CN116715257A - Comprehensive recovery method for waste lithium iron phosphate battery and lithium-aluminum-containing electrolyte - Google Patents

Comprehensive recovery method for waste lithium iron phosphate battery and lithium-aluminum-containing electrolyte Download PDF

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Publication number
CN116715257A
CN116715257A CN202310698823.5A CN202310698823A CN116715257A CN 116715257 A CN116715257 A CN 116715257A CN 202310698823 A CN202310698823 A CN 202310698823A CN 116715257 A CN116715257 A CN 116715257A
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Prior art keywords
lithium
iron phosphate
aluminum
solution
lithium iron
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CN202310698823.5A
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Chinese (zh)
Inventor
崔鹏媛
袁茂强
冯天意
张志勇
赵利萨
石启福
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Guifu Governor Hongpeng Chengxin Material Co ltd
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Guifu Governor Hongpeng Chengxin Material Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00Lithium compounds
    • C01D15/06Sulfates; Sulfites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16Purification
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a comprehensive recovery method of waste lithium iron phosphate batteries and lithium-containing aluminum electrolyte, which comprises the steps of carrying out sulfuric acid leaching on waste lithium iron phosphate battery powder, removing aluminum and copper, carrying out a calcium hydroxide leaching process on the lithium-containing aluminum electrolyte, mixing alkaline leaching solution of the lithium-containing aluminum electrolyte with acid leaching solution of lithium iron phosphate, adding hydrogen peroxide to oxidize and deposit iron, and carrying out deep purification on the solution after the iron deposit to remove fluorine and calcium, thereby obtaining pure lithium sulfate and sodium solution. According to the invention, the waste lithium iron phosphate battery and the lithium-containing aluminum electrolyte are comprehensively recycled, the alkaline leaching solution of the aluminum electrolyte is used for adjusting the pH value in the acid leaching solution, so that the auxiliary material cost in the process of recycling the lithium iron phosphate is reduced, the comprehensive utilization of the leaching solutions of the two processes is realized, and the method has the advantages of simplicity in operation, low auxiliary material cost and high recovery rate.

