CN115216622A - Method for recycling anode and cathode materials of ternary lithium battery - Google Patents
Method for recycling anode and cathode materials of ternary lithium battery Download PDFInfo
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- CN115216622A CN115216622A CN202210744766.5A CN202210744766A CN115216622A CN 115216622 A CN115216622 A CN 115216622A CN 202210744766 A CN202210744766 A CN 202210744766A CN 115216622 A CN115216622 A CN 115216622A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/006—Wet processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The application discloses a method for recycling positive and negative electrode materials of a ternary lithium battery, which comprises the following steps: plasma reduction: adding an auxiliary agent into the mixed powder of the anode and the cathode of the ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand; water leaching lithium manganese: adding water into the calcine, stirring and leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate; adjusting the value and precipitating manganese: adjusting the pH value of the first filtrate to obtain manganese hydroxide filter residue and a second filtrate; carbonizing and precipitating lithium: and adding carbonate into the second filtrate to obtain lithium carbonate filter residue. The method solves the technical problems that in the prior art, the ternary lithium battery resource recovery process is complex, the cost is high, and more impurities are extracted from the ternary lithium battery.
Description
Technical Field
The application relates to the technical field of metal composite materials, in particular to a method for recycling a positive electrode material and a negative electrode material of a ternary lithium battery.
Background
Nickel is one of strategic minerals in China, has an important position in emerging industries such as traditional stainless steel and new energy automobile batteries, and is regarded as 'strategic materials' by many countries. China is the largest world consuming country of nickel resources, but is also a poor nickel country. The reserves of laterite-nickel ore in China are small, the reserve of nickel resource is mainly nickel sulfide ore and is mainly distributed in Gansu (accounting for 57.8%), inner Mongolia (accounting for 19.4%), xinjiang (accounting for 7.6%) and the like. At present, more than 90% of nickel ore resources required by China come from Indonesia and Philippines, the external dependence of the nickel resources is maintained at a high level due to contradiction between supply and demand, and the continuous and stable supply of the nickel resources has great challenges.
Nickel is a transition metal element with a unique extra-nuclear electronic structure, and in the battery reaction, the transition metal nickel is subjected to valence change to achieve charge balance when lithium ions are removed, and can be changed from Ni 2+ Become Ni 3+ And then made of Ni 3+ To Ni 4+ The higher the nickel content in the ternary cathode material is, the more lithium ions can be extracted, and the higher the gram capacity of the cathode material is.
However, the main current process for recovering the anode powder and the cathode powder of the ternary lithium battery is a wet process, the main idea is to leach mixed metal salt solution in the waste, then separate the mixed metal salt solution through a plurality of extracting agents, and purify the mixed metal salt solution step by step into raw materials with high purity, such as nickel salt solution, cobalt salt solution, manganese salt solution, lithium salt and the like, the extraction process flow is long, a large amount of acid-base solution is used, the cost is high, and impurities in the extracted product are more.
Disclosure of Invention
The application mainly aims to provide a method for recycling a positive electrode material and a negative electrode material of a ternary lithium battery, and aims to solve the technical problems that in the prior art, the ternary lithium battery resource recycling process is complex, the cost is high, and more impurities are extracted from the ternary lithium battery.
In order to achieve the above object, the present application provides a method for recovering positive and negative electrode materials of a ternary lithium battery, which includes the following steps:
plasma reduction: adding an auxiliary agent into the mixed powder of the anode and the cathode of the ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand;
water leaching lithium manganese: adding water into the calcine, stirring and leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
adjusting the value and precipitating manganese: adjusting the pH value of the first filtrate to obtain manganese hydroxide filter residue and a second filtrate;
and (3) carbonizing and precipitating lithium: and adding carbonate into the second filtrate to obtain lithium carbonate filter residue.
Optionally, the auxiliary agent in the plasma reduction step comprises a reducing agent and an acidifying agent.
Optionally, the reducing agent includes one or more of lithium battery graphite negative electrode powder, activated carbon powder and coal powder.
