CN111118294A - Method for recycling valuable metals from waste lithium ion battery materials step by step - Google Patents
Method for recycling valuable metals from waste lithium ion battery materials step by step Download PDFInfo
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C22B5/00—General methods of reducing to metals
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention discloses a method for recovering valuable metals from waste lithium ion battery materials step by step, which comprises the following steps: mixing the anode material of the waste lithium ion battery with a carbon-containing solid reducing agent, or carrying out reduction roasting treatment on the anode and cathode mixture of the waste lithium ion battery at the temperature of 450-900 ℃, and crushing and grinding a roasted product; mixing the ground roasted product with water to form slurry, and injecting acid to control the pH value of the slurry to be 6-8 at room temperature to realize neutral leaching so as to obtain a lithium-rich leaching solution and neutral leaching slag; and carrying out low-intensity magnetic separation on the neutral leaching residue to obtain a non-magnetic product and a magnetic product containing at least one of nickel, cobalt and iron. The method can not only recover the valuable metals such as lithium, cobalt, nickel, iron, manganese and the like in the waste lithium ion battery materials step by step, but also has simple process, environmental protection and low cost.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery treatment, in particular to a method for recovering valuable metals from waste lithium ion battery materials step by step.
Background
Lithium ion batteries are widely used in the fields of portable equipment, electric vehicles, reserve power supplies, satellites and the like due to the advantages of high working voltage and specific energy, stable discharge voltage, light weight, small volume, long cycle life, no memory effect and the like. As the yield of lithium ion batteries increases, the amount of waste thereof also increases year by year. At present, a waste lithium ion battery material recovery system is not large-scale, the recovery rate is low, the cost is high, most of waste lithium ion batteries are not effectively treated, the environment is polluted, and a large amount of useful resources are wasted.
A great deal of research is carried out by researchers at home and abroad aiming at the treatment and recovery of the waste lithium ion battery, wherein the process combining hydrometallurgy, pyrometallurgy and wet pyrotechnics has remarkable characteristics. In the method for treating the anode material of the waste lithium ion battery, the recovery process based on hydrometallurgy is relatively mature, and the application in the industry is relatively wide. The lithium ion battery anode material mainly comprises lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary, nickel-cobalt-aluminum ternary material and the like. In order to recover valuable metals such as lithium, nickel, cobalt, manganese and the like, the most widely applied method is to react the cathode material with inorganic acid and add a reducing agent to leach out the valuable metals. In the process, valuable metals such as lithium, cobalt, nickel and the like are leached and then are sequentially separated, so that the problems of complicated separation procedures and difficult lithium recovery are inevitably generated.
Chinese patent CN103035977A discloses a method for recovering valuable metals from waste lithium ion batteries, which mainly adopts brine discharge → manual disassembly → alkali leaching separation (or low-temperature roasting) → reducing acid leaching (sulfuric acid + hydrogen peroxide) → chemical precipitation, so as to extract valuable metals from positive electrode materials. The method needs to consume a large amount of inorganic acid, needs to add a large amount of alkali for neutralization in the subsequent treatment process, has complex subsequent multi-metal separation and extraction process, low concentration of lithium ions in the liquid after extracting nickel and cobalt, difficult recovery, large consumption of raw materials, high cost and easy environmental pollution.
Chinese patent CN106129511A discloses a method for comprehensively recovering valuable metals from waste lithium ion battery materials, which mainly comprises the steps of mixing a waste lithium ion battery anode material with a reducing agent, carrying out reduction roasting treatment at the temperature of 500-750 ℃, and firstly adopting CO as a roasting product2Immersing in carbonized water to obtain aqueous solution of lithium bicarbonate for preparing Li2CO3Producing a product; valuable elements such as cobalt, nickel, manganese and the like in the water leaching residue are further leached out, and corresponding compound products are prepared after extraction and purification. The method realizes preferential extraction of lithium metal, but the subsequent multi-metal slag such as nickel, cobalt, manganese, aluminum and the like is still separated after being jointly leached, so that the method has the advantages of high acid consumption, high energy consumption, high cost and no environmental pollution.