Description

Comprehensive recovery method for waste lithium iron phosphate battery and lithium-aluminum-containing electrolyte
Technical Field
The invention relates to the technical field of resource recovery, in particular to a comprehensive recovery method of a waste lithium iron phosphate battery and a lithium-aluminum-containing electrolyte.
Background
In recent years, lithium ion batteries have been widely used in consumer electronics, electric vehicles and energy storage fields, and therefore, a large number of waste lithium ion batteries have been produced. It is reported that by 2020, 250 million waste lithium ion batteries, up to 50 ten thousand tons in weight, are responsible for a large number of waste lithium ion batteries. The waste lithium ion battery contains a large amount of valuable metal elements, and the valuable components of the positive electrode material in the lithium battery comprise Ni:10% -20%, co:5% -10%, mn:10% -15%, li:2 to 6 percent. The waste lithium ion batteries also have certain hazard, and because the waste lithium ion batteries retain partial electric quantity, the waste lithium ion batteries can be exploded due to improper treatment, and a large amount of heavy metals and organic electrolyte are also contained in the waste lithium batteries, the ecological environment can be greatly influenced, and therefore, the recycling of the waste lithium batteries is particularly important.
Lithium and its compounds are widely used in industrial fields, and the market is increasing in consumption and demand of lithium year by year, especially important for developing new lithium mineral sources. In the aluminum industry, a large amount of lithium-containing bauxite is mined and used to prepare metallurgical grade aluminum oxide after long operation of the aluminum electrolysis cell, the lithium element is enriched due to the difficulty of precipitation in the electrolyte. Lithium is extracted from the lithium-rich aluminum electrolyte, so that not only can the demand of the market on lithium resources be supplemented, but also the resource utilization of the lithium-rich aluminum electrolyte can be realized.
In the wet treatment process of the waste lithium iron phosphate, an acid leaching process is often adopted, but a large amount of alkali is also consumed in the subsequent purification and extraction process, so that the comprehensive recovery of the acid leaching liquid of the waste lithium iron phosphate and the alkali leaching liquid of the lithium-aluminum-containing electrolyte is considered, the auxiliary material cost is greatly reduced, and the method has the advantages of short working flow and convenient operation.
Disclosure of Invention
The invention aims to solve the problems and provide a comprehensive recovery method of waste lithium iron phosphate batteries and lithium-containing aluminum electrolyte. According to the invention, the waste lithium iron phosphate battery and the lithium-containing aluminum electrolyte are comprehensively recovered, the alkaline leaching solution of the aluminum electrolyte is used for adjusting the pH value in the acid leaching solution, the auxiliary material cost in the process of recovering the lithium iron phosphate is reduced, the comprehensive utilization of the leaching solutions of the two processes is realized, and the method has the advantages of simplicity in operation, low auxiliary material cost and high recovery rate.
The invention realizes the above purpose through the following technical scheme:
a comprehensive recovery method of waste lithium iron phosphate batteries and lithium-aluminum-containing electrolytes comprises the following steps:
step 1, mixing lithium-containing aluminum electrolyte with water in a certain proportion, adding a certain amount of calcium hydroxide after mixing, and reacting for a period of time at a certain temperature;
step 2, adding waste lithium iron phosphate black powder into the prepared sulfuric acid solution according to a certain liquid-solid ratio, and reacting for a period of time at a certain temperature;
step 3, adding a certain amount of iron powder into the waste lithium iron phosphate black acid leaching solution to remove copper and aluminum;
step 4, adding alkaline leaching solution of lithium-containing aluminum electrolyte into acid leaching solution of waste lithium iron phosphate black powder, and adding hydrogen peroxide to perform an iron precipitation process;
step 5, adding calcium hydroxide into the solution after iron precipitation to perform a defluorination process;
and 6, adding sodium carbonate into the defluorinated liquid to perform a calcium removal process, thereby obtaining pure lithium sulfate and sodium solution.
In the step 1, the water consumption is 2.5-6 times of the lithium-containing aluminum electrolyte mass, the calcium hydroxide consumption is 0.8-1.4 times of the lithium-containing aluminum electrolyte mass, the temperature is 60-90 ℃ and the time is 1-5h.
In the step 2, the liquid-solid ratio is 3-7, the concentration of the sulfuric acid solution is 1-1.6mol/L, the reaction time is 1-5h, and the temperature is 30-90 ℃.
Further, in the step 3, the first adding amount of the iron powder is 1 to 1.5 times of the molar amount of the copper powder, and the second adding amount of the iron powder is to maintain the pH value of the solution at 3 to 4.
In the further scheme, in the step 4, the dosage of the hydrogen peroxide is 1 to 1.2 times of the theoretical dosage.
In a further scheme, in the step 5, the dosage of the calcium hydroxide is that the pH is adjusted to 9-10.
In a further scheme, in the step 6, the adding amount of the sodium carbonate is 1.01-1.05 times of the theoretical using amount.
The invention has the beneficial effects that:
according to the comprehensive recovery method for the waste lithium iron phosphate battery and the lithium-aluminum-containing electrolyte, disclosed by the invention, the waste lithium iron phosphate battery and the lithium-aluminum-containing electrolyte are comprehensively recovered, so that the method has the advantages of low economic cost, safe and controllable leaching process, high recovery rate of lithium and manganese, industrial application prospect, reduced auxiliary material cost, simplicity in operation and high recovery rate, and is suitable for materials of different lithium-aluminum-containing electrolytes.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following description will briefly explain the practical drawings required in the embodiments or the prior art description, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
Taking 100g of waste lithium iron phosphate black powder, and adding 110g of H 2 SO 4 The liquid-solid ratio was 5, and the reaction was carried out at 55℃for 1 hour, at which time the leaching rate of lithium was 99.54% and the leaching rate of iron was 98.45%. 17g of iron powder was added to the lithium iron phosphate leachate to adjust the pH to 3.7, and at this time, the concentrations of copper and aluminum in the leachate were 0.005g/L and 0.006g/L. 100g of waste lithium-containing aluminum electrolyte is taken, 450ml of water is added, 120g of calcium hydroxide is added, and the reaction is carried out for 2.5 hours at the temperature of 85 ℃, at this time, the leaching rate of lithium is 92.5%. Mixing the lithium iron phosphate leaching solution and the aluminum electrolyte leaching solution, adding calcium hydroxide to adjust the pH value to 9.6, then reacting for 0.5h, adding 1.05 times of the theoretical dosage of sodium carbonate to react for 0.5h, and filtering to obtain a pure lithium sodium sulfate solution.
Lithium sulfate and sodium solution of example 1
li Fe Ca Mg Cu Al F pH
4.98 0.0009 0.006 0.0001 0.0028 0.001 0.003 9.6
Example 2
Taking 100g of waste lithium iron phosphate black powder, adding 118g of H 2 SO 4 The liquid-solid ratio was 4, and the reaction was carried out at 60℃for 2 hours, at which time the leaching rate of lithium was 99.82% and the leaching rate of iron was 99.95%. 15g of iron powder was added to the lithium iron phosphate leachate to adjust the pH to 3.1, and at this time, the concentrations of copper and aluminum in the leachate were 0.004g/L and 0.008g/L. 100g of waste lithium-containing aluminum electrolyte is taken, 500ml of water is added, 130g of calcium hydroxide is added, and the reaction is carried out for 3 hours at 80 ℃, at this time, the leaching rate of lithium is 94%. Mixing the lithium iron phosphate leaching solution and the aluminum electrolyte leaching solution, adding calcium hydroxide to adjust the pH value to 9.2, then reacting for 0.5h, adding 1.01 times of the theoretical dosage of sodium carbonate to react for 0.5h, and filtering to obtain a pure lithium sodium sulfate solution.
Lithium sulfate and sodium solution of example 2
li Fe Ca Mg Cu Al F pH
4.72 0.0009 0.004 0.0006 0.0023 0.007 0.005 9.2
Example 3
Taking 100g of waste lithium iron phosphate black powder, and adding 140g of H 2 SO 4 The liquid-solid ratio was 6, and the leaching rate of lithium was 99.77% and the leaching rate of iron was 98.53% at 70℃for 1 hour. 26g of iron powder was added to the lithium iron phosphate leachate to adjust the pH to 3.33, and at this time, the concentrations of copper and aluminum in the leachate were 0.007g/L and 0.009g/L. 100g of waste lithium-containing aluminum electrolyte is taken, 400ml of water is added, 110g of calcium hydroxide is added, and the reaction is carried out for 2 hours at 90 ℃, at this time, the leaching rate of lithium is 88.67%. Mixing the lithium iron phosphate leaching solution and the aluminum electrolyte leaching solution, adding calcium hydroxide to adjust the pH value to 10, then reacting for 0.5h, adding 1.08 times of the theoretical dosage of sodium carbonate to react for 0.5h, and filtering to obtain a pure lithium sodium sulfate solution.
Example 3 lithium sulfate and sodium solution
li Fe Ca Mg Cu Al F pH
4.66 0.0009 0.003 0.0001 0.0034 0.0067 0.001 10
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further. Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (7)