Optionally, the acidifying agent comprises a water-soluble compound comprising sulfate, hydrogen sulfate and/or chloride ions.
Optionally, the roasting temperature in the plasma reduction step is 600-900 ℃, and the roasting time is 3-6 hours.
Optionally, the firing in the plasma reduction step is in an oxygen-free condition, a reducing atmosphere, or a protective atmosphere.
Optionally, the reducing atmosphere comprises a hydrogen-argon mixed gas or a hydrogen-nitrogen mixed gas, the concentration of hydrogen in the hydrogen-argon mixed gas is 8-12%, and the concentration of hydrogen in the hydrogen-nitrogen mixed gas is 8-12%.
Optionally, the step of adding water to the calcine, stirring, leaching, and obtaining cobalt-doped nickel-based catalyst filter residue and first filtrate includes:
adding water with the mass of 4-7 times of the calcine, stirring, and controlling the leaching temperature to leach the calcine for 2-3 hours at the temperature of 70-98 ℃.
Optionally, the step of adjusting the pH value of the first filtrate to obtain a manganese hydroxide filter residue and a second filtrate includes:
and adding excessive liquid caustic soda into the first filtrate to adjust the pH value of the first filtrate to 8-13, controlling the reaction temperature at 60-80 ℃, and reacting for 0.5-2 hours to obtain manganese hydroxide filter residue and second filtrate.
Optionally, the step of adding carbonate to the second filtrate to obtain the lithium carbonate filter residue and the waste liquid includes:
and adding excessive sodium carbonate into the second filtrate, controlling the reaction temperature at 80-100 ℃, and reacting for 1-4 hours to obtain lithium carbonate filter residue and waste liquid.
The application provides a method for recovering anode and cathode materials of a ternary lithium battery, which comprises the steps of adding an auxiliary agent into mixed powder of the anode and the cathode of the ternary lithium battery through plasma reduction, mixing, and then feeding the mixed powder into a plasma reduction furnace for roasting to obtain roasted sand, so that manganese and lithium are converted into a metal salt solution of the manganese and the lithium, a large amount of nickel is combined with a small amount of cobalt and aluminum to form a nickel-based catalyst, and organic impurities in the mixed powder of the anode and the cathode of the ternary lithium battery are decomposed into carbon dioxide, water and other small molecules to be removed; then, lithium and manganese are soaked in water, namely, water is added into the calcine, the calcine is stirred and leached to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate, the separation of the filtrate containing manganese and lithium and the filter residue containing the cobalt-doped nickel-based catalyst is realized, further, the recovery of the cobalt-doped nickel-based catalyst is realized, further, the value is adjusted to precipitate manganese, namely, the pH value of the first filtrate is adjusted to obtain manganese hydroxide filter residue and second filtrate, the separation of manganese and lithium is realized, further, the recovery of manganese is realized, further, the lithium is precipitated through carbonization, namely, carbonate is added into the second filtrate to obtain lithium carbonate filter residue, the recovery of lithium is realized, further, the resource recycling of all components of the mixed powder of the positive electrode and the negative electrode of the waste ternary lithium battery is realized, compared with the mode that manganese, cobalt, nickel and lithium are sequentially recycled and impurity components are required to be removed in the prior art, the recycling method can be used for preparing nickel-based catalysts from nickel, cobalt, aluminum and other metals through a plasma reduction process, the prepared nickel-based catalysts can be directly put into use without further separation, so that the effective utilization of resources can be realized, the technological processes of separation and extraction of various metals can be simplified, reagents required by separation and extraction of various metals are reduced, the recycling cost is reduced, and the technical problems that the resource recycling process of the ternary lithium battery is complex, the cost is high and the extracted product has more impurities in the prior art are solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and, together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a schematic flow chart of an embodiment of a method for recycling an anode and cathode material of a ternary lithium battery according to the present application.
The implementation of the objectives, functional features, and advantages of the present application will be further described with reference to the accompanying drawings.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. It should be apparent that the described embodiments are only some 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 given herein without making any creative effort, shall fall within the protection scope of the present invention.