Disclosure of Invention
In order to solve the technical problems of long and complex process flow, high acid and alkali consumption, high cost, easy environmental pollution, difficult lithium recovery, low recovery rate and the like of various metal separation and extraction processes in the conventional waste lithium ion battery recovery method, the invention provides a method for recovering valuable metals from waste lithium ion battery materials step by step, which can not only recover the valuable metals such as lithium, cobalt, nickel, iron, manganese and the like from the waste lithium ion battery materials step by step, but also has the advantages of simple process, environmental friendliness, low cost, good economic benefit and environmental benefit and great industrial application prospect.
The purpose of the invention is realized by the following technical scheme:
a method for recovering valuable metals from waste lithium ion battery materials step by step comprises the following steps:
step 1, reduction roasting: mixing the anode material of the waste lithium ion battery with a carbon-containing solid reducing agent, or carrying out reduction roasting treatment on the anode and cathode mixture of the waste lithium ion battery at the temperature of 450-900 ℃, and crushing and grinding a roasted product to obtain a ground roasted product;
step 2, neutral leaching and extracting lithium: mixing the ground roasted product with water to form slurry, and injecting acid to control the pH value of the slurry to be 6-8 at room temperature to realize neutral leaching so as to obtain a lithium-rich leaching solution and neutral leaching slag; the lithium-rich leaching solution is used for preparing Li2CO3Producing a product;
step 3, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residue to obtain a non-magnetic product and a magnetic product containing at least one of nickel, cobalt and iron.
Preferably, the waste lithium ion battery positive electrode material is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary and nickel-cobalt-aluminum ternary materials.
Preferably, in the step 1, the carbon-containing solid reducing agent is one or a mixture of several of coal, coke, graphite and organic matters, and the sum of the carbon in the carbon-containing solid reducing agent and the carbon in the waste lithium ion battery material is 0.2-1 time of the sum of the masses of the valuable metals in the waste lithium ion battery material.
Preferably, in the step 1, the reduction roasting time is 1-4 hours, and the roasted product is crushed and ground to be more than 80% of the particle size below 0.074 mm.
Preferably, in the step 2, the ground roasted product and water are mixed into slurry according to a liquid-solid ratio of 1: 1-6: 1 and stirred, then dilute sulfuric acid or dilute hydrochloric acid is injected to adjust the pH value of the slurry to be 6-8, leaching is carried out for 0.5-2.5 hours at room temperature, and solid-liquid separation is carried out to obtain a lithium-rich leaching solution and neutral leaching residues.
Preferably, in the step 3, the magnetic field intensity of the low-intensity magnetic separation is 100 mT-600 mT.
Preferably, the ground roasted product obtained in step 1 is subjected to magnetic separation, and then the non-magnetic product is subjected to neutral leaching to extract lithium.
Preferably, the method further comprises the following steps: step 4, extracting nickel and cobalt: the magnetic product is leached by adopting oxidation acid leaching or oxidation ammonia leaching to leach nickel element and/or cobalt element, and corresponding compound products are prepared after extraction and purification.
Preferably, in the step 4, when the magnetic product is subjected to oxidation acid leaching, a leaching agent is one of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 0.5-3.5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and an oxidant is one or a mixture of air, oxygen and hydrogen peroxide; when the magnetic product is leached by ammonia oxide, a leaching agent is a mixed solution of ammonia water and one or two of ammonium salts of ammonium sulfate, ammonium carbonate and ammonium chloride, the concentration of the ammonium salt is 0.5-4 mol/L, the concentration of the ammonia water is 1-5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and an oxidant is one of air and oxygen.
Preferably, the method further comprises the following steps: step 5, extracting manganese or aluminum: and recovering manganese element or aluminum element from the nonmagnetic product through acid leaching and purification.