1. A comprehensive recovery method of waste lithium iron phosphate batteries and lithium-aluminum-containing electrolytes is characterized by comprising the following steps:
step 1, mixing lithium-containing aluminum electrolyte with water in a certain proportion, adding a certain amount of calcium hydroxide after mixing, and reacting for a period of time at a certain temperature;
step 2, adding waste lithium iron phosphate black powder into the prepared sulfuric acid solution according to a certain liquid-solid ratio, and reacting for a period of time at a certain temperature;
step 3, adding a certain amount of iron powder into the waste lithium iron phosphate black acid leaching solution to remove copper and aluminum;
step 4, adding alkaline leaching solution of lithium-containing aluminum electrolyte into acid leaching solution of waste lithium iron phosphate black powder, and adding hydrogen peroxide to perform an iron precipitation process;
step 5, adding calcium hydroxide into the solution after iron precipitation to perform a defluorination process;
and 6, adding sodium carbonate into the defluorinated liquid to perform a calcium removal process, thereby obtaining pure lithium sulfate and sodium solution.
2. The comprehensive recovery method of waste lithium iron phosphate batteries and lithium-aluminum-containing electrolytes according to claim 1, wherein in the step 1, the water consumption is 2.5-6 times of the mass of the lithium-aluminum-containing electrolytes, the calcium hydroxide consumption is 0.8-1.4 times of the mass of the lithium-aluminum-containing electrolytes, the temperature is 60-90 ℃ and the time is 1-5 hours.
3. The method for comprehensively recovering the waste lithium iron phosphate battery and the lithium-aluminum-containing electrolyte according to claim 1, wherein in the step 2, the liquid-solid ratio is 3-7, the concentration of sulfuric acid solution is 1-1.6mol/L, the reaction time is 1-5h, and the temperature is 30-90 ℃.
4. The method for comprehensively recovering the waste lithium iron phosphate battery and the lithium-aluminum-containing electrolyte according to claim 1, wherein in the step 3, the first addition amount of iron powder is 1-1.5 times of the molar amount of copper powder, and the second addition amount of iron powder is such that the pH value of the solution is maintained at 3-4.
5. The method for comprehensively recovering the waste lithium iron phosphate battery and the lithium-aluminum-containing electrolyte according to claim 1, wherein the hydrogen peroxide is 1-1.2 times of the theoretical amount in the step 4.
6. The method for comprehensively recovering waste lithium iron phosphate batteries and lithium-aluminum-containing electrolytes according to claim 1, wherein in the step 5, the dosage of calcium hydroxide is adjusted to be 9-10.
7. The method for comprehensively recovering waste lithium iron phosphate batteries and lithium-aluminum-containing electrolytes according to claim 1, wherein in the step 6, the addition amount of sodium carbonate is 1.01-1.05 times of the theoretical use amount.
CN202310698823.5A 2023-06-13 2023-06-13 Comprehensive recovery method for waste lithium iron phosphate battery and lithium-aluminum-containing electrolyte Pending CN116715257A (en)

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