Nickel is one of strategic minerals in China, has an important position in emerging industries such as traditional stainless steel and new energy automobile batteries, and is regarded as 'strategic materials' by many countries. China is the largest world consuming country of nickel resources, but is also a poor nickel country. China has little laterite nickel ore reserves, and the nickel resource reserves mainly adopt nickel sulfide ores and are mainly distributed in Gansu (accounting for 57.8%), inner Mongolia (accounting for 19.4%), xinjiang (accounting for 7.6%) and the like. At present, more than 90% of nickel ore resources required by China come from Indonesia and Philippines, the external dependence of the nickel resources is maintained at a high level due to contradiction between supply and demand, and the continuous and stable supply of the nickel resources has great challenges.
Nickel is a transition metal element with a unique extra-nuclear electronic structure, and in the battery reaction, the transition metal nickel is subjected to valence change to achieve charge balance when lithium ions are removed, and can be changed from Ni 2+ To Ni 3+ And then made of Ni 3+ To Ni 4+ The higher the nickel content in the ternary cathode material is, the more lithium ions can be extracted, and the higher the gram capacity of the cathode material is. Nickel is an ideal battery anode material element, and in recent years, ternary anode materials containing high content of nickel are developed rapidly.
At present, the mainstream process for recovering the anode powder and the cathode powder of the ternary lithium battery is a wet process, and the main idea is to leach mixed metal salt solution in waste materials, then separate the mixed metal salt solution through a plurality of extracting agents, and purify the mixed metal salt solution step by step into raw materials with higher purity, such as nickel salt solution, cobalt salt solution, manganese salt solution, lithium salt and the like, however, the existing wet process has the following problems:
firstly, the current wet process has longer process flow, more influence factors on the product quality, and higher cost due to the use of a large amount of acid-base solution.
Secondly, in the leaching process, graphite slag, newspaper waste slag and the like are inevitably used as solid waste or dangerous waste, and the third-party treatment cost is high.
Thirdly, the organic extractant and the solvent used in the extraction process have certain water solubility, which increases the difficulty of the subsequent treatment of the product and the extract, and the zero-discharge treatment cost of the wastewater is high.
Fourthly, the design capacity ratios of the extraction lines to nickel, cobalt and manganese are balanced and universal, so that higher capacity utilization rate must be maintained to ensure the production economy, and once the nickel, cobalt and manganese ratios at the raw material end are not balanced, the waste of the capacity of a certain line can be caused.
Fifth, the extraction separation of nickel, cobalt, and manganese is also sequential, and it is impossible to perform an alternative separation for a specific ratio of nickel, cobalt, and manganese before a new extraction system is developed.
Aiming at actual production and the development trend of the nickel-cobalt-manganese ternary lithium battery to the high-nickel battery in the future, the recycled mixed positive and negative electrode powder of the lithium battery contains a small amount of aluminum, copper, nickel, cobalt, manganese, graphite and organic binder impurities, and has complex components, so that the method for recycling the positive and negative electrode materials of the ternary lithium battery realizes the full-component resource recycling of the mixed positive and negative electrode powder of the waste nickel-cobalt-manganese ternary lithium battery, and overcomes the technical problems of complex resource recycling process, high cost and more extracted product impurities of the ternary lithium battery in the prior art.
In an embodiment of the method for recycling positive and negative electrode materials of a ternary lithium battery, referring to fig. 1, the method for recycling positive and negative electrode materials of a ternary lithium battery includes:
step S10, plasma reduction: adding an auxiliary agent into the mixed powder of the anode and the cathode of the ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand;
in this embodiment, it should be noted that the ternary lithium battery is a high-nickel ternary lithium battery, and the high-nickel ternary lithium battery is a lithium battery in which a high-nickel ternary material is used as a positive electrode material, and in an implementable manner, the molar content of nickel in the high-nickel ternary material is greater than or equal to 0.8.