According to the technical scheme provided by the invention, the carbon-containing solid reducing agent with lower cost is adopted to carry out low-temperature reduction roasting treatment on the anode material of the waste lithium ion battery, so that high-valence metal is reduced to low-valence metal, nickel and cobalt are converted into magnetic simple metal, and lithium is converted into Li2CO3. Due to Li2CO3The solubility in water is very low, and the lithium is difficult to extract by water leaching, so the Li is slowly dripped by the dilute acid in the invention2CO3The lithium-rich leaching solution reacts with acid to generate soluble lithium salt, the pH value is controlled to realize neutral selective leaching, lithium elements can be preferentially and selectively leached and extracted, metals such as nickel, cobalt, manganese and the like are remained in leaching residues, the purity of the lithium-rich leaching solution is high, and the problems of difficult lithium recovery and low recovery rate are solved. Meanwhile, the magnetic nickel and cobalt metal simple substances can be separated from oxides such as non-magnetic manganese oxide and the like through weak magnetic separation, so that the multi-metal in the waste lithium ion battery material is extracted and recovered step by step. The method can not only recover the valuable metals such as lithium, cobalt, nickel, iron, manganese and the like in the waste lithium ion battery materials step by step, but also has the advantages of simple process, environmental friendliness, low cost, good economic benefit and environmental benefit and larger industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic flow chart of the method for recovering valuable metals from waste lithium ion battery materials step by step.
Detailed Description
The technical solutions in the embodiments of the present invention are 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 embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The method for recovering valuable metals from waste lithium ion battery materials step by step provided by the invention is described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
As shown in fig. 1, a method for recovering valuable metals from waste lithium ion battery materials step by step may include the following steps:
step 1, reduction roasting: mixing the anode material of the waste lithium ion battery with a carbon-containing solid reducing agent, or carrying out reduction roasting treatment on the anode and cathode mixture of the waste lithium ion battery at the temperature of 450-900 ℃, and crushing and grinding a roasted product to obtain a ground roasted product.
Step 2, neutral leaching and extracting lithium: mixing the ground roasted product with water to form slurry, and injecting acid to control the pH value of the slurry to be 6-8 at room temperature to realize neutral leaching so as to obtain a lithium-rich leaching solution and neutral leaching slag; the lithium-rich leaching solution is used for preparing Li2CO3Producing a product;
step 3, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residue to obtain a non-magnetic product and a magnetic product containing at least one of nickel, cobalt and iron.
Step 4, extracting nickel and cobalt: the magnetic product is leached by adopting oxidation acid leaching or oxidation ammonia leaching to leach nickel element and/or cobalt element, and corresponding compound products are prepared after extraction and purification.
Step 5, extracting manganese or aluminum: and recovering manganese element or aluminum element from the nonmagnetic product through acid leaching and purification.
Specifically, the method for recovering valuable metals from waste lithium ion battery materials step by step comprises the following embodiments:
(1) the waste lithium ion battery positive electrode material is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary and nickel-cobalt-aluminum ternary materials.
(2) In the step 1, the carbon-containing solid reducing agent is one or a mixture of several of coal, coke, graphite and organic matters, and the sum of the carbon in the carbon-containing solid reducing agent and the carbon in the waste lithium ion battery material is 0.2-1 time of the sum of the mass of valuable metals in the waste lithium ion battery material.
(3) In the step 1, the reduction roasting time is 1-4 hours, and the roasted product is crushed and ground to be more than 80% of the granularity below 0.074 mm.
(4) In the step 2, the ground roasting product and water are mixed into slurry according to the liquid-solid ratio of 1: 1-6: 1 and stirred, then dilute sulfuric acid or dilute hydrochloric acid is injected to adjust the pH value of the slurry to be 6-8 (preferably the pH value is 6.5-7.5), leaching is carried out for 0.5-2.5 hours at room temperature, and solid-liquid separation is carried out to obtain a lithium-rich leaching solution and neutral leaching residues.
(5) In the step 3, the magnetic field intensity of the low-intensity magnetic separation is 100 mT-600 mT.
(6) In the step 4, a leaching agent for oxidation acid leaching is one of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 0.5-3.5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and an oxidant is one or a mixture of more of air, oxygen and hydrogen peroxide.
(7) In the step 4, the lixiviant for the ammonia oxidation leaching is a mixed solution of ammonia water and one or two of ammonium salts of ammonium sulfate, ammonium carbonate and ammonium chloride, the concentration of the ammonium salt is 0.5-4 mol/L, the concentration of the ammonia water is 1-5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and the oxidant is one of air and oxygen.
(8) In the step 5, the leaching agent for acid leaching of the non-magnetic product is one of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 0.5-3.5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, and the temperature is 20-90 ℃.
