washing the iron phosphate solution generated in the step (3), drying at 100 ℃ for 3h, and continuously carrying out air firing at 450 ℃ for 4h to obtain battery-grade iron phosphate, wherein the chemical analysis of the battery-grade iron phosphate is shown in Table 1.
Table 1 shows the chemical analysis of ferric phosphate prepared by dissolving lithium ferric phosphate with phosphoric acid as the cathode material
The above description is only for the specific implementation of the claimed patent, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the principle of the claimed patent, and these modifications and additions should also fall within the protection scope of the present application.
Claims (1)
1. A method for preparing battery-grade iron phosphate from a positive plate of a waste lithium iron phosphate battery is characterized by comprising the following steps:
(1) roasting the waste lithium iron phosphate positive plate disassembled from the battery at low temperature, crushing and screening to obtain an aluminum sheet and a positive material mainly containing lithium iron phosphate, and treating the positive material with an organic solvent after continuously ball-milling to remove organic matters;
(2) adding the anode material treated in the step (1) into a phosphoric acid solution, adding an oxidant while stirring, and heating to dissolve lithium iron phosphate;
(3) adding a ferrous iron source solution into an oxidant, adding an oxidized ferric iron source solution into the solution obtained in the step (2), and heating to generate iron phosphate slurry;
(4) filtering, washing, drying and dehydrating the iron phosphate slurry prepared in the step (3) to obtain battery-grade iron phosphate;
the low-temperature roasting temperature in the step (1) is 200-;
after the anode material is ball-milled, the particle size is less than or equal to 50 meshes;
the organic solvent in the step (1) is one or more of NMP, acetone, methanol and toluene;
the mass fraction of phosphoric acid in the phosphoric acid solution added in the step (2) is 10-85%, and the liquid-solid mass ratio of the phosphoric acid solution to the anode material is 3:1-7: 1;
in the step (2) and the step (3), the oxidizing agents are the same or different and can be one or more of hydrogen peroxide, sodium hypochlorite and ozone;
in the step (2), the heating temperature is 30-100 ℃, and the heating time is 0.5-4 h;
in the step (3), the ferrous iron source is selected from one or more of ferrous sulfate heptahydrate, ferrous nitrate and ferrous chloride, the oxidation temperature is 20-70 ℃, and the oxidation time is 0.2-3 h;
the molar ratio of the ferric iron source oxidized in the step (3) to the phosphoric acid added in the step (2) is 0.7:1-1.1:1, and after the ferric iron source is added, the heating temperature is 40-100 ℃ and the time is 0.5-5 h;
in the step (4), the drying temperature is 60-120 ℃, and the time is 1-4 h; the dehydration temperature is 450 ℃ and 700 ℃, and the time is 1-4 h.
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| CN110474123B (en) * | 2019-08-23 | 2022-08-09 | 贵州红星电子材料有限公司 | Comprehensive recovery method of waste lithium iron phosphate battery positive electrode material |
| CN110668413A (en) * | 2019-10-24 | 2020-01-10 | 自贡同发荣新材料有限公司 | Method for producing battery-grade iron phosphate by using waste lithium iron phosphate cathode material |
| CN111088430A (en) * | 2019-12-26 | 2020-05-01 | 甘肃睿思科新材料有限公司 | Recovery processing method of waste slurry of lithium battery positive electrode |
| CN111792635A (en) * | 2020-06-23 | 2020-10-20 | 湖南邦普循环科技有限公司 | Preparation method of anhydrous iron phosphate |
| CN113061723B (en) * | 2021-03-04 | 2023-01-20 | 长沙友合金属材料有限公司 | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate |
| CN113648670B (en) * | 2021-07-15 | 2023-03-10 | 广东邦普循环科技有限公司 | Method for recovering lithium battery slurry and equipment for recovering lithium battery slurry |
| CN115806279A (en) * | 2021-09-15 | 2023-03-17 | 贵州川恒化工股份有限公司 | Method for preparing iron phosphate by using iron-containing waste material |
| CN114920227A (en) * | 2022-05-16 | 2022-08-19 | 合肥国轩循环科技有限公司 | Production process for regenerating iron phosphate from lithium battery waste |
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| CN105375023A (en) * | 2014-08-13 | 2016-03-02 | 法拉赛斯能源公司 | Method for removing copper and aluminum from an electrode material, and process for recycling electrode material from waste lithium-ion batteries |
| CN108075202B (en) * | 2016-11-10 | 2020-06-23 | 北京中科百特科技有限公司 | Comprehensive recovery method of lithium iron phosphate anode material |
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| CN108878866B (en) * | 2018-06-28 | 2020-11-17 | 山东理工大学 | Method for preparing ternary material precursor and recovering lithium by using ternary cathode material of waste lithium ion battery |
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