Specifically, the recycled mixed positive and negative electrode powder of the ternary lithium battery is mixed with an auxiliary agent, the mixed positive and negative electrode powder of the ternary lithium battery with the auxiliary agent added thereto is weighed, and the mixture is sent to a plasma reduction furnace for roasting to obtain a roasted product, wherein the roasted product contains a water-soluble lithium salt and a water-soluble manganese salt, the auxiliary agent is a compound which is helpful for improving roasting efficiency and effect, and comprises a reducing agent, an acidifier and the like, the reducing agent can be a mixture of one or more of graphite negative electrode powder of a waste lithium ion battery, activated carbon powder, coal powder and the like, the adding amount of the reducing agent is such that lithium and manganese exist in the form of metal salts, and other transition metals can continuously exist in the form of metals or low-valence metal oxides, and can be determined by theoretical calculation or actual test results in combination with other process conditions, the embodiment is not limited, and the reducing agent also helps to remove organic binders and other organic impurities in the mixed positive and negative electrode powder of the ternary lithium battery, and the adding amount of the reducing agent is 1.4-4 times or 4.1.4 times of the theoretical calculation results or the actual test results, such as 1.4 times, 4 times of the theoretical calculation results and 4.4 times, for example, 4 times of the actual test results in an implementable manner; the acidifying agent can be a water-soluble compound containing sulfate, hydrogen sulfate and/or chloride ions, which is used to combine with lithium and manganese to form a water-soluble metal salt, so the amount of the acidifying agent added is only needed to combine lithium and manganese sufficiently to form a metal salt, and can be determined by theoretical calculation or actual test results in combination with other process conditions, but this is not limited to this, and in an implementable manner, the amount of the acidifying agent added can be slightly excessive compared to the theoretical calculation results and the actual test results, and in an implementable manner, can be 1.2 to 1.4 times, for example, 1.2 times, 1.3 times, 1.4 times, etc., of the theoretical calculation results or the actual test results.
Optionally, the auxiliary agent in the plasma reduction step comprises a reducing agent and an acidifying agent.
Optionally, the reducing agent includes one or more of lithium battery graphite negative electrode powder, activated carbon powder and coal powder.
Optionally, the acidifying agent comprises a water-soluble compound comprising sulfate, hydrogen sulfate and/or chloride ions.
Optionally, the firing in the plasma reduction step is in oxygen-free conditions, a reducing atmosphere, or a protective atmosphere.
In this embodiment, specifically, in the plasma reduction process, a certain amount of reducing gas or protective gas is introduced into the plasma reduction furnace, so that the baking process is in an oxygen-free condition, a reducing atmosphere or a protective atmosphere, where the reducing gas may be a hydrogen-argon mixed gas, a hydrogen-nitrogen mixed gas, or the like, the protective gas may be argon gas or nitrogen gas, and the reducing atmosphere is used to enable lithium and manganese to exist in the form of metal salt, and other transition metals may continue to exist in the form of metal or low-valence metal oxide, and simultaneously, is helpful for removing organic binders and other organic impurities in the positive and negative electrode mixed powder of the ternary lithium battery.
Optionally, the reducing atmosphere comprises a hydrogen-argon mixed gas or a hydrogen-nitrogen mixed gas, the concentration of hydrogen in the hydrogen-argon mixed gas is 8-12%, and the concentration of hydrogen in the hydrogen-nitrogen mixed gas is 8-12%.
In the present embodiment, the reducing atmosphere includes a hydrogen-argon mixture gas having a hydrogen gas concentration of 8 to 12%, for example, 8%, 10%, 12%, or the like, or a hydrogen-nitrogen mixture gas having a hydrogen gas concentration of 8 to 12%, for example, 8%, 10%, 12%, or the like.
Optionally, the roasting temperature in the plasma reduction step is 600-900 ℃, and the roasting time is 3-6 hours.
In this embodiment, specifically, the baking temperature of the baking in the plasma reduction step is 600 to 900 ℃, for example, 600 ℃, 782 ℃, 900 ℃ or the like, and the baking time is 3 to 6 hours, for example, 3 hours, 4.5 hours, 6 hours or the like.