(9) The execution sequence of step 2 and step 3 can be interchanged, namely: the levigated roasted product obtained in the step 1 can be subjected to neutral leaching to extract lithium, and then magnetic separation is performed on neutral leaching residues; the ground roasted product obtained in the step 1 can also be subjected to magnetic separation firstly, and then the non-magnetic product is subjected to neutral leaching to extract lithium.
Furthermore, the invention adopts the carbon-containing solid reducing agent with lower cost to carry out low-temperature reduction roasting treatment on the anode material of the waste lithium ion battery, so that high-valence metal in the anode material is reduced to low-valence metal, nickel and cobalt are converted into magnetic simple metal, and lithium is converted into Li2CO3. Due to Li2CO3The solubility in water is very low, and the lithium is difficult to extract by water leaching, so the Li is slowly dripped by the dilute acid in the invention2CO3The lithium-rich leaching solution reacts with acid to generate soluble lithium salt, the pH value is controlled to realize neutral selective leaching, lithium elements can be preferentially and selectively leached and extracted, metals such as nickel, cobalt, manganese and the like are remained in leaching residues, the purity of the lithium-rich leaching solution is high, and the problems of difficult lithium recovery and low recovery rate are solved. Meanwhile, the magnetic nickel and cobalt metal simple substances can be separated from oxides such as non-magnetic manganese oxide and the like through weak magnetic separation, so that the multi-metal in the waste lithium ion battery material is extracted and recovered step by step. The method realizes preferential selective lithium extraction and separation of nickel, cobalt and manganese, has the advantages of simple process, low cost, high recovery rate of valuable metals, wide applicability of waste lithium ion battery materials and the like, and has remarkable economic and social benefits.
In conclusion, the embodiment of the invention can not only recover valuable metals such as lithium, cobalt, nickel, iron, manganese and the like in the waste lithium ion battery materials step by step, but also has the advantages of simple process, environmental friendliness, low cost, good economic benefit and environmental benefit and great industrial application prospect.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the method for recovering valuable metals from waste lithium ion battery materials step by step in the present invention is described in detail below with specific examples.
Example 1
A method for recovering valuable metals from waste lithium ion battery materials step by step is used for treating waste lithium ion battery anode powder (the granularity is less than or equal to 0.5mm) containing 10.63% of cobalt, 6.50% of lithium, 28.30% of nickel, 11.75% of manganese and 3.75% of iron, and can comprise the following steps:
step 1A, reduction roasting: uniformly mixing 100g of the waste lithium ion battery anode powder and coke powder (as a carbon-containing solid reducing agent) with the fixed carbon content of 85%, wherein the fixed carbon mass of the coke powder is 0.5 times of the total mass of lithium, nickel, cobalt, manganese and iron in the waste lithium ion battery anode powder, carrying out reduction roasting treatment at the temperature of 700 ℃, the reduction roasting time is 2 hours, and crushing and grinding a roasted product until the granularity is less than 0.074mm and accounts for 90%, thereby obtaining a ground roasted product.
Step 2A, neutral leaching and lithium extraction: firstly, mixing the ground roasted product and water into slurry according to the liquid-solid ratio of 3:1, stirring, then adjusting the pH value of the slurry to about 7 by using dilute sulfuric acid with the concentration of 10g/L at room temperature, leaching for 1 hour, and carrying out solid-liquid separation to obtain a lithium-rich leaching solution and neutral leaching residues; the Li is prepared by precipitating the lithium-rich leaching solution with sodium carbonate2CO3And (5) producing the product.
Step 3A, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residues under the magnetic field strength of 100mT, thereby obtaining a magnetic product containing nickel, cobalt and iron and a non-magnetic product containing manganese oxide.
Step 4A, extracting nickel and cobalt: the magnetic product is leached by adopting oxidizing acid to leach nickel and cobalt elements in the magnetic product, a leaching agent is 2mol/L sulfuric acid, the solid-to-liquid ratio is 1:5, the leaching time is 4 hours, the temperature is 50 ℃, an oxidant is air, and a nickel-cobalt compound product is prepared after extraction and purification.
Step 5A, extracting manganese: and carrying out acid leaching on the nonmagnetic product, wherein a leaching agent is 2mol/L sulfuric acid, the solid-to-liquid ratio is 1:5, the leaching time is 2 hours, the temperature is 25 ℃, and the manganese element is purified and recovered.