It should be noted that when the temperature is not lower than 600 ℃, the reducing atmosphere and/or the reducing agent exist(ii) Gibbs free energy [ Δ G θ (kJ/mol) of reaction of manganese-containing oxide with acidifying agent]Negative, about-81.77 kJ/mol, i.e. the reaction proceeds spontaneously, the reaction product of manganese being a lower valent metal oxide, i.e. MnO, under oxidizing conditions and in the presence of an acidifying agent 2 (manganese dioxide) in the form of MnO in the presence of sufficient reducing agent or reducing conditions and in the presence of acidifying agent 2 Will be present in the form of a water-soluble metal salt, for example: manganese sulfate, manganese chloride, etc., while the other transition metals continue to exist as metal or lower-valent metal oxides, so that manganese can be converted into the form of water-soluble metal salts by controlling the reducing agent and/or reducing atmosphere sufficiently and controlling the acidifying agent sufficiently at a suitable temperature, thereby enabling manganese to be extracted from the mixture together with lithium by means of water leaching. The reduction temperature is controlled to be 600-900 ℃, the layered structure of the anode powder of the waste lithium ion battery can be fully repaired, and the activity of the nickel-based catalyst is improved.
Step S20, lithium manganese water leaching: adding water into the calcine, stirring and leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
in this embodiment, specifically, water is added to the calcine, and the mixture is stirred, so that the water-soluble lithium salt and the water-soluble manganese salt in the calcine are sufficiently dissolved in water, and after sufficient reaction, the precipitate is filtered to obtain a filter residue containing a nickel element and a cobalt element, and a first filtrate containing a lithium element and a manganese element, where after the filter residue containing the nickel element and the cobalt element is cleaned, the cobalt-doped nickel-based catalyst can be obtained. The introduction of cobalt enriches the surface oxygen defect of the catalyst, improves the dispersion and reduction degree of nickel, enhances the carbon dioxide adsorption activation capability and hydrogenation capability of the catalyst, and can effectively improve the catalytic activity of the nickel-based catalyst.
Optionally, the step of adding water to the calcine, stirring, leaching to obtain cobalt-doped nickel-based catalyst filter residue and a first filtrate comprises:
adding water with the mass of 4-7 times of the calcine, stirring, and controlling the leaching temperature to leach the calcine for 2-3 hours at the temperature of 70-98 ℃.
In this embodiment, specifically, water with a mass 4 to 7 times that of the calcine is added to the calcine, the mixture is stirred, the leaching temperature is controlled to be 70 to 98 ℃, such as 70 ℃, 85 ℃, 98 ℃ and the like, and the leaching temperature is controlled to be 2 to 3 hours, such as 2 hours, 2.5 hours, 3 hours and the like, by heating in a water bath or other heat preservation manners, so that the water-soluble lithium salt and the water-soluble manganese salt in the calcine can be sufficiently dissolved in the water, after sufficient reaction, the precipitate is filtered to obtain a filter residue containing a nickel element and a cobalt element, and a first filtrate containing a lithium element and a manganese element, and the filter residue containing a nickel element and a cobalt element is cleaned to obtain the cobalt-doped nickel-based catalyst.
Step S30, adjusting value and precipitating manganese: adjusting the pH value of the first filtrate to obtain manganese hydroxide filter residue and a second filtrate;
in this embodiment, specifically, an alkali is added to the first filtrate, the pH of the first filtrate is increased and adjusted, so that manganese in the first filtrate is combined with hydroxide ions to form a manganese hydroxide precipitate, and the manganese hydroxide residue containing a manganese element and the second filtrate containing a lithium element are obtained after filtering the precipitate, where the alkali may be a liquid alkali, a sodium hydroxide solution, a potassium hydroxide solution, or the like.
Optionally, the step of adjusting the pH value of the first filtrate to obtain a manganese hydroxide filter residue and a second filtrate includes:
and adding excessive liquid caustic soda into the first filtrate to adjust the pH value of the first filtrate to 8-13, controlling the reaction temperature to be 60-80 ℃, and reacting for 0.5-2 hours to obtain manganese hydroxide filter residue and second filtrate.