Through detection: the leaching rate of lithium, nickel, cobalt, iron and manganese reaches more than 98 percent.
Example 2
A method for recovering valuable metals from waste lithium ion battery materials step by step is used for processing a positive and negative electrode mixture (the granularity is less than or equal to 0.5mm) of a waste lithium ion battery containing 26.63% of cobalt, 5.50% of lithium and 30.48% of graphite, and can comprise the following steps:
step 1B, reduction roasting: and (2) carrying out reduction roasting treatment on 100g of the waste lithium ion battery anode and cathode mixture at the temperature of 600 ℃, wherein the reduction roasting time is 2 hours, and crushing and grinding the roasted product until the granularity is 85% below 0.074mm, so as to obtain a ground roasted product.
Step 2B, neutral leaching and extracting lithium: firstly, levigatingMixing the roasted product and water into slurry according to a liquid-solid ratio of 4:1, stirring, adjusting the pH value of the slurry to 6.5-7 by using 10g/L dilute sulfuric acid at room temperature, leaching for 1.5 hours, and performing solid-liquid separation to obtain a lithium-rich leaching solution and neutral leaching residues; the Li is prepared by precipitating the lithium-rich leaching solution with sodium carbonate2CO3And (5) producing the product.
Step 3B, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residues under the magnetic field strength of 200mT, thereby obtaining a magnetic product containing cobalt.
And step 4B, extracting cobalt: the cobalt element in the magnetic product is leached by oxidizing acid, the leaching agent is 1.5mol/L hydrochloric acid, the solid-liquid ratio is 1:4, the leaching time is 5 hours, the temperature is 80 ℃, the oxidant is air, and the cobalt compound product is prepared after extraction and purification.
Through detection: the leaching rate of lithium is more than 95 percent, and the recovery rate of cobalt reaches more than 95 percent.
Example 3
A method for recovering valuable metals from waste lithium ion battery materials step by step is used for treating waste lithium ion battery anode powder (the granularity is less than or equal to 0.5mm) containing 11.38 percent of cobalt, 6.92 percent of lithium, 35.46 percent of nickel and 10.90 percent of manganese, and can comprise the following steps:
step 1C, reduction roasting: 100g of the waste lithium ion battery anode powder and anthracite (as a carbon-containing solid reducing agent) with the fixed carbon content of 75 percent are uniformly mixed, wherein the fixed carbon mass of the anthracite is 0.4 time of the total mass of lithium, nickel, cobalt and manganese in the waste lithium ion battery anode powder, the reduction roasting treatment is carried out at the temperature of 650 ℃, the reduction roasting time is 2 hours, and the roasted product is crushed and ground to 80 percent with the granularity of less than 0.074mm, so that the ground roasted product is obtained.
Step 2C, neutral leaching and extracting lithium: firstly, mixing the ground roasted product and water into slurry according to a liquid-solid ratio of 3:1, stirring, then adjusting the pH value of the slurry to 7-7.5 by using 10g/L dilute sulfuric acid at room temperature, leaching for 2 hours, and carrying out solid-liquid separation to obtain a lithium-rich leaching solution and neutral leaching residues; the Li is prepared by precipitating the lithium-rich leaching solution with sodium carbonate2CO3Product(s)。
Step 3C, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residues under the magnetic field strength of 300mT, thereby obtaining a magnetic product containing nickel and cobalt and a non-magnetic product containing manganese oxide.
Step 4C, extracting nickel and cobalt: the magnetic product is extracted and leached by ammonia oxide to obtain nickel and cobalt elements, the concentration of ammonium sulfate is 1mol/L, the concentration of ammonia water is 3mol/L, the solid-to-liquid ratio is 1:5, the leaching time is 4 hours, the temperature is 60 ℃, the oxidant is air, and the nickel-cobalt compound product is prepared after extraction and purification.
Step 5C, extracting manganese: and carrying out acid leaching on the nonmagnetic product, wherein a leaching agent is 2mol/L sulfuric acid, the solid-to-liquid ratio is 1:5, the leaching time is 2 hours, the temperature is 55 ℃, and the manganese element is purified and recovered.
Through detection: the leaching rate of lithium, nickel, cobalt and manganese reaches more than 95 percent.