In this embodiment, specifically, an excess amount of liquid alkali is added to the first filtrate, the pH of the first filtrate is adjusted to be in a range of 8 to 13, and the reaction temperature is controlled to be 60 to 80 ℃, for example, 60 ℃, 72 ℃, 80 ℃, and the like, so that manganese in the first filtrate sufficiently reacts with hydroxide ions for 0.5 to 2 hours, for example, 0.5 hour, 1 hour, 2 hours, and the like, to form a manganese hydroxide precipitate, and the precipitate is filtered to obtain a manganese hydroxide residue containing manganese elements, and a second filtrate containing lithium elements, wherein the alkali may be liquid alkali, sodium hydroxide solution, and/or potassium hydroxide solution, and the excess amount of liquid alkali is more than the theoretical addition amount of liquid alkali, and in a practical manner, the excess amount of liquid alkali may be 1.2 to 1.4 times, for example, 1.2 times, 1.3 times, 1.4 times, and the like of liquid alkali, and the theoretical addition amount of liquid alkali may be calculated theoretically or actually determined by combining with other process conditions, and the excess amount of liquid alkali may be determined to ensure that the purity of the excess manganese hydroxide ions is sufficiently increased, and the subsequent lithium hydroxide precipitate may also be formed without limitation.
Step S40, carbonizing and precipitating lithium: and adding carbonate into the second filtrate to obtain lithium carbonate filter residue.
In this embodiment, specifically, carbonate is added to the second filtrate to introduce carbonate ions into the second filtrate, so that lithium element in the second filtrate is combined with the carbonate ions to form a lithium carbonate precipitate, and the lithium carbonate residue is obtained after filtering the precipitate, where the carbonate may be a solid sodium carbonate and/or potassium carbonate solution, and the like.
Optionally, the step of adding carbonate to the second filtrate to obtain a lithium carbonate filter residue and a waste liquid includes:
and adding excessive sodium carbonate into the second filtrate, controlling the reaction temperature at 80-100 ℃, and reacting for 1-4 hours to obtain lithium carbonate filter residue and waste liquid.
In this embodiment, specifically, an excess amount of soda ash is added to the second filtrate to introduce carbonate ions into the second filtrate, and at the same time, the reaction temperature is controlled at 80-100 ℃, for example, 80 ℃, 88 ℃, 100 ℃ and the like, so that the lithium element in the second filtrate and the carbonate ions sufficiently react for 1-4 hours, for example, 1 hour, 2.5 hours, 4 hours and the like, to form a lithium carbonate precipitate, and the lithium carbonate precipitate is filtered to obtain a lithium carbonate filter residue, where the carbonate may be a solid sodium carbonate and/or potassium carbonate solution and the excess amount of soda ash refers to a theoretical addition amount exceeding the soda ash, and in an implementable manner, the excess amount of soda ash may be 1.2-1.4 times, for example, 1.2 times, 1.3 times, 1.4 times and the like of a theoretical addition amount of soda ash, and may be determined by theoretical calculation or actual test results in combination with other process conditions, which, without limitation, the excess amount of soda ash is used to ensure that the carbonate ions are excessive, and further, so that the lithium element may sufficiently combine with the carbonate ions to form lithium carbonate ions, and the recovery rate of lithium carbonate ions can be increased.
In the embodiment, through plasma reduction, namely, adding an auxiliary agent into the mixed powder of the positive electrode and the negative electrode of the ternary lithium battery, mixing, and then feeding the mixture into a plasma reduction furnace for roasting to obtain calcine, the purpose of converting manganese and lithium into a metal salt solution of the manganese and the lithium is achieved, a large amount of nickel is combined with a small amount of cobalt and aluminum to form a nickel-based catalyst, and meanwhile, organic impurities in the mixed powder of the positive electrode and the negative electrode of the ternary lithium battery are decomposed into small molecules such as carbon dioxide and water to be removed; further leaching lithium and manganese by water, namely adding water into the calcine, stirring and leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate, realizing the separation of the filtrate containing manganese and lithium and the filter residue containing the cobalt-doped nickel-based catalyst, further realizing the recovery of the cobalt-doped nickel-based catalyst, further precipitating manganese by adjusting the value, namely adjusting the pH value of the first filtrate to obtain manganese hydroxide filter residue and second filtrate, realizing the separation of manganese and lithium, further realizing the recovery of manganese, further precipitating lithium by carbonization, namely adding carbonate into the second filtrate to obtain lithium carbonate filter residue, realizing the recovery of lithium, further realizing the resource recycling of all components of the mixed powder of the positive electrode and the negative electrode of the waste ternary lithium battery, compared with the mode that manganese, cobalt, nickel and lithium are sequentially recovered and impurity components are required to be removed in the prior art, the recovery method can prepare nickel-based catalysts from nickel, cobalt, aluminum and other metals through a plasma reduction process, the prepared nickel-based catalysts can be directly put into use without further separation, not only can realize effective utilization of resources, but also can simplify the process flow of separation and extraction of various metals, reduce reagents required by separation and extraction of various metals, reduce recovery cost, and overcome the technical problems that the resource recovery process of the ternary lithium battery in the prior art is complex, the cost is high and the extracted product has more impurities.
In order to further understand the present application, the following specifically describes the method for recycling the positive and negative electrode materials of the ternary lithium battery, which is provided by the present application, with reference to an embodiment. Commercial raw materials were used in the examples of the present invention.
Example 1
Adding graphite powder and ammonium bisulfate into mixed powder of a positive electrode and a negative electrode of a ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand, wherein the roasting temperature is 600 ℃, the roasting time is 6 hours, and hydrogen and argon mixed gas with the hydrogen concentration of 10 percent is introduced into the plasma reduction furnace in the roasting process;
adding water with the mass being 4 times that of the roasted product into the roasted product, stirring the mixture, and leaching the mixture for 3 hours at the temperature of 98 ℃ to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
adding 1.2 times of the theoretical addition amount of liquid caustic soda into the first filtrate, adjusting the pH value of the first filtrate to 8-13, controlling the reaction temperature at 60 ℃, and reacting for 2 hours to obtain manganese hydroxide filter residue and second filtrate;
and adding 1.2 times of the theoretical addition amount of the sodium carbonate into the second filtrate, controlling the reaction temperature at 80 ℃, and reacting for 4 hours to obtain lithium carbonate filter residue and waste liquid.
Example 2
Adding activated carbon powder and ammonium chloride into mixed powder of a positive electrode and a negative electrode of a ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand, wherein the roasting temperature is 900 ℃, the roasting time is 3 hours, and hydrogen-nitrogen mixed gas with the hydrogen concentration of 10% is introduced into the plasma reduction furnace in the roasting process;
adding water with the mass being 7 times that of the calcined sand, stirring, leaching for 2 hours at the temperature of 70 ℃ to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
adding 1.4 times of theoretical addition amount of liquid alkali into the first filtrate, adjusting the pH value of the first filtrate to 8-13, controlling the reaction temperature at 80 ℃, and reacting for 0.5 hour to obtain manganese hydroxide filter residue and second filtrate;
and adding 1.4 times of the theoretical addition amount of the sodium carbonate into the second filtrate, controlling the reaction temperature at 100 ℃, and reacting for 1 hour to obtain lithium carbonate filter residue and waste liquid.