Example 4
A method for recovering valuable metals from waste lithium ion battery materials step by step is used for processing waste lithium ion battery anode powder (the granularity is less than or equal to 0.5mm) containing 16.63% of nickel, 6.50% of lithium and 45.23% of manganese, and can comprise the following steps:
step 1D, reduction roasting: 100g of the waste lithium ion battery anode powder and anthracite (as a carbon-containing solid reducing agent) with the fixed carbon content of 85 percent are uniformly mixed, wherein the fixed carbon mass of the anthracite is 0.3 time of the total mass of lithium, nickel and manganese in the waste lithium ion battery anode powder, the reduction roasting treatment is carried out at the temperature of 800 ℃, the reduction roasting time is 2 hours, and the roasted product is crushed and ground to 85 percent with the granularity of below 0.074mm, so that the ground roasted product is obtained.
Step 2D, neutral leaching and extracting lithium: firstly, mixing the ground roasted product and water into slurry according to a liquid-solid ratio of 3:1, stirring, then adjusting the pH value of the slurry to 6.5-7 by using 10g/L dilute sulfuric acid at room temperature, leaching for 1.5 hours, and carrying out solid-liquid separation to obtain a lithium-rich leaching solution and neutral leaching residues; the Li is prepared by precipitating the lithium-rich leaching solution with sodium carbonate2CO3And (5) producing the product.
Step 3D, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residues under the magnetic field strength of 500mT, thereby obtaining a magnetic product containing nickel and a non-magnetic product containing manganese oxide.
Step 4D, extracting nickel: the magnetic product is leached by adopting oxidizing ammonia to leach nickel and cobalt elements in the magnetic product, the concentration of ammonium carbonate is 1mol/L, the concentration of ammonia water is 2mol/L, the solid-to-liquid ratio is 1:4, the leaching time is 5 hours, the temperature is 60 ℃, an oxidant is air, and a nickel-cobalt compound product is prepared after extraction and purification.
Step 5D, extracting manganese: and carrying out acid leaching on the nonmagnetic product, wherein a leaching agent is 1.5mol/L sulfuric acid, the solid-to-liquid ratio is 1:5, the leaching time is 2 hours, the temperature is 35 ℃, and the manganese element is purified and recovered.
Through detection: the leaching rate of lithium, nickel and manganese reaches more than 95 percent.
Example 5
A method for recycling valuable metals from waste lithium ion battery materials step by step is used for processing a waste lithium ion battery anode and cathode mixture (the granularity is less than or equal to 0.5mm) containing 7.96% of cobalt, 5.95% of lithium, 32.03% of nickel, 9.42% of manganese and 14.79% of carbon, and can comprise the following steps:
step 1E, reduction roasting: and (2) carrying out reduction roasting treatment on 100g of the waste lithium ion battery anode and cathode mixture at the temperature of 500 ℃, wherein the reduction roasting time is 3.5 hours, and crushing and grinding the roasted product until the granularity is less than 0.074mm and accounts for 95%, so as to obtain a ground roasted product.
Step 2E, neutral leaching and extracting lithium: firstly, mixing the ground roasted product and water into slurry according to the liquid-solid ratio of 5:1, stirring, then adjusting the pH value of the slurry to about 7 by using dilute hydrochloric acid with the concentration of 10g/L at room temperature, leaching for 1 hour, and carrying out solid-liquid separation to obtain a lithium-rich leaching solution and neutral leaching residues; the Li is prepared by precipitating the lithium-rich leaching solution with sodium carbonate2CO3And (5) producing the product.
Step 3E, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residues under the magnetic field strength of 350mT, thereby obtaining a magnetic product containing nickel and cobalt and a non-magnetic product containing manganese oxide.
Step 4E, extracting nickel and cobalt: the magnetic product is leached by using oxidizing acid to leach nickel and cobalt elements in the magnetic product, a leaching agent is 3mol/L sulfuric acid, the solid-to-liquid ratio is 1:10, the leaching time is 6 hours, the temperature is 90 ℃, an oxidant is air, and a nickel-cobalt compound product is prepared after extraction and purification.
Step 5E, extracting manganese: and carrying out acid leaching on the nonmagnetic product, wherein a leaching agent is 1mol/L sulfuric acid, the solid-to-liquid ratio is 1:4, the leaching time is 6 hours, the temperature is 90 ℃, and the manganese element is purified and recovered.