Example 3
Adding coal powder and ammonium sulfate into the mixed powder of the anode and the cathode of the ternary lithium battery, mixing, and then feeding the mixture into a plasma reduction furnace for roasting to obtain roasted sand, wherein the roasting temperature is 750 ℃, the roasting time is 5 hours, and hydrogen-argon mixed gas with the hydrogen concentration of 10% is introduced into the plasma reduction furnace in the roasting process;
adding 6 times of water by mass into the calcine, stirring, leaching for 2.5 hours at the temperature of 85 ℃ to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
adding 1.3 times of the theoretical addition amount of liquid caustic soda into the first filtrate, adjusting the pH value of the first filtrate to 8-13, controlling the reaction temperature at 75 ℃, and reacting for 1 hour to obtain manganese hydroxide filter residue and second filtrate;
and adding 1.3 times of the theoretical addition amount of the sodium carbonate into the second filtrate, controlling the reaction temperature at 95 ℃, and reacting for 2 hours to obtain lithium carbonate filter residue and waste liquid.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings, or which are directly or indirectly applied to other related technical fields, are included in the scope of the present application.
Claims (10)
1. A method for recycling positive and negative electrode materials of a ternary lithium battery is characterized by comprising the following steps;
plasma reduction: adding an auxiliary agent into the mixed powder of the anode and the cathode of the ternary lithium battery, mixing, and then feeding into a plasma reduction furnace for roasting to obtain roasted sand;
water leaching lithium manganese: adding water into the calcine, stirring and leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate;
adjusting the value and precipitating manganese: adjusting the pH value of the first filtrate to obtain manganese hydroxide filter residue and a second filtrate;
carbonizing and precipitating lithium: and adding carbonate into the second filtrate to obtain lithium carbonate filter residue.
2. The method for recycling positive and negative electrode materials for a ternary lithium battery as claimed in claim 1, wherein the auxiliary in the step of plasma reduction comprises a reducing agent and an acidifying agent.
3. The method for recycling the anode and cathode materials of the ternary lithium battery as claimed in claim 2, wherein the reducing agent comprises one or a mixture of more of graphite cathode powder, activated carbon powder and coal powder of the lithium battery.
4. The method for recovering a positive-negative electrode material for a ternary lithium battery as claimed in claim 2, wherein the acidifying agent comprises a water-soluble compound containing sulfate, hydrogen sulfate and/or chloride ions.
5. The method for recovering positive and negative electrode materials of a ternary lithium battery as claimed in claim 1, wherein the baking temperature in the step of plasma reduction is 600 to 900 ℃ and the baking time is 3 to 6 hours.
6. The method for recycling positive and negative electrode materials of a ternary lithium battery as claimed in claim 1, wherein the baking in the plasma reduction step is performed under oxygen-free conditions, in a reducing atmosphere, or in a protective atmosphere.
7. The method for recycling the anode and cathode materials of the ternary lithium battery as claimed in claim 6, wherein the reducing atmosphere comprises a hydrogen-argon mixed gas or a hydrogen-nitrogen mixed gas, the concentration of hydrogen in the hydrogen-argon mixed gas is 8-12%, and the concentration of hydrogen in the hydrogen-nitrogen mixed gas is 8-12%.
8. The method for recovering the anode and cathode materials of the ternary lithium battery as claimed in claim 1, wherein the step of adding water to the calcine, stirring, leaching to obtain cobalt-doped nickel-based catalyst filter residue and first filtrate comprises:
adding water with the mass of 4-7 times of the calcine, stirring, and controlling the leaching temperature to leach the calcine for 2-3 hours at the temperature of 70-98 ℃.
9. The method for recycling the anode and cathode materials of the ternary lithium battery as claimed in claim 1, wherein the step of adjusting the pH value of the first filtrate to obtain the manganese hydroxide filter residue and the second filtrate comprises:
and adding excessive liquid caustic soda into the first filtrate to adjust the pH value of the first filtrate to 8-13, controlling the reaction temperature to be 60-80 ℃, and reacting for 0.5-2 hours to obtain manganese hydroxide filter residue and second filtrate.
10. The method for recovering the anode and cathode materials of the ternary lithium battery as claimed in claim 1, wherein the step of adding carbonate to the second filtrate to obtain the lithium carbonate filter residue and the waste solution comprises:
and adding excessive sodium carbonate into the second filtrate, controlling the reaction temperature at 80-100 ℃, and reacting for 1-4 hours to obtain lithium carbonate filter residue and waste liquid.
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