Through detection: the leaching rates of lithium, nickel, cobalt and manganese are 93.68%, 92.81%, 98.81% and 96.72% respectively.
In conclusion, the embodiment of the invention can not only recover valuable metals such as lithium, cobalt, nickel, iron, manganese and the like in the waste lithium ion battery materials step by step, but also has the advantages of simple process, environmental friendliness, low cost, good economic benefit and environmental benefit and great industrial application prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for recovering valuable metals from waste lithium ion battery materials step by step is characterized by comprising the following steps:
step 1, reduction roasting: mixing the anode material of the waste lithium ion battery with a carbon-containing solid reducing agent, or carrying out reduction roasting treatment on the anode and cathode mixture of the waste lithium ion battery at the temperature of 450-900 ℃, and crushing and grinding a roasted product to obtain a ground roasted product;
step 2, neutral leaching and extracting lithium: mixing the ground roasted product with water to form slurry, and injecting acid to control the pH value of the slurry to be 6-8 at room temperature to realize neutral leaching, thereby obtaining a lithium-rich leaching solution and neutral leaching slag(ii) a The lithium-rich leaching solution is used for preparing Li2CO3Producing a product;
step 3, magnetic separation: and carrying out low-intensity magnetic separation on the neutral leaching residue to obtain a non-magnetic product and a magnetic product containing at least one of nickel, cobalt and iron.
2. The method for recycling valuable metals from waste lithium ion battery materials in a stepwise manner according to claim 1, wherein the waste lithium ion battery positive electrode material is one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, nickel cobalt binary, nickel manganese binary, cobalt manganese binary, nickel cobalt manganese ternary, and nickel cobalt aluminum ternary.
3. The method for recycling valuable metals from waste lithium ion battery materials step by step according to claim 1 or 2, characterized in that in the step 1, the carbon-containing solid reducing agent is one or a mixture of coal, coke, graphite and organic matters, and the sum of the carbon in the carbon-containing solid reducing agent and the carbon in the waste lithium ion battery materials is 0.2-1 times of the sum of the valuable metals in the waste lithium ion battery materials.
4. The method for recycling valuable metals from waste lithium ion battery materials step by step according to claim 1 or 2, characterized in that, in the step 1, the reduction roasting time is 1-4 hours, and the roasted product is crushed and ground to a particle size of less than 0.074mm, which is more than 80%.
5. The method for recycling valuable metals from waste lithium ion battery materials in steps of 1 or 2, wherein in the step 2, the ground roasted product and water are mixed into slurry according to a liquid-solid ratio of 1: 1-6: 1 and are stirred, then dilute sulfuric acid or dilute hydrochloric acid is injected to adjust the pH value of the slurry to be 6-8, the slurry is leached for 0.5-2.5 hours at room temperature, and the lithium-rich leachate and neutral leaching residues are obtained through solid-liquid separation.
6. The method for recovering valuable metals from waste lithium ion battery materials step by step according to claim 1 or 2, characterized in that in the step 3, the magnetic field intensity of the low-intensity magnetic separation is 100 mT-600 mT.
7. The method for recovering valuable metals from waste lithium ion battery materials step by step according to claim 1 or 2, characterized in that the ground roasted product obtained in step 1 is subjected to magnetic separation, and then the non-magnetic product is subjected to neutral leaching to extract lithium.
8. The method for recovering valuable metals from waste lithium ion battery materials in a stepwise manner according to claim 1 or 2, characterized by further comprising:
step 4, extracting nickel and cobalt: the magnetic product is leached by adopting oxidation acid leaching or oxidation ammonia leaching to leach nickel element and/or cobalt element, and corresponding compound products are prepared after extraction and purification.
9. The method for recovering valuable metals from waste lithium ion battery materials step by step according to claim 8, wherein in the step 4, when the magnetic product is subjected to oxidation acid leaching, a leaching agent is one of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 0.5-3.5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and an oxidant is one or a mixture of air, oxygen and hydrogen peroxide;
when the magnetic product is leached by ammonia oxide, a leaching agent is a mixed solution of ammonia water and one or two of ammonium salts of ammonium sulfate, ammonium carbonate and ammonium chloride, the concentration of the ammonium salt is 0.5-4 mol/L, the concentration of the ammonia water is 1-5 mol/L, the solid-to-liquid ratio is 1: 3-1: 10, the leaching time is 1-8 hours, the temperature is 20-90 ℃, and an oxidant is one of air and oxygen.
10. The method for recovering valuable metals from waste lithium ion battery materials in a stepwise manner according to claim 1 or 2, characterized by further comprising:
step 5, extracting manganese or aluminum: and recovering manganese element or aluminum element from the nonmagnetic product through acid leaching and purification.
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| WO2024041398A1 (en) * | 2022-08-26 | 2024-02-29 | 赣州天奇循环环保科技有限公司 | Multi-component recycling method for spent lithium-ion battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593606A (en) * | 2015-01-14 | 2015-05-06 | 上海交通大学 | Method for recycling positive-negative electrode defective materials of waste lithium waste lithium cobalt oxide lithium-ion batteries |
| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN107994288A (en) * | 2017-12-14 | 2018-05-04 | 眉山顺应动力电池材料有限公司 | Valuable metal recovery method in waste and old nickle cobalt lithium manganate ternary cell positive material |
| CN109750155A (en) * | 2019-01-08 | 2019-05-14 | 安徽工业大学 | A method of the Call Provision from waste lithium ion cell anode material |
| CN109881008A (en) * | 2019-02-27 | 2019-06-14 | 广西银亿新材料有限公司 | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery |
| CN110079671A (en) * | 2019-04-23 | 2019-08-02 | 北京科技大学 | A kind of method of waste and old lithium ion battery valuable element synthetical recovery |
-
2020
- 2020-01-15 CN CN202010042979.4A patent/CN111118294A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593606A (en) * | 2015-01-14 | 2015-05-06 | 上海交通大学 | Method for recycling positive-negative electrode defective materials of waste lithium waste lithium cobalt oxide lithium-ion batteries |
| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN107994288A (en) * | 2017-12-14 | 2018-05-04 | 眉山顺应动力电池材料有限公司 | Valuable metal recovery method in waste and old nickle cobalt lithium manganate ternary cell positive material |
| CN109750155A (en) * | 2019-01-08 | 2019-05-14 | 安徽工业大学 | A method of the Call Provision from waste lithium ion cell anode material |
| CN109881008A (en) * | 2019-02-27 | 2019-06-14 | 广西银亿新材料有限公司 | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery |
| CN110079671A (en) * | 2019-04-23 | 2019-08-02 | 北京科技大学 | A kind of method of waste and old lithium ion battery valuable element synthetical recovery |
Cited By (42)
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| CN112048621A (en) * | 2020-07-20 | 2020-12-08 | 浙江天能新材料有限公司 | Method for recovering cobalt and lithium from waste lithium cobalt oxide batteries |
| CN111945006A (en) * | 2020-08-21 | 2020-11-17 | 昆明理工大学 | Method for separating and recovering valuable metals in lithium ion battery roasting product |
| CN112093787A (en) * | 2020-09-27 | 2020-12-18 | 中钢集团南京新材料研究院有限公司 | Method for recycling and preparing olivine type five-element high-entropy lithium battery precursor |
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| WO2023126557A1 (en) * | 2021-12-31 | 2023-07-06 | Consejo Superior De Investigaciones Científicas (Csic) | Method for obtaining li, ni and co from discarded lithium ion batteries |
| ES2945487A1 (en) * | 2021-12-31 | 2023-07-03 | Consejo Superior Investigacion | Procedure for obtaining Li, Ni and Co from discarded lithium ion batteries (Machine-translation by Google Translate, not legally binding) |
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| CN116425136B (en) * | 2023-05-06 | 2023-12-19 | 浙江南化防腐设备有限公司 | Method for purifying and recycling battery-grade ferric phosphate from lithium-extracted ferrophosphorus slag |
| CN116425136A (en) * | 2023-05-06 | 2023-07-14 | 浙江南化防腐设备有限公司 | Method for purifying and recycling battery-grade ferric phosphate from lithium-extracted ferrophosphorus slag |
| CN117551867A (en) * | 2024-01-10 | 2024-02-13 | 矿冶科技集团有限公司 | Treatment method of titanium-containing blast furnace slag |
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